Pyrolisis and Gasification

Commission of the European Communities
G3
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Edited by
G.L. FERRER
. MANIATIS
A . BUEKENS
A.V. BRIDGWATER
E1S E VI ER A P P L I ED S C H N E I
PYROLYSIS AND GASIFICATION
Proceedings of an international conference held in Luxembourg, 23-25 May

1989.
PYROLYSIS AND
GASIFICATION
Edited by
G. L. FERRER
Commission of the European Communities, Brussek,
Belgium
K. MANIATIS
pert to the Commission of the European Communities, Brussels, Belgium
A. BUEKENS
Vrije Univ ersiteit Brussel, Belgium
. V. BRIDGWATER
University of Aston, Birmingham, UK
ELSEVIER APPLIED SCIENCE

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Pyrolysis and gasification.
1. Energy sources: Biomass. Thermochemistry
I. Ferrer, G. L.
662'.6
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PREFACE
Thermochemical processing of renewable resources and solid fuels has become a

strong contender to partially replace the energy dependance of the European
Community on imported hydrocarbon fuels and the Commission is supporting R & D as
well as Demonstration projects In this field. Similarly in the US, Canada and the
Developing Countries numerous projects have been carried out on fundamental as well
as industrial scale projects on Pyrolysis and Gasification. Such technologies are
therefore of increasing importance worldwide, not only because they can provide a
source of energy but also because they can be utilized to dispose off various industrial
wastes in an environmentally acceptable way.
Though interesting results and experiences have certainly been achieved, several
problems still remain and their solution will strongly influence the commercialisation
of Pyrolysis and Gasification all over the world.
It was the need to critically evaluate the progress achieved in this field and to draw
up recommendations for future work which prompted the Directorate General for
Energy of the Commission of the European Communities to organise this International
Conference with the assistance of the Directorate General for Information, Marketing
and Innovation.
While invited speakers from the Commission, EC countries, US, Canada and the World
Bank presented overviews on all aspects of Pyrolysis and Gasification processes such
as Feedstock Pretreatment and Characterisation, Gasification and Pyrolysis
Technologies, Products Upgrading and Utilization as well as Environmental and
Economic aspects, researchers and industrialists from 20 countries presented their
results and views in oral as well as poster presentations. The Workshops and Panel
Discussions gave the opportunity to all participants to express their opinion so that
realistic recommendations for future R & D and Demonstration activities could be
drawn up.
About 200 participants representing Administrations, Governmental Institutions,
Universities and mainly the Industry attended the Conference. This is a fresh proof of
the significance in recent years of Pyrolysis and Gasification technologies.
The Editors express their graditute to all the participants for their contributions as
well as to the Chairmen and Rapporteurs who assisted in making this a successful
Conference and we are confident that the contents of this proceedings will be a
valuable tool and source of information to all those working in the field.
G.L. FERRER
. MAN I ATIS
. BUEKENS
A.V.BRIDGWATER
vu
CONTENTS
PREFACE
SESSION I
OPENING SESSION AND COUNTRY OVERVIEWS
ACTIVITIES AND RESULTS OF THE COMMISSION DEMONSTRATION

PROGRAMME IN THE SECTOR OF GASIFICATION AND PYROLYSIS
G.L. FERRER, General Directorate for Energy, Commission
of the European Communities, Brussels, Belgium
COMMUNITY R&D STRATEGY IN THE FIELD OF BIOMASS PYROLYSIS

AND GASIFICATION
G. GRASSI, Directorate General for Science Research and
Development, Commission of the European Communities
PROGRESS IN PYROLYSIS AND GASIFICATION OF BIOMASS:

AN OVERVIEW OF RESEARCH IN THE UNITED STATES
J. DIEBOLD, D. STEVENS, Solar Energy Research Institute,
Golden, Colorado, USA
14
OVERVIEW OF THERMOCHEMICAL CONVERSION OF BIOMASS IN CANADA

R.D. HAYES, Bioenergy Research and Development Technology
Branch, Energy, Mines and Resources Canada, Ottawa, Canada
28
RAPPORTEUR'S REPORT ON SESSION I

C H . NELS, Federal Office for the Environment, Berlin
40
SESSION II
PRE-TREATMENT AND CHARACTERIZATION
PRETREATMENT AND CHARACTERIZATION OF FEEDSTOCKS

C.P. MITCHELL, Forestry Department, Aberdeen University,
Aberdeen, UK, A.V. BRIDGWATER, Chemical Engineering
Department, Aston University, Birmingham, UK
43
PROCESSING OF URBAN WASTE TO PROVIDE FEEDSTOCK FOR

FUEL/ENERGY RECOVERY
J.R. BARTON, Warren Spring Laboratory, Department of
Trade and Industry, UK
57
CHARACTERIZATION OF CARBON CONTAINING MATERIALS WITH RESPECT

TO PYROLYSIS AND GASIFICATION
H.J. MHLEN, W. WANZL, K.H. VAN HEEK,
Bergbau-Forschung GmbH, Essen, FRG
72
VIU
KTI ACTIVITIES IN THE FIELD OF BIOMASS PYROLYSIS
L. ANTONELLI, Vice President, Director of Alternative Energies
Department, Kinetics Technology International SPA, Rome, Italy
85
BIOMASS FUELS AND GASIFICATION

J. CARRE, L. LACROSSE, Y. SCHENKEL, Center for Agronomical
Researches (CRA), Gembloux, Belgium
F. RURIHOSE, Universit Catholique de Louvain (UCL),
Louvain-la-Neuve, Belgium
93
USAGE OF CARBON BLACK AND ACTIVATED CARBON IN RELATION TO INPUT

AND TECHNICAL ASPECTS OF THE PYROLYSIS PROCESS
B. BILITEWSKI, G. H K R D T L E , K. MAREK, Intecus, Associated
Engineers for Environmental Protection Technologies, Berlin
98
RAPPORTEUR'S REPORT ON SESSION II

C. ESNOUF, Cemagref, Antony Cedex, France
106
SESSION III
PYROLYSIS, GASIFICATION AND LIQUEFACTION TECHNOLOGIES
BIOMASS GASIFICATION: PAST EXPERIENCES AND FUTURE
PROSPECTS IN DEVELOPING COUNTRIES
M.S. MENDIS, Industry and Energy Department,
The World Bank, Washington DC, USA
111
GASIFICATION AND PYROLYSIS OF BIOMASS IN EUROPE

A.A.CM. BEENACKERS, Department of Chemical Engineering,
University of Groningen, Groningen, The Netherlands
A.V. BRIDGWATER, Chemical Engineering Department,
Aston University, Birmingham, UK
129
A SURVEY OF BIOMASS
R. CAPART, A.
Department of
University of
LIQUEFACTION PROCESSES
ELAMIN, S. AMMAR, M. GELUS,
Chemical Engineering,
Technology, Compigne, France
158
THE GEORGIA TECH ENTRAINED FLOW PYROLYSIS PROCESS

R.J. KOVAC, D.J. O'NEIL, Georgia Institute
of Technology, Atlanta, Georgia, USA
169
PILOT PLANT DEMONSTRATION OF USED TIRES VACUUM PYROLYSIS

C. ROY, Universit Laval, Department of Chemical
Engineering, Quebec, Canada
J. UNSWORTH, Petro-Tire Inc., Hamilton, Ontario, Canada
180
FLUIDIZED BED PYROLYSIS OF SEWAGE SLUDGE

U. BELLMANN, A.B. KUMMER, Y. YING, W. KAMINSKY,
Institute for Technical and Macromolecular Chemistry,
University of Hamburg, FRG
190
IX
RAPPORTEUR'S REPORT ON SESSION III
PYROLYSIS GASIFICATION AND LIQUEFACTION TECHNOLOGIES
A.V. BRIDGWATER, Aston University, Birmingham, UK
195
SESSION IV
PYROLYSIS CASE STUDIES
SUGARS FROM CELLULOSICS BY THE WATERLOO FAST PYROLYSIS PROCESS
D.S. SCOTT, J. PISKORZ, D. RADLEIN, S. CZERNIK,
Department of Chemical Engineering, University of Waterloo,
Waterloo, Ontario, Canada
201
PRODUCTION OF BENZOLES AND ACTIVE CARBON FROM WASTE RUBBER AND PLASTIC
MATERIALS BY MEANS OF PYROLYSIS WITH SIMULTANEOUS POST-CRA CKING
R. CYPRES, B. BETTENS, Universit Libre de Bruxelles (ULB),
Brussels, Belgium
209
CHEMICALS FROM ALMOND SHELLS BY PYROLYSIS IN FLUIDIZED BED

R. FONT, A. MARCELLA, E. VERDU, J. DEVESA, Divisin de
Ingenieria Qumica, Universidad de Alicante, Spain
230
BIOMASS PYROLYSIS IN MOLTEN SALTS FOR FUEL PRODUCTION

J.. MAUND, D.M. EARP, Department of Chemical Engineering
and Applied Chemistry, Aston University, Birmingham, UK
238
FLASH PYROLYSIS OF SULCIS COAL

L. CONTI, G. SCANO, Dipartimento di Chimica,
Universit' di Sassari, Sassari, Italy
246
RAPPORTEUR'S REPORT ON SESSION IV

D.J. O'NEIL, Georgia Institute of Technology,
Atlanta, Georgia, USA
250
SESSION V
GASIFICATION CASE STUDIES
PERFORMANCE OF A PILOT SCALE FLUIDIZED BED GASIFIER
FUELLED BY RICE HUSKS
HARTINIATI, A. SOEMARDJO, M. YOUVIAL,
LSDE-BPP Teknologi, Indonesian Energy Research
Laboratory, Puspiptek - Serpong, Indonesia
257
ELECTRICAL ENERGY FROM BIOMASS'

F. FONZI, Italenergie S.p.a., Sulmona AQ, Italy
264
FLUIDIZED BED GASIFICATION OF WOOD: PERFORMANCE OF A

DEMONSTRATION PLA NT
K. MANIATIS, A. BUEKENS, Department of Chemical
Engineering and Industrial Chemistry, Free University
of Brussels, Belgium
A.V. BRIDGWATER, Department of Chemical Engineering,
274
A NATIONAL PROGRAM ON IMPLEMENTATION OF BIOMASS GASIFICATION

PROCESS IN INDONESIA. SCENARIO, PROGRESS AND ECONOMIC EVALUATION
H. SUSANTO, S. REKSOWARDOJO, Department of Chemical
Engineering, ITB, Bandung, Indonesia
282
GASIFICATION AND PYROLYSIS OF STRAW - RESEARCH IN DENMARK

G. OLSEN, P.H. PEDERSEN, O. HENRIKSEN, E. KOFOED,
Laboratory for Energetics, Technical University of
Denmark, Lyngby, Denmark
290
AN INVESTIGATION INTO THE GASIFICATION OF LOW QUALITY

COAL WITH OXYGEN ENRICHED AIR IN A FIXED BED GASIFIER
A.D. ENGELBRECHT, Division of Energy Technology,
CSIR, Pretoria, South Africa
296
PRESSURIZED FLUIDIZED BED GASIFICATION OF PEAT

E. KURKELA, P. STAHLBERG, W. MOJTAHEDI, M. NIEMINEN
Technical Research Centre of Finland, Laboratory of
Fuel Processing Technology, Espoo, Finland
304
RAPPORTEUR'S REPORT ON SESSION V

K. MANIATIS, Free University of Brussels, Belgium
A.A.CM. BEENACKERS, Groningen University, The Netherlands
312
SESSION VI
UPGRADING, CLEAN OP AND UTILIZATION OF PRODUCTS
GAS PURIFICATION: A REVIEW OF THE AVAILABLE
METHODS OF GAS CLEANING
P. GUIGON, J.F. LARGE, Universit de
Technologie de Compigne, France
317
WHAT CAN WE DO WITH PYROLYSIS OILS?

E. CHURIN, B. DELMON, Universit Catholique de Louvain,
326
COMPOSITION, PURIFICATION AND USE OF PRODUCER GAS

J. VAN DER WEIDE, J.J. SEPPEN, TNO Road-Vehicles
Research Institute, Delft, The Netherlands
334
RAPPORTEUR'S REPORT ON SESSION VI

UPGRADING, CLEAN UP AND UTILIZATION OF PRODUCTS
J. DIEBOLD, SERI, Colorado, USA
342
SESSION VII
ECONOMIC, ENVIRONMENTAL AND LEGAL ASPECTS
ECONOMIC AND MARKET OPPORTUNITIES FOR BIOMASS DERIVED FUELS
A.V. BRIDGWATER, Energy Research Group, Chemical
Engineering and Applied Chemistry Department,
347
XI
ENVIRONMENTAL PROBLEMS IN THE USE OF BIOMASS FUELS
GLOBAL AND LOCAL ASPECTS
P. GIRARD, Centre Technique Forestier Tropical,
Nogent-sur-Marne, France
372
WASTE MANAGEMENT AND PYROLYSIS:

CURRENT SITUATION, TRENDS AND PROSPECTS
C H . NELS, Federal Office for the Environment, Berlin
379
RAPPORTEUR'S REPORT ON SESSION VII

R. FABRY, Commission of the European Communities,
Brussels, Belgium
387
WORKSHOPS
WORKSHOP 1 - PRETREATMENT AND CHARACTERIZATION
Chairman: J. BARTON
Rapporteur: J. PISKORZ
391
WORKSHOP 2 - PYROLYSIS
A.V. BRIDGWATER, Energy Research Group, Chemical
Engineering Department, Aston University, Birmingham, UK
C. ROY, Universit Laval, Dpartement de gnie chimique,
Quebec, Canada
394
WORKSHOP 3 - GASIFICATION TECHNOLOGY AND ECONOMICS

Y. SOLANTAUSTA, Laboratory of Fuel Processing
Technology, Technical Research Centre of Finland
A.A.CM. BEENACKERS, Department of Chemical Engineering,
University of Groningen, The Netherlands
396
WORKSHOP 4 - PYROLYSIS AND UTILIZATION

E. CHURIN, Universit Catholique de Louvain,
399
POSTERS PRESENTED
SECTION I
PRE-TREATMENT, PRODUCTS AND OTHER ASPECTS
FULL-SCALE DEMONSTRATION PROJECTS OF THE EUROPEAN COMMUNITY
IN THE FIELD OF PYROLYSIS, GASIFICATION AND CARBONISATION OF
BIOMASS AND WASTE
R. FABRY, G.L. FERRER, Directorate General for Energy,
Commission of the European Communities, Brussels
K. MANIATIS, Free University of Brussels, Belgium
405
THE USE OF WOOD AS FUEL IN MALAYSIA

W.K. HOI, Forest Research Institute of Malaysia,
Kuala Lumpur, Malaysia
411
XU
SELECTED ASPECTS, EXPLANATIONS AND STATEMENTS IN ACCORDANCE AND
ANALOGY TO THE BIT GRANULATION-TECHNOLOGY
J.M. DISS, F.W. HOCHHEIM, Directorate General and General
Management of the incorporated company B.I.T. SA, Luxembourg
417
THERMOCHEMICAL DENSIFICATION OF BIOMASS

- A KINETIC APPROACH TO PROCESS DEVELOPMENT
D.P. KOULLAS, N.S. ABATZOGLOU, E.G. KOUKIOS,
Department of Chemical Engineering,
National Technical University of Athens, Greece
420
PREPARATION AND USE OF CHARCOAL : WATER SLURRIES

C. ESNOUF, S. GAUDEMARD, Cemagref, Antony Cedex, France,
G. ANTONINI, O. FRANCOIS, Universit de Technologie
de Compiegne, Compiegne Cedex, France,
C. MEZERETTE, CTFT, Nogent-sur-Marne, France
425
TREATMENT OF PYROLYSIS OIL WITH COMPRESSED CARBON DIOXIDE

V. BRANDANI, G. DEL RE, G. DI GIACOMO, D. FLAMMINI
University of L'Aquila, Department of Chemistry
Chemical Engineering and Materials., L'Aquila, Italy
430
ACTIVATED CARBON FROM EUCALYPTUS KRAFT LIGNIN

J.J. RODRIGUEZ, T. CORDERO, J. RODRIGUEZ-MIRASOL,
A. SIMON, A. BATALLER, Departments of Chemical
Engineering and Mechanical Engineering, University of
Malaga, Malaga, Spain
435
ACTIVATED CARBONS FROM CHROMIUM-TANNED LEATHER WASTE

M.A. MARTINEZ-SANCHEZ, C. ORGILES-BARCELO, Asociacin de
Investigacin de las Industrias del Calzado y Conexas,
Alicante, Spain
J.M. MARTIN-MARTINEZ, F. RODRIGUEZ-REINOSO, Departamento
de Qumica Inorgnica e Ingenieria Qumica. Universidad
de Alicante, Alicante, Spain
439
MOTOR FUELS FROM PYROLYTIC LIGNINS

J. PISKORZ, P. MAJERSKI, D. RADLEIN, D.S. SCOTT,
Department of Chemical Engineering, University of
444
ROLE OF CHROMIUM OXIDE IN THE TEXTURE OF CARBONS FROM LEATHER

J.M. MARTIN-MARTINEZ, F. RODRIGUEZ-REINOSO, Departamento
de Qumica Inorgnica e Ingenieria Qumica, Universidad
de Alicante, Alicante, Spain
M.A. MARTINEZ-SANCHEZ, C. ORGILES-BARCELO, Asociacin de
Investigacin de las Industrias del Calzado y Conexas,
Alicante, Spain
452
INFLUENCE OF THE POROSITY OF CARBON IN Fe/Carbon CATALYSTS

J.M. MARTIN-MARTINEZ, Departamento de Qumica
Inorgnica e Ingenieria Qumica, Universidad de
Alicante, Alicante, Spain
M.A. VANNICE, Department of Chemical Engineering,
The Pennsylvania State University, Pennsylvania, USA
457
XIII
DEVELOPMENT AND CONSTRUCTION OF A SAMPLING LINE FOR WOOD

PYROLYSIS EMISSIONS
J. LACHENAL, J.M. TOLEDO, Laboratoire National d'Essai,
Trappes, France
C. MEZERETTE, A.M. VERGNET, Centre Technique
Forestier Tropical, Dpartement du CIRAD,
Nogent-sur-Marne, France
462
FURNACE FOR BIOFUELS THERMAL UTILIZATION

W. BLASIAK, B. ZETHRAEUS, R. COLLIN, Royal Institute of
Technology, Department of Heat and Furnace Technology,
Stockholm, Sweden
W. GAJEWSKI, J. ZAJDEL, Technical University of
Czestochowa, Institute of Heat Machinery, Poland
468
INVESTIGATION OF TOXIC COMPONENTS IN PRODUCTS FROM MUNICIPAL

WASTE - SEWAGE SLUDGE PYROLYSIS
H. RSSLER, U. PRSCH, W. KAMINSKY, Institut fr
Technische und Makromolekulare Chemie, Universitt
Hamburg, Hamburg, FRG
473
RESEARCH ON TAR CRACKING AND APPLICATION OF TAR

G. OLSEN, Laboratory for Energetics, Technical
University of Denmark
479
THE FUEL PROPERTIES OF HYDROCARBON LIQUIDS DERIVED FROM

PYROLYSIS OF WASTE
P.T. WILLIAMS, D.T. TAYLOR, Department of Fuel
and Energy, The University of Leeds, Leeds, UK
486
ENVIRONMENTAL AND PUBLIC HEALTH ASPECTS OF GASIFIER SYSTEMS

J. WILLOCX, Consultant, Londerzeel, Belgium
A BUEKENS, Professor, Vrije Universiteit Brussel,
Brussels, Belgium
492
CHARACTERIZATION OF WOOD CONSTITUENTS BY PYROLYSIS

- FIELD IONIZATION MASS SPECTROMETRY
H.R. SCHULTEN, Fachhochschule Fresenius, Department of
Trace Analysis, Wiesbaden, FRG
497
CHARACTERIZATION OF WOOD BY PYROLYSIS

- FIELD IONIZATION MASS SPECTROMETRY
H.R. SCHULTEN, Fachhochschule Fresenius, Department of
Trace Analysis, Wiesbaden, FRG
J.M. HALKET, Department of Chemical Pathology, Queen
Charlotte's and Chelsea Hospital, London, UK
505
SECTION 2
PYROLYSIS TECHNOLOGY
PYROLYSIS OF HAZARDOUS WASTE OIL
U. STEFFENSEN, J. FRANCK, R. RAHNENFHRER, W. KAMINSKY
Institute for Technical and Macromolecular Chemistry,
517
XIV
ENERGAS SEWAGE SLUDGE PYROLYSIS

H.F. HINRICHS, H. MULLER, ENERGAS, Gesellschaft zur
Energiegewinnung aus Mll und Kohle mbH, FRG
522
COGENERATION PYROLYSIS
G. BONINO, Biomass Energies Integrated Systems, Turin, Italy
527
CARBONISATION OF LARGE WOOD PIECES IN A LABORATORY RETORT:

PRODUCT ANALYSIS AND ENERGY A SSSESSMENT
N. SHAH, P. GIRARD, Energie Division, CTFT,
NogentsurMarne, France
R. CAPART, Departement Genie Chimique, UTC,
Compiegne, France
530
MILD PYROLYSIS PROCESS IMPROVES STEAM CYCLE EFFICIENCY

P. GRAVERSEN, R.M. HUMMELSHJ, . JENSLEV, COWIconsult,
Consulting Engineers and Planners AS, Virum, Denmark
536
FLASH PYROLYSIS OF BIOMASS FOR LIQUID FUELS

S.A. BRIDGE, A.V. BRIDGWATER, Energy Research Group,
Department of Chemical Engineering and Applied
Chemistry, Aston University, Birmingham, UK
541
GASIFICATION OF REFUSE, A PROCESS OF SFW

H. HUMMELSIEP, . FUNK, SaarbergFernwrme GmbH,
Saarbrcken, FRG
547
A CATALYTIC GASIFICATION PROCESS OF BIOMASS

J. MUNCK, Dansk Termo Industri/I. Krger AS, Soborg, Denmark
551
AGRICULTURAL WASTES FOR ELECTRICITY GENERA TION

C. ESNOUF, M. HEERAH, Cemagref, Antony Cedex, France
554
PYROLYSIS PROCESS FOR RECYCLING FOREST AND AGRICULTURAL WASTES

FOR RECUPERATING BIOMA SS ENERGY
B. GROUX, R. GUIOL, Ph. POUSAZ, BioAlternative, S.A .
Engollon, Switzerland
559
PYROLYSIS OF GREEK LIGNITES

A.A. LAPPAS, I.A. VA SA LOS, Aristotelian University of
Thessaloniki, Thessaloniki, Greece
563
DIRECT MASSS SPECTROMETRIC STUDY OF PYROLYSIS BEHAVIOUR OF BIOMASS

AND ITS CONSTITUENTS UNDER DIFFERENT IONIZATION CONDITIONS.
MS AND MSMS STUDY OF THE PRIMARY PYROLYSIS MECHANISMS
P.L. DESBENE, M. ESSAYEGH, B. DESMAZIERES, C. LANGE,
J.J. BA SSELIER, Laboratoire de Chimie Organique Structurale,
Universit" P. et M. Curie, Paris, France
568
A TWIN BED PYROLYSERCOMBUSTOR FLUID BED SYSTEM FOR THERMAL

PROCESSING OF URBAN WASTE
H. MASSON, Seghers Engineering, Willebroek, Belgium
A. BUEKENS, . MANIATIS, Free University of Brussels, Belgium,
J. SCHOETERS, Groep , Leuven, Belgium
574
XV
PMMA PYROLYSIS FUNDAMENTALS AND EXPERIMENTAL INVESTIGA TION
. BUEKENS, F. DE WOLF, Free University of Brussels, Belgium
J. SCHOETERS, KIH Groep , Leuven, Belgium
580
PYROLYSIS OF EXHAUSTED OLIVE HUSKS COUPLED WITH TWOSTAGES

THERMAL DECOMPOSITION OF AQUEOUS OLIVE OIL MILLS EFFLUENTS
G. DI GIACOMO, G. DEL RE, University of L'Aquila, L'Aquila,
Italy, E. BONFITTO, S. IACOBONI, Regione Abruzzo, Avezzano,
Italy, . BRUNETTI, E..E.., Centro Ricerche Casaccia,
Rome, Italy
586
SECTION 3
GASIFICATION TECHNOLOGY
STUDY OF BIOMASS GASIFICATION UNDER PRESSURE
R. CAPART, M. GELUS, N. LESGOURGUES, Z. LI,
Technology, Compiegne Cedex, France
593
GASIFICATION OF CHARCOAL IN MALAYSIA

W.K. HOI, Forest Research Institute of Malaysia,
Kuala Lumpur, Malaysia
598
UPDRAFT GASIFICATION OF WASTE FUELS

P. STHLBERG, E. KURKELA, VTT, Laboratory of Fuel
Processing Technology, Espoo, Finland
H. FILEN, . SALO, Bioneer Oy, Hmeenlinna, Finland
603
PEAT PLANT IN OULU SYNTHESIS GAS PRODUCTION FROM

PEAT BY FLUIDBED GASIFICATION
K. SIPIL, C. WILN, E. KURKELA, A. MOILANEN, VTT
Laboratory of Fuel Processing Technology, Espoo, Finland
J. KOLJONEN, Kemira Oy, Oulu, Finland
608
DEVELOPMENT OF A DOWNDRAFT MOVING BED BIOMASS GASIFIER

R. BILBAO, J. LANA, P. GARCIA, J. ARAUZO,
Zaragoza, Zaragoza, Spain
613
STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED.

EFFECT OF THE TYPE OF FEEDSTOCK
J. CORELLA, J. HERGUIDO, J. GONZALEZSAIZ, Chemical
Engineering Department (Faculty of Science),
University of Zaragoza, Zaragoza, Spain
618
STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED WITH A

SECONDARY CATALYTIC REACTOR I. RESULTS WITH THE
SECONDARY REACTOR EMPTY AND WITH SAND
J. CORELLA, M.P. AZNAR, . CEBRIAN, J.I. IGLESIAS,
M.P. MARTINEZ, Chemical Engineering Department,
University of Zaragoza, Zaragoza, Spain
624
XVI
STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED WITH A
SECONDARY CATALYTIC BED. - II. TAR CRACKING WITH DOLOMITE(S)
IN THE SECONDARY REACTOR
M.P. AZNAR, J. DELGADO, J. CORELLA, J. LAHOZ,
Chemical Engineering Department, University of
Zaragoza, Zaragoza, Spain
629
FIXED BED GASIFICATION OF LIGNOCELLULOSIC BIOMASS

THE CEMAGREF PROCESS
S. GAUDEMARD, J.J. BECKER, Cemagref, Antony Cedex, France
635
STUDY ON MARKED PRODUCTS OF WOOD GASIFICATION MECHANISMS

WITH THE AIM OF PRODUCING CLEAN GASES
S. CASTILLO, S. BENNINI, G. GAS, J.P. TRAVERSE,
Universit Paul Sabatier, Toulouse, France
640
REDUCTION ZONE HEIGHT DETERMINATION IN SOLID WASTE

GASIFICATION PROCESS IN A SHAFT FURNACE
J. WANDRASZ, K. WALECZEK, The Silesian
Technical University, Poland
646
COMPUTER MODELLING OF FLUIDIZED BED GASIFICATION

J.M. DOUBLE, E.L. SMITH, A.V. BRIDGWATER,
Energy Research Group, Department of Chemical
Engineering and Applied Chemistry, Aston
University, Birmingham, UK
651
THREE-PHASE WOOD GASIFIER SYSTEM EASIMODR

H. MICHEL-KIM, Efeu GmbH, Research and
Development for Energy and Environment, Schwelm, FRG
656
LIST OF PARTICIPANTS
661
INDEX OF AUTHORS
677
SESSION I
ACTIVITIES AND RESULTS OF THE

COMMISSION DEMONSTRATION PROGRAMME IN THE SECTOR OF
GASIFICATION AND PYROLYSIS
G.L. FERRER
General Directorate for Energy
Coma I ss Ion of the European Communities
200 rue de la Lol
1049 Brussels Belgium
Summary
The demonstration programme In the "Blomass and energy from waste" sector
Is outlined In general, with particular reference to the subject of
"Pyrolysls and Gasification".
Comments are made on certain results obtained
general trends can be concluded.
In the Member States and
The results of finished projects and of measures still In progress

Indicate that these technologies, especially pyrolysls, will develop In
Mediterranean countries where the conditions of blomass supply lend
themselves better to conversion of the blomass In the form of stockable
fuels.
The Energy Demonstration Programme Introduced In 1978 by the Directorate

General for Energy of the Commission of the European Communities provides
financial support for demonstration projects of an Innovatory nature and
Industrial scale in respect of energy saving, renewable energy sources
and substitutes for hydrocarbons.
Demonstrations projects are defined as any project which on a real scale
amounts to the application of an Innovative technology or a new
application of a proven technology and helps to establish the technical
and economic feasibility of a process before advancing to commercial
exploitt Ion.
These projects form the link between the research and development phase
upstream, possibly backed by a pilot project, and the commercial
exploitation phase downstream.
Since 1978 an Invitation to submit proposals for demonstration projects
has been published each year In the Official Journal of the European
Communities, and each year a certain number of projects considered to be
of considerable technological and economic Interest are provided with
finance by the Commission to cover part of the technical and economic
risks Inherent In the project.
From 1978 to 1988 (Table 1) some 1631 projects have been selected from
the huge number put forward In response to the annual Invitation to
submit proposals Issued by the Commission and financial support totalling
841 Mio ECU (1 007 Mio $) has been awarded. This Community programme,
which Is the largest In the world, Is accompanied by national programmes
In the Member States of the European Community.
T A B L E
DEMONSTRATION PROJECTS 1978-1988
Total proposals
S 176
Total accepted projects
1 631
CEC support
841 Mio ECU - 1 007 Mio $
Under the iomass and Energy from Waste Sector of this Programme some 191
projects (Table 2) have been awarded support totalling 87,4 Mio ECU
(101,6 Mio $ ) .
TAB L E
BIOMASS AND ENERGY FROM WASTE
Total accepted projects
191
CEC support
87,4 Mio ECU - 101,6 Mio $
Total cost of projects
311 Mio ECU - 361,8 Mio $
Some of these projects will be described to you In the course of the

Seminar's technical sessions. The projects which have been selected can
be divided Into 11 sub-sectors shown In Table 3. For the most part they
fall Into one of the two main catagorles, "biological conversion" and
"thermochemlcal conversion" of blomass and waste.
T A B L E
BIOMASS ANO ENERGY FROM WASTE
01.
02.
03.
04.
05.
06.
07.
08.
09.
10.
11.
SUBSECTORS
PROJECTS
Biomass Harvesting
Energy crops
Treatment of waste
Biogas
Refuse Derived Fuel
Direct combustion
Gasification and Pyrolysls
Compost
Fuels and chemicals (biol. treat.)
Fuels and chemicals (thermo-chem. treat.)
Proteins
Total
4
3
18
70
14
40
24
7
1
9
1_
191
Some 90X of biological conversion projects selected, 66 out of 70

projects, concern the production and use of biogas from animal litter,
urban waste or effluent from the agro-food Industry. This Is a major subsector of the programme.
Some 50X of the 87 thermochemlcal conversion projects selected are
concerned
with
direct
combustion,
27%
with
gasification
and
carbonization, and 16% with the production and use of refuse-derived
fuels (RDF).
In each sub-sector the projects In progress or completed are designed to
establish the technical feasibility of new concepts and to evaluate the
economic profitability of the projects, and In each of these sub-sectors
projects successfully completed have or will give rise to multiplication,
with considerable impact In terms of energy and the environment.
Treatment by gasification and pyrolysls of solid urban waste still seems
to present certain problems whereas the pyrolysls and gasification of
wood seems set for reasonable success.
In the short term It seems unlikely that these technologies are destined
for extensive application, and there is clearly a need for demonstration
measures before maximum use of their Interesting potential can be
achieved.
The results obtained so far In the demonstration programme, although in
no great quantity, nonetheless allow certain basic observations to be
made on the technologies of gasification and pyrolysls.
The first point to be made is the growing interest In pyrolysls in most
southern European countries, with Italy to the fore due to the numerous
R&D activities tied up with the Leben-Abruzzo project.
In Germany various gasification of wood and wood waste techniques have

had success although marketing of these facilities has not always had
equally positive results.
In France some experiments Into the pyrolysls of solid urban waste have
encountered technical and economic problems whereas wood gasification and
torefactlon projects have demonstrated the reliability of these
techniques.
In Belgium, finally, certain ongoing experiments have had problems due
mainly, as In other countries elsewhere, to the low cost of oil.
For other Community countries
conclusions to be drawn.
too
The feeling remains, however, that

to a greater degree, pyrolysls are
the possibilities opened In future
non-food uses may Increase to some
few
data
are
available
for
any
the technologies of gasification and,

becoming particularly attractive, and
by the release of cultivated land for
extent the use of these processes.
However, there Is still the problem of their profitability.

Studies currently In progress and environmental requirements, which are
still difficult to quantify, should provide a better Idea of the
economics of these technologies, taking Into account not only the energy
value of the products to be treated but also the far more general Impact
that the use of blomass for energy purposes can generate.
The demonstration project of the Commission's Directorate-General for
Energy will draw to an end In 1989. An Invitation to submit proposals has
been published recently in the Official Journal, and projects on the
pyrolysls and gasification of biomass and waste in general may still be
submitted and accepted. However, regardless of the results of projects
still to come. It can already be said that this sector of the
demonstration programme has made a solid contribution to the spread of
the technologies of gasification and pyrolysls. The projects In process
and the results obtained, even though negative In some cases, have shown
the way and pinpointed the problems on which greater effort should be
concentrated.
We are now starting to reap the benefits of this vast programme, which,
complementing measures taken at national level In the individual Member
States, has led to technological maturity and process reliability in
every respect.
The Directorate-General for Energy is proud to have contributed, and to
continue to do so, to solving the common problem, which is not
exclusively an energy one, of Increasingly efficient use of blomass and
waste In an overall context reflecting nature protection, the use of
local resources and the conservation of Jobs.
This conference will be different from many others being held elsewhere
on this subject through Its mainly demonstration nature of the results
obtained and the guidelines that should emerge for future action In
Commission programmes.
COMMUNITY RSD STRATEGY IN THE FIELD OF BIOMASS PYROLYSIS

AND GASIFICATION
G. GRASSI
Directorate General for Science Research and Development,
Commission of the European Communities
1. INTRODUCTION
The immense stock of chemical energy, represented by vegetal matter
(biomass) ,
constantly produced on the earth will play the role of a
strategic and the only renewable industrial energy resource in the long term
future. Its exploitation on a large scale will offer supplementary important
benefits such as rural development,
environmental land and atmosphere
improvement, better climatic stability etc.
The biomass potential in the European Community is estimated at around
600 million ton/year (dry matter) and its likely utilisation is as follows:
Energy utilisation
Industrial utilisation
Chemicals and organic fertilisers
300 million ton/year

80 million ton/year
220 million ton/year
So, the energy sector should get the largest share of the resource. Of
course, the development and speed of penetration of the bio-energy sector
will depend largely on the future supply cost of biomass (30/60 ECU/ton (dm)
actually in Europe); on the cost of the conversion technology; and (mainly)
on the cost of imported oil.
Among the several conversion technologies so far developed in the
Community (direct combustion,
air gasification,
advanced gasification,
pyrolysis, liquefaction, catalytic conversion, bio-gasification) pyrolysis
today appears very promising and best suited to the implementation of large
biomass schemes like the LEBEN - Industrial projects. In fact pyrolysis or
synthetic-oil can be competitive on a relatively small scale of production.
This may also allow for large-scale biomass exploitation, the adoption of
modular conversion units with capacity in the range of 2:10 ton/hr, to match
in the most convenient way, the more or less productive and/or dispersed
resource available.
2. BIOMASS CONVERSION INTO FUELS

The energy content (fixed carbon) of biomass can be exploited by
direct combustion or after conversion (and eventual upgrading) into a more
valuable fuel by physical, biological or thermochemical processes. My
presentation today will be limited to these last conversion methods ; in
particular to the state-of-the-art and the future development of pyrolysis
and gasification technologies.
In Table 1, Table 2 and Figure 1 a summary of the main characteristics
of thermochemical conversion processes and products is presented (Ref:
A. Bridgwater, Aston University - workshop on LEBEN-PROJECTS/ Feb. 1989,
Brussels).
TABLE 1. Thermochemical Conversion Technologies and Products
Technology
Primary Product
A pplication
Pyrolysis generally
gas
liquid
solid char
fuel gas
oil or liquid fuel substitution
solid fuel or slurry fuel
Flash pyrolysis
liquid mostly
Slow pyrolysis
solid char mostly
Liquefaction
liquid
Gasification
gas
fuel gas
Combustion
heat
heating
TABLE 2. Secondary Products and Sources
Secondary Product
Source
Oxygenate Fuels
Methanol
Fuel alcohol
Gasification
Gasification
Hydrocarbo Fuels
Gasoline
Process
Synthesis
Synthesis
Pyrolysis
Pyrolysis
Liquefaction
Gasification via methanol
Hydrotreating
Zeolites
Hydrotreating
MTG
Diesel
Pyrolysis
Pyrolysis
Liquefaction
Gasification via methanol
Hydrotreating
Zeolite + MOGD
Hydrotreating
MCGD
Fuel oil
Pyrolysis
Liquefaction
Stabilisation
Stabilisation
Pyrolysis
Gasification
Turbine
Engine or turbine
Gasification
Pyrolysis
Liquefaction
Synthesis
Extraction and/or Conversion
Power
Power
Chemicals
Ammonia
Speciality chemicals
CONVERSION I
: TECHNOLOGY s
/ / ,
. V . PRIMARY A '
'/,- PRODUCTS . V
;i PROCESSING
I TECHNOLOGY
/ / / /
\ \ \ DAR Y V S \ \ ' .
-///
PRODUCTS '.-'/-';
\ \ \ \ \
\ f/t \// \.S\/ \f \f/ \\ .. \ */ \ /S\SS\ t/ '
\
V S
S
/
\ \ S \ \ S
MOONQ
Slurry fuel
LIQUEFACTION
Fig. 1. Primary and secondary products from thermochemical

biomass processing
Primary Products
The primary products can be gas, liquid and/or solid char, depending
on the conversion technology employed. Most of the present interest centres
on liquid products due to their high energy density and potential for
premium liquid fuel substitution.
As far as biomass conversion is concerned, I would like to recall here
that:
(a) the basic strategic considerations for the present and future R&D
programmes of the Commission suggest the production of two types of liquid
"biofuels":
Bio-ethanol from sugar or starch (by advanced technologies and new
crops) for the transportation market and which should develop at a
significant rate after the year 2000 (presently given low emphasis by
the Commission) ;
Synthetic-oil
(pyrolytic-oil)
from
lignocellulosic
material
for
general thermal application, as a real substitute for the extensive
oil import market, which could be conveniently produced (technically
and economically) in the medium term (five years).
All other types of biomass fuels can, of course, be regarded as being
of interest and deserve consideration, but only as a tactical means to solve
local and time limited problems, or due to the particular characteristics of
residues (i.e. municipal wastes, manure, sludges, etc.).
10
(b) In the EC the potential displacement by these two types of fuels is very
large and it has been estimated at:
2.2 million
imports).
barrels
OE/day
for
Europe
(about
24% of
total
oil
(c) Biofuels should then be considered an important element in the

Community's energy mix,
whether viewed from the security perspective
(domestic
renewable
feedstock),
socio-economic
impact
(source
of
competitive, intensive manpower activity), rural development contribution,
market dimensions (not saturable demand), environmental improvement (new
uses for agricultural and marginal land, no sulphur, CO2, better climatic
conditions etc.) or technological (industrial) competitiveness.
International collaboration could speed up the progress of pyrolytic
biomass conversion technologies for the following reasons :
(a) Within the framework of the general EC-Canada Agreement, DG XII has
proposed a collaborative programme on "pyrolysis and up-grading of pyrolytic
fuels".
Furthermore,
an international industrial consortium has been
constituted for the implementation of the first "fast pyrolysis pilot plant"
in Spain,
the construction being foreseen at the end of 1989. This
technology should be able to convert lignocellulosic biomass into 60% oil +
10% charcoal + gas (energy efficiency > 80%).
(b) DG XII is joining efforts with DG XVII and DG I for a collaboration with
Brazil and other countries in the bio-energy sector.
(c) In parallel, transfer of technologies to and from Europe is now under
consideration and specific negotiation has already been carried out.
Importance of Regional Biomass Schemes
Biomass is a diluted dispersed resource, therefore there is a need to
implement large projects, probably on a regional scale, to appreciate the
importance and full value of these benefits.
There is general consensus that large-scale exploitation of biomass by
multi-sectorial, innovative and integrated technologies will constitute a
real instrument of rural development.
The
involvement of
regional/national
authorities
then becomes
essential, as a guarantee for large investments as well as their ability to
ensure the continuity of supply,
the control of the cost of biomass
resources in the long term, and to facilitate the market development of this
renewable natural resource.
At present, several regions in Europe are considering the possibility
of implementing major activities in the sector of biomass and of synthetic
oil (pyrolytic fuel) production, as well as other kinds of conversion for
energy and industry.
For these types of project, multi-sectoral integration of large market
industrial activities with the bio-energy sector makes them more attractive
and profitable in terms of economics.
Pyrolysis
Pyrolytic fuel (synthetic oil) has a strategic value because, as a
liquid, its handling, storage, transportation and utilisation are similar to
that of bunker-oil; its heating power is fair (above 6 000 kcal/kg) and its
11
specific gravity higher (1.2 gr/cm) . As it can be used immediately in the
existing utilisation systems, this does not require expensive actions for
market promotion and it can be considered as a fuel for general thermal
applications (steam and electricity production).
Preliminary research results show the possibility of modern bio-energy
technologies reaching promising markets which are:
general thermal applications (heat-steam production);
thermal power stations for electricity production ;
gas-turbine/steam-turbine electricity plant (combined cycles);
conventional refineries.
Through this technology, the penetration and exploitation of biomass
for energy production could be accelerated and implemented on a very large
scale, by the adoption of modular standardised plants for synthetic liquid
fuel production.
Furthermore,
such a conversion product could also be
utilised at a later stage as a raw material for chemicals.
Another activity, inspired by the Commission and already considered of
interest by important industrial groups (Mannesmann, VEBA, etc.), is the
development of mobile pyrolysis plants, mounted on tracks. These plants are
aimed at the production of pyrolytic fuels from biomass harvested by smallholders. This could also allow the creation of service companies, which
could contribute to a rapid expansion of this activity.
Concerning the state-of-the-art and the progress of pyrolysis
technology, we can confirm that:
This old technology disappeared by and large during the last 40 years.
Up to now only a low level of activity in Europe (seven years).
However, the general situation in Europe is now improving solely as a
consequence of the RSD programme initiated and managed by DG XII of the
Commission. Several experimental activities have been carried out over the
past seven years or are now under implementation in several countries (F, I,
FRG, B, E, GR) . Large industrial organisations (mainly German, i.e.
Mannesmann, Preussag, VEBA, Bayer) are interested.
In some cases European industry has offered a full guarantee of this
technology. As a consequence, it was possible to perform on a realistic
basis an initial techno-economic evaluation for the bio-energy sector of the
LEBEN-Projects (see Figure 2 ) .
It is important to note that advanced pyrolysis technologies also
exist outside Europe and in particular in Canada and the USA.
These,
however,
are only at a laboratory stage. European advanced commercial
technology can be made available in five to ten years through a continuous
R&D effort focussed on conversion efficiency,
quality of products and
reduction of specific investment.
The forecast on conversion investment costs evolution, is as follows:
at present:
in 1993:
around 2000:
For comparison,
North Sea:
Middle East:
7 US$/barrel OE
4 US$/barrel OE
2 US$/barrel OE
specific investment costs for oil exploration (1987)
8-10 /barrel
2 /barrel
5o
$/BARREL OF OIL EQUIVALENT
- $5 (Social and
salaries)
- $1.8 (Exchange)
III
+ $ 8 / b a r r e l for
dssulphurisation
ECU/t (dm)
F i g . 2.
to
13
An interesting development concerns pyrolytic oil upgrading, through
the adoption of ZSM-5zeolite conversion directly on pyrolysis vapours. A 20%
yield of gasoline on wood looks feasible. Assuming a cost for biomass of
35 ECU/t, the gasoline could be produced at a cost of around 175 ECU/t
(actual market price:
150 ECU/t),
if the phenolic fraction was to be
recovered (to obtain phenolic raw material for phenolformaldehyde type of
resin) and sold at 335 ECU/t (actual cost 670 ECU/t).
Small capacity decentralised gasoline production plants could result
from such activity and would be of great interest especially for remote
areas in developing countries.
CONCLUSIONS
Biomass for energy has great potential in the Community (around
300 Mt/year);
thus biofuel production should be seriously considered a
significant element in the Community's energy mix.
Large-scale exploitation of biomass presents the following benefits :
(1)
(2)
(3)
(4)
(5)
(6)
potential energy contribution: around 1 0 % of primary energy needs;

contribution to industrial needs: possibility of covering 100% of the
EC deficit, around the year 2000;
social impact: 600 000 new jobs in the Community for the bio-energy
sector alone;
large exploitation of biomass could constitute an important instrument
for rural development
improvement of environment and quality of life;
stimulation of industrial competitiveness in this new sector of
activity;
Multi-sectoral integration of large market activities improves the

economic results of a comprehensive massive exploitation of biomass.
Integrated projects on a regional level appear to be the correct
dimension for an optimal exploitation of biomass.
As far as the bio-energy by-sector is concerned, the production of
synthetic liquid fuels (pyrolysis), as a substitute for oil, for refineries
and for general thermal application (heat and electricity production) looks
very promising and better suited in the short and medium term in the frame
of agro-energy-industrial projects (LEBEN).
By means of integration of markets,
progress of technology and
development of crops, production of this type of synthetic fuel will, in a
relatively short term, become competitive in southern Europe and in five to
ten years also in northern Europe.
14
PROGRESS IN PYROLYSIS AND GASIFICATION OF BIOHASS:
AN OVERVIEW OF RESEARCH IN THE UNITED STATES
J. DIEBOLD and D. STEVENS
Solar Energy Research Institute
Golden, CO 80401
Summary
The United States Department of Energy (U.S. DOE) is conducting
research to produce liquid transportation fuels from biomass and
municipal waste. Research in the thermochemical conversion area
includes production of both methanol and gasoline. Methanol is
produced by gasifying the biomass feedstock to produce a mediumenergy synthesis gas, which then can be cleaned, conditioned, and
catalytically converted to methanol. Gasoline is produced by first
generating biocrude oils through high or low pressure pyrolytic
processes. Catalytic upgrading of the intermediate, biocrude oil
product yields hydrocarbon products, which can be used directly
as gasoline or as octane enhancers depending upon the catalytic
process employed. A summary of the thermochemical program within
the U.S. DOE is presented.
1.
INTRODUCTION
Until the discovery of large quantities of low cost petroleum and
natural gas in the early 1900's, wood supplied a significant proportion
of the energy requirements for heat and power. Combustion of wood in
various sized boilers produced steam to heat buildings, power industrial
machinery, and even power transportation vehicles such as ships, trains,
and farm machinery.
Today, it is estimated that biomass provides about 3 quadrillion
BTU's of energy per year in the United States. This corresponds with
about 4% of the annual U.S. energy demand. This energy comes primarily
from the combustion of wood and other forms of biomass to provide steam
and process heat. This contribution is very significant in relation to
other energy resources. Nuclear energy generation, for example, provides
about 4 to 5 % of the nation's energy supply.
With proper resource
management and the development of efficient conversion processes, it has
been estimated that biomass resources can provide an even greater
fraction of this nation's energy supply. (1)
Liquid fuels derived from biomass are expected to contribute
significantly to this energy potential.
As an abundant, renewable,
domestic energy resource, biomass can help the United States reduce its
dependence on imported oil. Biomass is the only renewable energy source
capable of supplying liquid transportation fuels. Thermochemical
conversion processes offer efficient methods for converting biomass to
liquid hydrocarbon fuels through a variety of processes. At present,
thermochemical research sponsored by the U.S. DOE is focussed on the
production of methanol or gasoline. Thermal conversion processes are
well suited to the conversion of wood and crop residues, which account
15
for the vast majority of the biomass resources in the United States.
These processes can convert all of the organic materials in the
feedstocks to liquid fuel products, with water and carbon dioxide as
byproducts. In addition, the thermochemical processes and their products
are relatively insensitive to variations in the feedstock.
Harvested biomass is typically a solid material having a low energy
density, as well as a tendency to biodegrade during storage. With the
advent of petroleum fuels, society has become very dependent upon fuels
which can be conveniently stored in a form having a very high energy
density and which can be transported and metered into a combustor as a
fluid.
For example, the energy contained in a volume of aromatic
gasoline is equivalent to that in 4 volumes of solid softwood or 8
volumes of sawdust.
Relative to coal, biomass is extremely easy to
liquefy or gasify due to its high reactivity. This characteristic makes
biomass a prime candidate for the production of liquids or synthesis
gases, which may be upgraded to transportation fuels. The diversity of
biomass suggests that fairly small conversion plants would be very
desirable, which can be quickly developed and constructed.
Thus, the
conversion of biomass to liquid transportation fuels would favorably
impact local economies by the creation of employment opportunities in
rural areas.
Although the extent of the world's petroleum resources have been
traditionally underestimated, it is generally agreed that petroleum is
a finite resource and the only real question is when, not if, will
alternate sources of liquid transportation fuels be needed. However,
most of the world is dependent upon oil fields which are remote from the
consumer and upon long shipping routes and/or pipelines which will prove
to be very difficult to protect. Consequently, the next oil shortage
will most likely be caused by political decisions or by accidents, rather
than to depletion of the world's petroleum resources. Biomass resources
provide a secure fuel source, which is immune to these types of
disruptions.
Biomass also provides a method to help ameliorate carbon dioxide
emissions to the atmosphere. Recent concerns about the rising levels of
carbon dioxide in the atmosphere, implicate the widespread combustion of
fossil fuels. Since the use of biomass as a fuel involves the recycling
of atmospheric carbon rather than the conversion of fossilized carbon to
atmospheric carbon, future methods to reduce carbon dioxide emissions
should include the increased use of biomass as a source of fuel. This
implies the need for the development of technology related to the
conversion of biomass to more conventional forms of fuel.
The U.S. Department of Energy is sponsoring research on the
production of fuels through its Biomass and Municipal Waste Technology
Division. This research includes the development of energy crops and
their conversion to fuels using biological or thermochemical processes.
The biological processes typically produce plant oils, methane, or
ethanol.
The thermochemical processes produce: a) methanol from
synthesis gases having a medium energy content; or b) biocrude liquids
for subsequent refining to a hydrocarbon gasoline, via catalytic cracking
or hydrognation.
The potential impact of this research would be a
seven-fold increase in the contribution of biomass to the energy consumed
in the United States from the current level of about 3% to a little over
20%. (1) For this large a contribution to the energy supply, successful
research must be completed in biomass production, as well as in the
conversion processes. Actual deployment of the several thousand biomass
16
refineries would require a major industrial investment, which will not
take place until the economics are made more feasible through research.
This paper is an overview of research and development sponsored by
the U.S. DOE in the technology area of the pyrolysis and gasification of
biomass and municipal-refuse-derived fuel (RDF). This research includes
the upgrading of these intermediate liquids an/or gases to methanol or
gasoline. The reader is referred to the proceedings of four recent major
symposia (1-4) for additional detail in specific areas discussed in this
paper.
2.
CONVERSION OF BIOMASS TO METHANOL

The conversion of biomass to methanol first involves the
gasification of the biomass to a gas which is primarily composed of
hydrogen and carbon monoxide, with very little inert gases such as
nitrogen or methane, and virtually no sulfur compounds nor tars. Once
these synthesis gases have been generated in the proper proportions, the
technology to convert them to methanol is commercially available.
Therefore, the development of the conversion of syngases to methanol has
been left to industry. The gasification of biomass to produce a clean
synthesis fuel gas has been studied extensively over the last eight years
with the successful development of four process development units (PDU's)
involving quite different reactor designs. Two of these used partial
combustion with oxygen to directly supply the heat needed for
gasification including: a downdraft fixed bed (SERI/Syngas) and a single
fluidized bed (IGT).
The other two used heat which was transferred
indirectly to the gasification zone from separate combustion processes,
including: a dual-fluidized bed (Battelle-Columbus) and a single
fluidized bed (University of Missouri-Rolla).
To better understand
pyrolysis and gasification, DOE is continuing research into the
mechanisms involved and the catalytic removal of residual tars. DOE is
completing limited work on gasification development.
Gasification research Research into the actual mechanisms involved
during the gasification of biomass and pelletized RDF is being carried
out at SERI and also at the University of Washington. This research will
be valuable to the design and operation of fixed-bed or slow-moving-bed
gasifiers.
In the SERI research, a single cylindrical particle of
biomass or pelleted RDF is instrumented and placed in a preheated
reactor, which is swept by a flow of a mixture of nitrogen and oxygen.
The pellet is heated from all sides. The temperatures of the surface and
the center of the particle, the weight, and the energy flux are all
measured in real time during the pyrolysis and/or flaming combustion of
the single particle. A very thin, visually transparent coating of gold
on the glass reactor wall acts as an infrared radiation shield to reduce
heat losses to a low level, while allowing the pellet decomposition to
be visually observed and photographed.
Empirical equations have been
derived which predict the time of pyrolysis (or flaming combustion), the
heat required for pyrolysis, and the ash content as a function of
temperature, initial moisture content, oxygen in the carrier gas, and
relative amounts of plastics, metals, and newspaper in RDF pellets. A
mathematical model based on scientific principles was shown to predict
the temperatures and weight loss of the pellet quite well. (5-7)
In complimentary research at the University of Washington, a single
pellet of biomass or RDF is radiantly heated from only one surface to
result in a one-dimensional heat flux. The surface and several internal
temperatures of the pellet are monitored during the test, and the
17
pyrolyss products collected.
Empirical equations have been derived
showing the interactions of the process variables for both softwood
pellets of varying density and for RDF pellets. Mathematical models,
based on scientific principles, are in progress involving heat transfer
considerations and global chemical kinetics. (8,9)
Gasification development U.S. DOE is completing research on one of
the promising pyrolysis reactor designs, a fluidized bed.
A major
technical area, which has been addressed with the past gasification
research is how to transfer the necessary heat into the bed that is
required to pyrolyze the biomass. In addition to oxygen-blown gasifiers,
DOE has examined indirect methods of providing heat. Indirect heating of
the fluidized bed through heat-exchange surfaces immersed in the bed has
the potential of operational simplicity and possibly a smaller reactor
size.
Research into the heat transfer between heat-exchange tubes immersed
in a fluidized-bed gasifier at the University of Missouri-Rolla showed
that the factor limiting the heat transfer to the bed was the heat
transfer between the inside of the tube and the hot combustion gases.
Recent research by MTCI, Inc. has been directed toward the improvement
of this limiting heat transfer. Rather than merely increasing the hot
gas velocities to increase the heat transfer rates (which requires more
input of mechanical energy to the blower on the combustor) ,
MTCI
replaced the conventional pressurized combustor with a pulsed combustor.
The pulsed combustor concept is over 50 years old, but some of the
benefits are only now being realized. The pulsed combustor consists of
a combustion chamber fitted with a long exhaust pipe which is sized to
produce a resonating, traveling pressure wave. Valves open when the
combustor pressure is low to allow a fresh charge of fuel and air to
enter without the need for a mechanical blower. In the MTCI design, the
mechanical valves are replaced by aerodynamically sized inlet and outlet
ports. In the resonance tube, the combustion gases experience very high
velocities because the forward and backward velocities of the resonating
gases are superimposed upon the net gas velocity. This resonating gas
flow resulted in an increase in transfer of heat to a fluidized-bed
gasifier by a multiple of between four and five times greater. Data in
the literature suggest that an order of magnitude increase in heat
transfer over that attained with conventional turbulent flow can be
attained through the use of resonating gaseous heat transfer. (10) With
the use of calcium carbonate as the fluidized-bed material, relatively
high hydrogen and low tar yields were obtained, apparently due to
catalytic effects of the calcium.
With funding from the Office of
Industrial Programs in DOE, this system has also been used to gasify
black liquor from the Kraft pulping process in steam. This resulted in
gases containing very high levels of hydrogen and carbon dioxide and low
levels of tars and carbon monoxide, apparently due to catalytic effects
of the sodium present in the black liquor and in the sodium carbonate bed
material. (11)
Catalytic reduction of tars in gasification The use of synthesis
gases in conventional methanol synthesis systems requires that the levels
of pyrolytic tars be very low.
Research at the Pacific Northwest
Laboratory (PNL) has investigated the use of catalysts to reduce tars.
A primary fluidized gasifier was operated, followed by a secondary
fluidized bed in which the catalysts were placed. The catalysts appear
to function by reacting with the tars to form coke and then to promote
the oxidation of that coke to form gases. Inputs to this secondary bed
18
were steam-gasification vapor products and enough air to prevent catalyst
deactivation by oxidizing the coke deposits as they formed.
The
oxidation very specifically gasified the coke on the catalysts to result
in greatly increased the gas yields. Even with 0.4 g of air added to the
secondary reactor per g of wood feed, the nitrogen composition in the
gaseous products did not change significantly from the original value in
the dirty gases. The remaining hydrocarbons in the gases were primarily
volatile aromatic compounds, which were not be expected to be troublesome
for most applications. (12)
Using the MB/MS, SERI will soon be
initiating a study to screen different catalysts for the reduction of
residual pyrolytic tars.
3.
CONVERSION OF BIOMASS TO GASOLINE

The U.S. DOE is also sponsoring research to convert biomass to
gasoline hydrocarbons. This research is focussed on first converting the
biomass to a biocrude oil or vapor and then upgrading the intermediate
to gasoline.
Gasoline is completely compatible with the existing
distribution and vehicle systems; it naturally produces low aldehyde
emissions; and it has a greater energy content.
With the modern
computer-controlled automobile engines coupled with catalytic mufflers,
hydrocarbon gasolines would be expected to produce very low levels of
pollution in the form of carbon monoxide, aldehydes, and unburned
hydrocarbons.
These considerations have led to the development of processes to
convert biomass to gasoline. Three process routes have been investigated
to make gasoline intermediates from biomass:
a)
liquefaction in a
pressurized solvent to produce a biocrude oil having a low oxygen
content; b) liquefaction of biomass at low pressures with slow pyrolysis;
and c) fast pyrolysis of biomass at low pressure to form a biocrude oil
having a high oxygen content.
Two upgrading processes have been
investigated: a) catalytic deoxygenation of the biocrude oils with
pressurized hydrogen; and b) cracking and deoxygenating the biocrude
vapors with zeolite catalysts at atmospheric pressures.
Liquefaction of biomass in pressurized solvents The liquefaction
of biomass in pressurized solvents was demonstrated at Albany, OR in the
late 1970's. This process was operated at 20.8 MPa pressure, 20 minutes
residence time, and with a sodium carbonate catalyst. Since the early
1980's, research in this area was shifted to the University of Arizona
and has focussed on improving the solids content of the slurry of biomass
solids fed into the high pressure reactor. Higher contents of biomass
in the feed, allow a smaller, more economical reactor vessel to be used
for a given throughput. Mixtures containing as much as 60% wood flour
in product oil have been pumped into pressurized containers, using a
modified extruder originally designed to extrude plastics. With this
technique, early liquefaction experiments at the University of Arizona
were conducted at 375 to 400 C, 5.5 to 21 MPa pressure, 40% wood flour
in Albany oil with a residence time of between one and four hours, and
both with and without carbon monoxide and sodium bicarbonate catalyst.
Recent experimentation was directed toward the recycling of the product
oil containing approximately 40% fresh wood flour, along with water and
carbon monoxide to result in a carrier oil composed primarily of material
made at the University of Arizona. The fluid product distilled from the
carrier oil had a heating value of 37 MJ/kg (16,000 BTU/lb), a residual
oxygen content of 7 to 10%.
The oil yield was close to that
theoretically attainable. (13)
19
Liquefaction of biomass at low pressures with slow pyrolvsis The
product slates from the slow heating of loose mixtures of RDF materials
at atmospheric pressures in a retort swept with helium has been
researched at Argonne National Laboratory. Final temperatures of 475 C
were used. Sample sizes were varied between 1 and 50 g. The yields of
tar and solid residue from newsprint were reported to be 25 to 30% and
21 to 26% respectively at heating rates of 5 C/m. The effect of heating
rates between 5 and 30 C/m were found to be negligible. The influence
of polyethylene in the feed was seen only in the tars collected after the
first of a series of condensers, as deduced through the use of IR
spectral analysis. The presence of polyethylene in a kraft paper feed
decreased the low viscosity of the tars by a third. (14)
The yields
of condensates are consistent with those reported for RDF components
previously reported by the New York University with similar sample sizes
and slow heating rates of between 12 and 136 C/m. (15) It appears that
slow heating rates of around 136 C/m and slower in a retort produce lower
yields of organic condensates from RDF compared to other processes which
use faster heating rates.
Liquefaction of biomass at low pressure with fast pyrolvsis Fast
pyrolysis processes can be used for biomass liquefaction at atmospheric
pressures, vapor residence times of less than a second, and intermediate
temperatures of around 500 C. The fast pyrolysis condensates have about
the same oxygen content and energy per unit weight as the feedstock.
However, when produced with only the water of pyrolysis present, they are
very fluid at room temperature and have a specific gravity of about 1.25.
Due its relatively low projected cost, fast pyrolysis is currently
thought by the International Energy Agency's Liquefaction Activity to be
advantageous depending upon the end use of the product. (16)
Basic research into the pyrolysis of biomass and RDF has been
recently studied at the Solar Energy Research Institute (SERI) using the
molecular beam mass spectrometer (MB/MS) to study the pyrolysis vapors
and gases in real time as they evolve from the pyrolyzing particles.
Over 50 different samples of biomass and RDF were pyrolyzed and analyzed
by the MB/MS scanning over the mass ranges of 10 to 250. Multivariate
analysis of this very extensive data set was used to determine that there
were 13 factors that explained over 90% of the variance in the data.
Interpretation of the data resulted in the identification of six major
chemical compound classes to explain the 13 factors. To determine the
effect of process variables, a statistically designed set of experiments
was conducted to look at the effects on the six compound classes
identified in the feedstock screening tests. Empirical equations were
fitted to the data and used to generate parametric plots showing the
effect of different variables.
In addition, a set of 50 different
pyrolysis oils, most of which were part of the IEA set of pyrolysis and
gasification oils, were analyzed on the MB/MS. Multivariate analysis was
also used to reduce this data set to a similar set of six major chemical
compound classes.
An empirical equation was fit to the data which
predicted the size of the distillable fraction based on the relative
amounts of the various compound classes. (17,18)
Applied research in fast pyrolysis at the Georgia Tech Research
Institute has used an entrained-flow reactor. In this system, powdered
wood (0.30 to 0.42 mm) is entrained in a straight tube by a flow of
stoichiometrically combusted flue gases.
The heat for pyrolysis is
supplied by these carrier gases.
If the carrier gases are too hot,
20
significant losses from the first-formed vapors take place to result in
higher overall gas yields.
Consequently, fairly large amounts of
tempered carrier gases at 745 C were used at a carrier-gas-to-biomass
weight ratio of about 8 to supply the heat of pyrolysis to maximize the
yield of pyrolysis oils. The diameter of the entrained-flow reactor is
currently 15 cm and the length is 4.4 m, which results in a residence
time of one to two seconds. This residence time is a compromise between
the length of time needed to pyrolyze the size of particles fed on a
once-through basis and the need to minimize the time which the pyrolysis
vapors spend in the reactor. Feeding rates are typically about 15 kg/hr
and have resulted in reported yields of 58% organic condensates (moisture
free) and 12% char (maf feed) with a total mass closure of 101%
(including the large amount of carrier gases).
The pyrolyzate is
recovered along with the water formed in the combustion used to directly
heat the carrier gases, as well as any water formed during pyrolysis,
or which was present as moisture in the feed, resulting in condensates
containing about half water. (19,20)
A different type of entrained-flow reactor has been developed at
SERI specifically for the fast pyrolysis of biomass. In this reactor,
the feed is entrained at very high velocities (calculated to be about 400
m/s) in a tube having an inside diameter of 1 cm into a vortex reactor
having a diameter of 13 cm and a length of 0.69 m. The feed particles
are forced to slide on the hot cylindrical wall in a helical path as they
pass through the reactor. The sliding contact of the particles on the
wall results in very high heat transfer to the particle so that ablative
pyrolysis is thought to take place. Partially pyrolyzed particles exit
the reactor tangentially, are mixed with fresh feed, and are recycled
back to the carrier gas ejector, where they are re-accelerated by the
supersonic carrier gas. The recycle loop decouples the residence times
of the solids and the vapors, which allows the vortex reactor to be
insensitive to the particle size of the feed. The small amount of char
which is formed is also recycled until it is attrited to a fine powder
(-50 micrometer). (21) A mathematical model based on first principles
suggests that the typical 2-mm thick feed particle will make about 30
passes during a total residence time of 1 to 2 seconds through the
reactor before it is completely pyrolyzed.
Operation of this small
reactor is typically at 13 to 20 kg/hr of dry sawdust (-3 mm) with a
carrier-gas-to-biomass weight ratio of 1 to 1.5. Yields on a dry feed
basis have been 67% condensates (55% moisture-free organic liquids), 13%
char, 14% net pyrolysis gases, and 12% water of pyrolysis for a mass
closure of 94% of the feed (a 98% mass closure, if the nitrogen carrier
gas is included in the calculations) . (22) This reactor has recently
been modified to allow it to pyrolyze RDF, which contains tramp metals
and other inert solids. Preliminary operation with RDF indicates that
the plastic derived condensates interact with the lignocellulosic derived
condensates to form an asphalt appearing material. (23,24) The asphalt
nature of these condensates contrasts with the low viscosity reported as
a result of slow pyrolysis. (17)
An alternate approach to effect the sliding contact between a hot
surface and the biomass to be rapidly pyrolyzed has been under
development at the Colorado School of Mines (CSM). The CSM reactor uses
two specially grooved disks made of copper, which are stacked one on top
of the other. The biomass or RDF is centrally fed between the heated
disks. As the bottom disk is rotated at 4 to 80 rpm, the feed particles
make their way to the circumference of the disks in a spiral path and are
allowed to fall to a cooler zone. The vapors and gases pass between the
21
heated disks and also exit at the circumference of the disks and pass out
of the reactor to the condensers. The disks had a diameter of 6.4 cm.
Feeding rates were 13 to 210 g/h. Maximum reported liquid yields from
sawdust were 54% (including moisture) at disk temperatures of 600 C, a
flow of nitrogen purge gas of 0.5 g N2 per g of sawdust, and a feeding
rate of 13 g/h. (25,26) If the developmental challenges can be met, the
CSM pyrolysis reactor offers a greater decoupling of the purge or carrier
gas flow rates than is possible with other fast pyrolysis reactors, e.g.
entrained flow, vortex, or fluidized bed reactors.
Characterization of organic condensates formed by thermochemical
processes
The pyrolysis and gasification processes mentioned above
produce condensates which vary in their characteristics depending upon
the nature of the process.
In particular, time spent at high
temperatures increases gas formation, but also changes the nature of the
surviving organic condensates. A recent study by PNL of condensates made
with short residence times at temperatures from 450 to 900 C revealed
that the primary pyrolysis condensates which form at 450-500 C do not
contain polycyclic aromatic hydrocarbons (PAH's) and are not carcinogenic
to mice. However, as the pyrolysis temperatures are raised, the amount
of PAH's increases along with the carcinogenicity to mice. In fact, the
tars formed above 800 C appeared to be slightly more carcinogenic to the
mice than was the reference material, benzo(a)pyrene. (27)
The nature of the oxygenated oils and tars formed by the various
pyrolysis processes is such that they are not equivalent to a petroleum
crude oil and they require different refining techniques to be developed.
The oils formed in pressurized solvents have tended to have a high
phenolic content, whereas, the oils formed by fast pyrolysis have a very
high oxygen content. These biocrude oils could be used as boiler or
turbine fuels without refining. However, neither of the biocrude oils
can distilled into usable gasoline or diesel fractions, rather both of
them must be deoxygenated to be
converted hydrocarbons and usable
transportation fuels. Two such deoxygenation processes have been under
development: a) hydrognation with cobalt-molybdenum catalysts at high
pressures, and b) cracking with zeolite catalysts with no added hydrogen
at atmospheric pressures.
Upgrading of pyrolysis products by hydrognation The upgrading of
pyrolysis oils, formed at both high and low pressures, through catalytic
hydrognation has been under investigation at PNL. Early work used oils
formed at high pressures in the Albany (PERC) process with a sulfided
cobalt-molybdenum catalyst at 13.8 MPa hydrogen pressure, 350 to 450 C,
and a liquid hourly space velocity (LHSV) of
0.1 volume of oil per
volume of catalyst per hour to produce a hydrocarbon product boiling
primarily in the gasoline range. (28) More recently, this work has been
expanded to oils formed by the fast pyrolysis of biomass at atmospheric
pressures made at Georgia Tech, SERI, as well as those from Canada and
peat derived oils from Finland. The fast pyrolysis oils must first be
stabilized by deoxygenation in the presence of hydrogen at low
temperatures to avoid polymerizing the feedstock. After
stabilization,
the fast-pyrolysis oils are partially deoxygenated and have many
properties in common with the oils formed at high pressure.
The
stabilized pyrolysis oils can then be hydrodeoxygenated at higher
temperatures to form a gasoline product similar to that made from the
high pressure oils.
Originally, this two-step process was conducted
separately at a pressure of 13.8 MPa hydrogen, temperatures of 275 and
22
350 C, and liquid hourly space velocities of 0.6 and 0.1 in the first and
second reactors, respectively. Yields on a dry wood basis from pyrolysis
oils made by Georgia Tech were about 25 wt% of hydrocarbon product
containing only 1.3 wt% oxygen. More recently, this two-step process was
combined into a single, non-isothermal reactor at 13.8 MPa, which
maintained the inlet temperature at around 260 C and the outlet
temperature at around 375 C. With a LHSV of 0.1 volume of oil per volume
of catalyst per hour, the fast, pyrolysis oil from SERI was converted into
a product which contained only 1.3 wt% oxygen, a hydrogen-to-carbon ratio
of 1.68, and 73 vol% boiling in the gasoline range (C5 to 225 C ) . Liquid
product yields of about 20 wt% were reported based on the dry wood feed.
The cause for the difference in yields has not been addressed. (29)
Octane tests of the gasoline products, combined from several preliminary
hydrognation experiments of the Albany oils, indicated a research octane
of 77. (29,30) Based on the fairly high hydrogen-to-carbon ratio and the
medium octane value, it is highly probable that the octane level could
be raised by optimizing the process or by removing some of the hydrogen
in a subsequent reforming step to increase the aromatic content, as is
commonly done in a typical petroleum refinery, i.e. with "Platforming".
Zeolite upgrading of pyrolysis oil vapors at low pressures
An
alternate method to the high pressure upgrading of the pyrolysis oil is
with the use of zeolite catalysts at atmospheric pressures without added
hydrogen.
These catalysts were introduced to the petroleum industry
about 30 years ago and have found widespread use in the catalytic
cracking of heavy petroleum fractions to increase the yield of gasoline.
More recently, Mobil has developed zeolite catalysts which have pore
sizes small enough to allow production of toluene and similar gasoline
compounds. This H-ZSM-5 catalyst is now in commercial use in New Zealand
to convert methanol to gasoline.
Although the molecular weight of the
condensed pyrolysis oils has been found to be typically between 500 and
2000, researchers at SERI determined that the pyrolysis vapors had much
lower molecular weights of typically less than 200. The molecular size
and shape of most of the identified compounds were small enough to enter
the H-ZSM-5 pore.
Preliminary experiments with H-ZSM-5 catalyst
furnished by Mobil confirmed that a small amount of catalyst was
sufficient to change the product slate from the oxygenated pyrolysis
vapors to a highly aromatic gasoline product.
This process has been
studied extensively using the MB/MS which allowed the product slate to
be examined in real time as the catalyst aged in a fixed bed of 10 g of
H-ZSM-5 catalyst. A process variable study was conducted to identify
optimum operating conditions, which were found to be quite different from
those used to convert methanol to gasoline. Empirical equations were fit
to the data to result in parametric contour plots illustrating the
effects of the process variables on the yields. (31,32,33) Concurrently,
research has been conducted with a larger fixed-bed reactor having 100
g of catalyst and fed a small slipstream of fresh pyrolysis vapors
directly from the vortex reactor at SERI. (34,35) Hydrocarbon product
yields, including olefins, have been around 15 wt% of the dry feed, when
using steam as the carrier gas and a weight hourly space velocity of
between 1 and 4 g wood per g catalyst per hour at 525 C. Recent research
has been directed toward recovery of the gaseous olefins as part of the
gasoline product. The gasoline produced consists primarily of alkylated
benzenes, e.g. toluene, xylenes, ethyl benzene, and isopropyl benzene
(eumene). These compounds are present in today's commercial gasolines
and their effect is to raise the octane value. (36,37) Similar impure
23
streams (mixed xylenes) in a petroleum refinery are typically worth one
and a half times the value of unleaded gasoline. The upgrading of fastpyrolysis oils with zeolites has also been studied at
Georgia Tech
Research Institute, but detailed results have not yet been released.
(19,20)
Technoeconomic assessments (38) Technoeconomic assessments were
recently made by Science Applications, Inc. (SAI) to compare two methods
of upgrading fast pyrolysis products to gasoline. Each of the two
processes were evaluated at their present stage of development, as well
as, at the expected future stage of mature development. In the process
being studied at PNL, the condensed fast pyrolysis oils, made by an
entrained-flow process similar to that of Georgia Tech, are fed to a high
pressure reactor where in the present case the oils are first
deoxygenated in the presence of hydrogen at relatively low temperatures
to stabilize the oils to prevent polymerization reactions.
The
stabilized oil is then treated with hydrogen at higher temperatures to
complete the hydrodeoxygenation process. Hydrogen is made by steam
reforming and shifting of the byproduct gases. This hydrognation process
is relatively complex and capital intensive, but is said to have the
potential of very high hydrocarbon yields of about 32% by weight of the
dry feed. Liquid hourly space velocities of 1.0 and 0.1 were assumed for
the "current" two-step hydrognation process. A LHSV of 0.5 was assumed
for the "future" non-isothermal hydrognation process in a single
reactor.
The other process, which is being studied by SERI, is based on the
immediate conversion of the hot organic vapors, formed by fast pyrolysis
in the vortex reactor, before they are allowed to cool and condense. In
this process at atmospheric pressures, the hot carrier steam, pyrolysis
gases, and vapors are passed through a catalytic cracking reactor loaded
with H-ZSM-5 catalyst. With a gas residence time of a few seconds, an
equivalent LHSV of 2.5 was assumed to give complete conversion of the
oxygenated organic pyrolysis vapors to the hydrocarbon products, water,
and oxides of carbon. The process stream was then condensed and the
olefinic gases adsorbed from the off-gases and recycled. This process
is thought to have lower potential gasoline yields of 24% of the dry
biomass feed, but is less capital intensive per unit weight of biomass
fed than high pressure hydrognation.
The present technoeconomics of both processes were examined in light
of the state-of-the-art as it existed at the time of the beginning of the
study:
a 15 wt% yield for hydrognation; and 10% yields for zeolite
cracking. The annual cost assumed for the capital was equivalent to a
simple amortization over 20 years of the total capital investment at 15%
annual interest without any subsidies or tax considerations. The assumed
cost of the feedstock was $27.50 per dry tonne.
As expected, the
research on these processes is only partially completed and established
research goals have not yet been reached. For this reason, projected
production costs in a plant fed 908 tonnes of dry biomass per day were
not economically attractive at $2.64 per gallon via hydrognation and
$2.92 per gallon via catalytic cracking. Incorporation of more recent
yields and process information would result in lower predicted production
costs for both processes.
If future research and development are successful, the economics
improve substantially. The future hydrognation process is projected to
require a capital investment of $74.4 M to result in a cost of $0.96 per
gallon of medium octane gasoline. The future zeolite cracking process
24
was projected to require a capital investment of $47.8 M to result in a
cost of $1.05 per gallon of high octane gasoline blending stock. These
projected production costs are very sensitive to the relative success of
research and development to achieve the gasoline yields assumed. Within
the accuracy of the study, the projected production costs are equivalent
for the two different gasolines.
4. COMMERCIALIZATION OF DOE DEVELOPED TECHNOLOGY
There are several private firms which are involved with the
commercialization of biomass gasification in the United States. Most of
this work has involved air blown, low-energy gasifiers for fuel purposes.
Approximately 20 gasifiers are currently in operation
including, for
example, a unit which provides boiler fuel for a hospital in Rome,
Georgia. Other units are being planned. Technology based on a downdraft
gasifier developed by the DOE program at SERI is being used by Syngas,
Inc. to develop gasification systems to produce electricity in New York.
Another gasifier, based on the vortex reactor is being planned by
Pyrotech to operate in California.
There currently are no firms with commercial gasifiers to produce
a medium-energy gas, which could be utilized as a synthesis gas. To
encourage such a development and to facilitate the commercialization of
a process to make methanol from biomass, the U.S. DOE has recently
announced that it is looking for an industrial partner to share the cost
of the scale-up of a gasifier system to produce a medium-energy gas.
This would be at the 15 to 25 tonne per day size. A formal request for
proposal is soon to be issued to those U.S. companies indicating an
interest to share at least 50% of the cost of the project. The U.S. DOE
funding for this project is projected to be about $5M over the life of
the development. (42)
5. FUTURE TRENDS IN THERMOCHEMICAL CONVERSION IN THE U.S.
The DOE funding available for thermochemical conversion has steadily
declined in recent years. Cutbacks in the research program during the
current fiscal year resulted in the cancellation of all thermochemical
programs, except those at SERI.
The research and development of the
zeolite upgrading of the pyrolysis oils to improve yields at lower cost
and the pyrolysis of RDF in the vortex reactor to optimize organic vapor
yields will continue at SERI, but at reduced levels compared to prior
years.
This funding decline is at a time when the world is looking for
methods to reduce the emission of carbon dioxide through the curtailment
of the use of fossil fuels. Since the use of biomass as a fuel recycles
carbon dioxide over the course of a few years, it will not be a net
contributor to the "greenhouse" effect. In future years, the funding for
alternate sources of methanol and gasoline may be more optimistic.
6. CONCLUSIONS
The U.S. DOE has successfully transferred the technology for
gasification to produce low-energy gases and commercialization of this
technology is underway. Gasification of biomass to produce medium-energy
gases for methanol synthesis is still being researched at a low level of
effort and a pilot plant demonstration project is planned, in which the
U.S. DOE will share the cost of development with a private firm. Most
thermochemical research in the last few years has been directed toward
the production of liquid hydrocarbon fuels, i.e. gasoline.
Using
pyrolysis oils formed during the fast pyrolysis of biomass, two promising
25
processes to make gasoline have been researched concurrently. This work
will also examine the use of RDF feedstocks to produce gasoline.
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gases" in Ref. (1), pp. 87-100.
WHITE, D.H. and WOLF, D. (1988) "A dvances in direct biomass
liquefaction by the extruder-feeder method" in Ref. (1), pp. 5766 and Ref. (2), pp. 827-853.
HELDT, J.E. and MALLYA, N. (1988) "Experiments on basic mechanisms
of pyrolysis" in Ref. (1), pp. 221-236.
KA ISER, E.R. and FRIEDMAN, S.B. (1968) "The pyrolysis of refuse
components", Combustion. May, pp. 31-36.
ELLIOTT, D.C, BA KER, E.G., BECKMA N, D., SOLA NTA USTA , Y.,
TULENHEIMO, V., OSTMA N, ., GEVERT, S.B., HORNELL, C , and
KJELLSTROM, B. (1989) "A technical and economic analysis of direct
biomass liquefaction" in Ref. (4).
EVA NS, R.J., MILNE, T.A ., and FILLEY, J. (1988) "Mass
spectrometric studies of municipal solid waste pyrolysis" in Ref.
(1), pp.209-219.
26
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(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
(31)
(32)
(33)
(34)
(35)
(36)
(37)
(38)
(39)
(40)
EVANS, R.J., and MILNE, T.A. (1988) "Mass spectromctric studies of

the relationship of pyrolysis oil composition to formation
mechanisms and feedstock composition" in Ref. (2), pp. 264-279.
KOVAC, R. (1988) "Production and upgrading of biomass pyrolysis
oils" in Ref. (1), pp. 5-20.
KOVAC, R. (1989) "Liquid biofuels production by an entrained
pyrolysis process" in Ref. (4).
DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Production of primary oils
in a vortex reactor" in Ref. (3), pp. 31-40.
DIEBOLD, J.P. and POWER, A.J. (1988) "Engineering aspects of the
vortex reactor to produce primary pyrolysis oil vapors for use in
resins and adhesives" in Ref. (2), pp. 609-628.
SCAHILL, J.W. and DIEBOLD, J.P. (1988) "Adaptation of the SERI
vortex reactor for RDF pyrolysis" in Ref. (1), pp. 237-246.
DIEBOLD, J.P., EVANS, R.J., and SCAHILL, J.W. (1989) "Fast
pyrolysis of RDF to produce fuel oils, char, and a metal-rich byproduct" in Ref. (4).
REED, T.B. (1988) "Principles and operation of a novel "pyrolysis
mill" in Ref. (1), pp.247-258.
REED, T.B. (1988) "Contact pyrolysis in a pyrolysis mill" in Ref.
(2), pp. 192-202.
ELLIOTT, D.C. (1988) "Relation of reaction time and temperature to
chemical composition of pyrolysis oils" in Ref. (3), pp. 55-65.
BAKER, E.G. and ELLIOTT, D.C. (1988) "Catalytic hydrognation of
biomass-derived oils" in Ref. (3), pp. 228-240.
BAKER, E.G. and ELLIOTT, D.C. (1988) "Catalytic upgrading of
biomass pyrolysis oils" in Ref. (2), pp. 883-895.
ELLIOTT, D.C. and BAKER, E.G. (1988) "Catalytic hydrotreating
processes for upgrading biocrude oils" in Ref. (1), pp. 45-56.
EVANS, R.J. and MILNE, T.A. (1988) "Molecular-beam massspectrometric studies of wood vapor and model compounds over an HZSM-5 catalyst" in Ref. (3), pp. 311-327.
EVANS, R.J., FILLEY, J., and MILNE, T.A. (1988) "Molecular beam
mass spectrometric studies of H-ZSM-5 activity during wood
pyrolysis product conversion" in Ref. (1), pp. 33-43.
MILNE, T.A., EVANS, R.J., and FILLEY, J. (1988) "Molecular beam
mass spectrometric studies of H-ZSM-5 activity during wood
pyrolysis product conversion" in Ref. (3), pp. 910-926.
DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Biomass to gasoline:
upgrading pyrolysis vapors to aromatic gasoline with zeolite
catalysts at atmospheric pressure" in Ref. (3), pp. 264-276.
DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Conversion of wood to
aromatic gasoline with zeolite catalysts", Energy Propress. Vol.
8, No.l, 59-65.
SCAHILL, J.W., DIEBOLD, J.P., and POWER, A.J. (1988) "Engineering
aspects of upgrading pyrolysis oil using zeolites" in Ref.(2), pp.
927-940.
DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Zeolite catalysts for
producing hydrocarbon fuels from biomass" in Ref. (1), pp. 21-32.
WAN, E.I. and FRASER, M.D. (1988) "Economic assessment of
producing liquid transportation fuels from biomass" in Ref. (1) ,
pp. 111-121.
GRABOSKI, M.S. (1989) Private communication with J.P. Diebold on
April 21.
AYRES, W. (1987) "Commercial application of wood derived oil",
Enerpv Propress. Vol.7, No. 2, 77-79.
27
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(42)
AYRES, W. (1989) Private communication with J.P. Diebold on April

21.
ANON,(1989) Commerce Business Daily. Jan. 6.
28
OVERVIEW OF THERMOCHEMICAL CONVERSION OF
BIOMASS IN CANADA
R.D. HAYES
Bioenergy Research and Development
Technology Branch
Energy, Mines and Resources Canada
Ottawa, Canada K1A 0E4
Summa ry
Thermochemical conversion of biomass in Canada has undergone a
considerable transformation in approach and expectations over the
last
ten
years.
A decade
ago, the promise
of
early
commercialization quickly evaporated and was replaced by a more
realistic assessment that the potential would likely not materialize
except over the longer term. More recently this outlook has been
modified slightly in the wake of unanticipated research progress and
the surfacing of some special near term market applications.
1.
INTRODUCTION AND HISTORY
During the late 1970's and early 80's there was a short-lived
perception of panic in energy security accompanied by exaggerated claims
of technical readiness of thermochemical conversion applications. Several
premature commercial demonstrations in the U.S.A. of pyrolysis and
gasification failed technically and financially.
Governments and
investors became understandably cautious therefore when further approached
by technology vendors.
American communities that once considered
gasification and pyrolysis of municipal solid wastes as environmentally
attractive alternatives to relieve pressure on decreased availability of
landfill sites for urban refuse, turned their attention to mass
incineration and refuse derived fuel (RDF) combustion applications.
Though environmentally less attractive in terms of emissions, combustion
offered less technical and financial risk than did the more exotic
thermochemical conversion options.
Canada was somewhat behind the U.S.A., having felt less apparent
impact from the energy supply disruptions of 1973 and 1979. In those days
also there was less pressure to find alternatives to landfilling of wastes
than there was in many U.S. cities, or, as there is in some Canadian
cities today.
Canadian thermochemical conversion research, then in its
infancy, therefore focussed its effort on the long term.
It assumed a
lengthy timeframe to mature innovative process developments. In theory,
this new breed of technologies would presumably become technically ready
for the 1990's or 2 1 s t century, in a world eager to embrace bioenergy,
particularly from wood, as a sustainable and environmentally attractive
energy resource.
29
The ultimate vision of some researchers was to refine biomass in a
manner analogous to petroleum that would eventually lead to alternative
transportation
fuels, preferably high quality gasoline, plus a host of
high value byproduct specialty chemicals. As the bubble burst on high
world oil prices, the sense of urgency to accelerate RSD diminished.
Admittedly, severe federal budget reductions for energy RSD also had its
predictable effect on the "sense of urgency".
Except for one major
project, gasification research in Canada all but disappeared by 1984. The
pyrolysis/liquefaction research community collectively agreed to back off
from upgrading studies, and concentrated instead on perfecting their
processes for primary oil production.
Over the past decade, the science has become better understood and
technical advances have actually surpassed earlier expectations.
Some
laboratories have begun to re-activate their upgrading research.
Scientists and engineers have broadened the scope of experimental
conditions and gained a much deeper understanding of the chemical
transformations of complex feedstocks to multiple products.
A new vision of conversion and product opportunities has begun to
reshape our view of the timeframe for commercialization.
The long term
perspective remains paramount, and perhaps even more so since the global
call for environmentally sustainable economic development by the
Brundtland Commission report, "Our Common Future"l
In addition to the long-term vision, technical progress in the
identification of several high valued specialty chemicale in wood
pyrolysis oil may be the market hook (albeit a small market) required to
help finance the high costs of staged scale-up from laboratory, process
development unit, pilot plant, small commercial demonstration and
eventually to full-scale commercial reality.
Several other near term opportunities
have also
surfaced.
Environmental pressures have influenced the trial experimentation of
biomass pyrolysis liquefaction technologies on non-woody feedstocks such
as used tires, petroleum sludges, sewage sludge, and, once again,
municipal solid wastes. Impending environmental regulatory controls
on
waste incineration and increasing costs for landfilling may create a
climate more ideal for fully contained emission-free thermochemical
processes.
Researchers, industry and government have all become more creative in
building a diversified, yet comprehensive, portfolio of thermochemical
conversion opportunities for the commercial world.
Though nothing
thoroughly new has emerged, the past ten years have seen an evolution from
a subject of technical curiosity to one of concerted effort toward cost
effective products for the marketplace, some sooner than others.
2.
PROSPECTIVE APPLICATIONS OF TECHNOLOGY (PAT)
A broader diversified portfolio, as referred to above, presents a

major challenge to the RSD planner. Added to this challenge is the everpresent restraints in government RSD funding.
This challenge has
necessitated a major overhaul in organizing RSD priorities in the context
of assessing a balance in both near and long term commercialization and
environmental opportunities and needs.
30
The commercialization process for a new technology as defined within
the Energy Diversity Division of Energy Mines & Resources Canada includes
everything germane including opportunity identification, the actual
research, development, technical evaluation, and demonstration as well as
the determination of current and projected economic feasibilities, current
and future market, expected timeframes for commercialization, standards
development, and many other factors affecting market introduction and pene
tration. Once these elements have been assessed and analyzed for the
various feedstock/conversion' technology pathways, priorities could be estab
lished with respect to activities that government can, should, or must, do
and those that government should not, or cannot afford, to support.
The first step in the process is to organize the four basic elements
of a technology by resource (eg. biomass, wastes, peat etc.), process(es),
product(s), and market application.
The particular feedstock combined
with specific conversion processes and a particular market application of
products result in what we define as a Prospective
Application
of
Technology or PAT.
The picture can become rather complex especially
when considering combinations of thermochemical, biochemical and
fractionation technologies that might be otherwise overlooked during
conventional analysis.
In order to illustrate many of the various
combinations pictorially, we have constructed a 'PAT map.'
Figure 1 is a simplified version of a 'PAT map' for thermochemical
technologies.
One can visualize perhaps one hundred or more probable
combinations of resources, processes, products, and market applications.
The product possibilities alone include a vast array of oils, gases,
chars, carbon black, sugars, fermentation products, high value specialty
chemicals, medium value commodity chemicals, olefins, gasoline and
gasoline components, diesel fuel, and other materials. Figure 2 is a more
general PAT map encompasing most bioenergy technologies.
FIGURE I
Prospective A pplications of Technology

< Thermochemical)
IzBfffla.,!!
ition
Thermochemical
Processes;
"
Thermochemie al
and/or
biochemical
Processes
pyrolysis
hydrotreating
catalytic
solvent pressurized
partial oxidation
oxygen gasification
soivoiyss
hydrothermolysis
product separation
etc.
y Ian s
lionln
attractive*/
votatile
TvTvl
Various combinations of thermochemical,
biochemical, ex tract lon/fract Jona tion and
derlvatlzatlon processes
CMA
oletins
"*
diesel /urt
BTX
phenolic denVaoVes
synthesis gas
carbon
black
acetic acid
gaso/ine components
'llavoursl aromas
charcoal
aahevelbnders
lm, mol. m lignns
31
Figure I I
PROSPECTIVE APPLICATIONS OF
| MATERIALS
TECHNOLOGY
PREPARATION]
JPRETREATMENT
FRACTIONATION
THERMOCHEMICAL
COMBUSTION
GASIFICATION
PYROLYSIS
CATALYSIS
HYDROTHERMOLYSIS
SOLVOLVSIS. ETC...
EXTRACTIVES
VARIOUS COMBINATIONS OF BIOCHEMICAL

THERMOCHEMICAL. FRACTIONATION, EXTRACTION
AND D ERIVATIZATION PROCESSES
THERMOCHEM-UPGRAOING
FUEL OIL GAS CMA ACETIC ACID

RESINS FIBERS SUGAR ENZYMES
OLEFINS BTX METHANE CARBON BLACK GASOLINE AD D ITIVES OLIGOMERS
FURFURAL D IESEL FUEL SYNTHESIS GAS
HEAT ALCOHOLS
A
D HESIVES'BIN
D ERS
PHENOLIC D ERIVATIVES CHARCOAL GASOLINE FLAVOURS/AROMAS
LOW MOL WT. LIGNINS
MANY FERMENTATION PROD UCTS ETC.
RESIDENTIAL. COMMERCIAL INSTITUTIONAL AND IND USTRIAL BLOGS.. PULP AND PAPER , AGRICULTURE &
FISHERIES. UTILITIES. FOOD AND
BEVERAGE. FOREST PROD UCTS IND USTRY. NORTHERN COMMUNITIES
TRANSPORTATION. INTERNATIONAL AID
AND
EXPORT. REFINERIES
HEAVY IND USTRY. BRICK. LIME AND CEMENT ETC.
Our view of the world of thermochemical conversion of biomass is no

longer limited to merely the pyrolysis or gasification of wood to heating
oil and gas. Thermochemical conversion is not treated in isolation from
biochemical, fractionation or derivatization processes. Even considering
a single process technology, the variation in process conditions,
catalysts, reactants, or feedstocks can impact the range and output of
possible product combinations.
The second step will be to select a handful of promising PA Ts, and
perform an analysis of expected technical progress, economic feasibility,
market penetration, and timeframe for commercialization. In theory, this
should provide government (and industry) with a rationale for desirable
government (and industry) activities in those PA T's such as research,
development, demonstration, detailed engineering, market studies, economic
and financial analysis, information dissemination, standards formulation,
etc.
Some of the so-called 'thermochemical PA Ts' that are not typically
represented at thermochemical conversion of biomass conferences, but which
are included or planned for in Energy, Mines and Resources' Bioenergy R&D
program planning include the following:
thermochemical treatment of plant oils (oilseed, tall oil) to produce
high cetane diesel fuel.
biochemical and thermochemical derived lignin that is thermally or
thermochemically treated with or without catalysts to produce gasoline
and other chemicals.
32
c
product derivation of thermochemical and biochemical lignins (eg.

resins, adhesives, cement dispersants).
thermochemical treatment of the steam fractionated cellulose component
of biomass.
direct steam (thermal) production of adhesives with a fibre byproduct
suitable for molding, pelletizing, or thermochemical or biochemical
processing.
calcium magnesium acetate (CMA) production a3 a road de-icer from
aqueous effluents (ie. dilute acetic acid) of pyrolysis and biochemical
processes.
investigation of wheat chaff as a thermo- or biochemical conversion
feedstock.
methanation of pyrolysis aqueous effluents.
separation of short and long fibers of hardwoods where pulp would be
processed from the long fibers and fuels processed biochemically or
thermochemically from the lower value short fibers.
source separated and/or prescreened, or raw, municipal wastes that
undergo thermochemical or biochemical conversion with or without
pretreatment/fractionation.
3.
EMR's BIOENERRY DEVELOPMENT PROGRAM
Table 1 shows the historical trend in Canadian federal government

spending on bioenergy RSD including biomass production and conversion.
Table 2 is a breakdown of thermochemical R&D expenditures relative to
other conversion technology areas.
3.1
BRIEF REVIEW OF NON-THERMOC.HEMICAL R&D
The following is a cursory view of

technical areas other than thermochemical.
Canadian
R&D
activities
in
The combustion area's main focus of effort is the evaluation and

improvement of industrial and residential combusto! performance and
emissions.
Also included has been support to Environment Canada's
National Incinerator Test and Evaluation Program (NITEP) and the
development of standards for performance, safety and emissions of
residential wood burning appliances.
The biomass
handling/preparation area includes research in
biomass materials handling, storage, drying, beneficiation, and
preparation. This research is seen to provide necessary infrastructural
support for all biomass conversion processes, but more importantly, to
improve biomass fuel quality with objectives to improve biomass combustion
performance and to reduce emissions. Examples of developments include a
bin, silo and non-consolidating feeder system that regulates the
controlled and non-disrupted feeding of hog fuel and chips to burners, a
device to exclude frozen lumps of hog fuel and chips to burners, a
continuous moisture sensor to provide improved combustion control of
biomass of varying water content, and a low energy grinder to powder wood
suitable for suspension-fired boilers.
The biochemical area receives the largest allocation of funds, in
part due to increasing industrial leverage provided by cost-shared R&D.
Much of the impetus for this area comes from mid-term (1990's) competitive
potential to enter the transportation fuel market with biomass derived
33
Table
25
S/MILUONS
Federal Bioenergy R&D Funding

r^ , m
20
S-
IOBPsTjs man
82
83
84
85
86
Table
87
88
89
II
1988/89 Bioenergy R&D

Expenditure Forecast
35.4%
Combustion
Biomass
Handling/
Preparation
Thermo
chemical
Bio
chemical
Infor
mation
Tech/
Transfer
90
34
ethanol based blends and oxygenates and the longer term potential of neat
ethanol fuel along with value added byproducts. The program is divided
into a number of areas including enzymatic and acid hydrolysis of
lignocellulosics, steam and extrusion pretreatment
and biomass
fractionation, novel fermentation engineering, biotechnology of enzymes
and microorganisms,
anaerobic
digestion,
characterization
and
derivatization of lignin, and the development of non-ethanol byproduct
streams, among others.
The rate of achievements in this area over the
past four years rivals that in the thermochemical area.
The lure and
promise of biotechnology and the recent accelerated progress are likely
the major factors in attracting
industry participation in an area that
was viewed by our program as very long term as of only five or six years
ago.
3.2
CANADA'S MAINSTREAM BIOMASS THERMOCHEMICAL CONVERSION RSD
An approach has evolved in Canada whereby, unlike earlier efforts, a

whole range of products and reactants are now considered.
Products
include gases and oils of varying quality, sugar solutions in high yield,
chemicals (olefins, phenolics, as well as high value specialty chemicals),
gasoline
or
diesel
fuel,
and
higher
value
carbon
products.
Diversification of reactants include whole biomass, fractionated biomass
components, peat, and muncipal solid waste, including source-separated
wastes such as used tires. Another area of research is the treatment, and
especially, the conversion, of waste aqueous effluents from thermochemical
conversions into value-added co-products.
Left unprocessed, these
effluents would otherwise incur a cost for waste treatment.
3.2.1
GASIFICATION
Canadian developments in biomass gasification for the production of

low, medium and high energy gases have enjoyed world technical acclaim
over the past decade, but there has been a disappointing uptake by
Canadian industry. The cautious attitude of our industry appears to have
been due largely to premature and unsuccessful attempts in the US to
commercialize immature technologies during the latter '70s and early '80s.
A possible revival of interest in gasification technology applications
appears to be for replacing industrial boilers that use oil and for
municipal energy from waste projects.
The work to complete ongoing
projects will continue, although at a reduced level, and any impetus for
an expanded government program will likely wait for stronger industry
confidence, interest, and cost share. Application of Canadian technology
in developing countries may hold some promise.
Large scale (10 tonnes/hour) gasification technology, developed
through the Biosyn project offers a world leading technology in
pressurized, air or oxygen fed, fluidized-bed gasification that can be
adapted to the production of synthesis gas for methanol production or low
energy gas for other applications such as space heating, gas turbines or
industrial diesel engine operation.
Another portion of the gasification research funds is directed to the
development of a small scale gasifier that is designed to use wet wood and
produce a clean gas. The Heuristic gasifier is a two-stage reactor that,
in principle, operates similarly to a downdraft design. The first stage
is an updraft gasifier where producer gas and condensible vapours (tars)
35
are routed through a hot char bed below. The tars are to be cracked in
the second stage.
The project now underway is to modify the gasifier,
optimize the operating parameters, and enhance cracking in the second
stage.
3.2.2
LIOUEFAC.TION/PYROLYSIS
In 1985, research in the direct liquefaction of biomass was expected

to wind down because the rapid commercialization that was expected to
occur in the early '8 0s did not materialize. The plan was to conclude as
much of the work as possible, revert to lower cost basic research, and
pursue a strategy of chemicals from liquefaction.
Then in 1986 there
appeared to be a turnaround in commercial interest.
Unprecedented
technical achievements started to renew aspirations and industry interest
in exploiting selected market niches for pyrolysis products.
The
following is a brief review of current projects.
McGill University
Over the past several years researchers W.J.M. Douglas and D.G.
Cooper at McGill University have been studying an
interesting
thermochemical approach to wood liquefaction using aqueous hydrogen iodide
at fairly mild conditions of pressure and temperature (125C) . Still far
from certain is the exact nature of the liquid products and the
techno-economic practicality of hydrogen iodide recovery and recycle. On
the positive side, in addition to the low severity conditions of reaction,
the process removes about 80% of the oxygen in the wood, and the char
yield is low.
University of Toronto
D.G.B. Boocock and co-workers at the University of Toronto have
undertaken the investigation of steam pyrolysis or hydrothermolysis of
wood. Based on their earlier work, they recently designed and constructed
a laboratory scale cascade autoclave which can accommodate up to 100 g of
wood chips or 170 g of a single larger piece (3.8 cm reactor I.D., 600ml
volume).
It is rated at 24.1 MPa (3500 psi.) at 350C allowing for 7.6
MPa (1100 psi) gas overpressure above the vapour pressure of water at that
temperature. Replicated results indicate that oil yield increases with
increased chip size. Dry product oil yields are high (up to 50%) with no
solids contamination, and the oil is easily separable from the aqueous
phase.
Coupled with an upgrading process, this technology may someday
lend itself well to commercialization.
In addition to their process development work, Professor Boocock's
group has contributed greatly to the basic understanding of biomass
liquefaction, especially through their scanning electron microscopic
studies.
The group at the University of Toronto is also performing
upgrading studies through the catalytic hydrotreatment of model compounds.
Of potential interest too is their discovery in 1984 that a particular
clone of hybrid poplar yielded 6% phenol.
This discovery raises the
prospect of matching processes more closely with specific feedstocks in
the interest of optimizing a particular product slate. Efforts are now
beginning to genetically engineer trees that are designed for specific
process/product applications.
36
Universit de Sherbrooke
E. Chornet, R.P. Overend and co-workers at the Universit de
Sherbrooke have been working on a liquefaction process in pressurized
solvent for some years. Their approach involves an overall integration of
biomass pretreatment, fractionation, acid processing, thermochemical and
biochemical treatment.
Funding for research at Sherbrooke in the areas of peat and wood
conversion is provided by a number of sources, including Energy, Mines &
Resources.
The program there involves a comprehensive variety of
fundamental studies, product engineering and technology development at
laboratory and pilot plant levels.
Examples of approaches under
investigation include a thermo-mechanical-chemical treatment to
fractionate and liquefy biomass including steam treatment, thermocatalytic
conversion of fractionated products such as lignin to monomers, ethylene
glycol solvolysis/liquefaction, acid/thermal/shear treatment of biomass
and cellulose, and a variety of biochemical investigations in combination
with thermochemical techniques. In association with other laboratories,
the chemical engineering laboratory of Professor Chornet is especially
well equipped for analytical characterization of products derived from
their various reaction systems.
University of Waterloo
D.S. Scott, J. Piskorz, D. Radlein and co-workers at the University
of Waterloo are well known for their fluidized bed flash pyrolysis
development, also known as the WFPP (Waterloo Fast Pyrolysis Process). A
number of companies and the European Economic Community have indicated
their interest in collaborating with the Waterloo group.
The WFPP
actually includes five process options as follows :
1. Direct thermal processing at 450-550C, atmospheric pressure, and
about 500 ms vapour residence time. They report high liquid yield
(80% including water, based on input wood) that is a suitable fuel for
conventional boilers.
2. By varying the process conditions and adopting a mild sulphuric acid
pretreatment of wood followed by fluidized bed thermopyrolysis, the
WFPP produces a high yield and concentration of anhydro-sugars rather
than oil products. Their reproducible yields of sugars from pure
cellulose are about 80% of theoretical in a concentrated form. One
can easily speculate whether this development could challenge some of
the equally exciting biochemical conversion methode of converting
lignocellulosics to fermentable sugars.
3. Waterloo's hydrogasification work has been technically highly
successful, resulting in 75% conversion of wood carbon to methane via
pyrolysis over a nickel-alumina catalyst with hydrogen at about 550C
and 440 ms vapour residence time.
4. Under current investigation is a fourth process option of producing
polyolefins from wood in a catalyzed reaction. Apart from the use of
catalysts, the process equipment and operating conditions are very
similar for all of the above process options.
37
5. The Waterloo group is also performing upgrading research by
catalyticly hydrotreating pyrolysis oil fractions, especially lignin,
in a continuous pressurized reactor.
University of Western Ontario
Although not currently funded by Energy, Mines & Resources, M.
Bergougnou, R. Graham and co-workers have developed an Ultra-Rapid
Pyrolysis or Ultrapyrolysis process at the University of Western Ontario.
Although there are similarities in this work and the research at the
University of Waterloo, there are important differences.
Whereas the
Waterloo process utilizes fluidized-bed heat transfer. Professor
Bergougnou employees a very rapid (30ms) mixing and heat transfer in a
vortical contactor or vortactor followed by a plug-flow entrained-bed down
flow reactor (50-900ms) and quenching (30ms) with cryogenic nitrogen in a
cryovortactor.
Dissimilar to the Waterloo process are the process
conditions (650-1000C, 50-900 ms residence time), and the main product at
these temperatures is gas rather than liquid. Since pyrolytic fuel gas
production has not been of high priority in Canada's bioenergy RSD
strategy, the current objective, in collaboration with Ensyn Engineering,
(see below) is the production of chemicals and, in particular olefins.
It is interesting to note here that the Universities of Waterloo and
Western Ontario conducted an extensive data comparison from each of their
reactor systems. Using selected data from both groups at around 500 ms
residence time, liquid and gas production data were plotted vs
temperature.
The temperature ranges were as follows:
Waterloo at
400-750C, and Western Ontario at 650-900C.
With combined data for
each of the gas yield vs temperature and liquid yield vs temperature
respectively there was remarkable agreement of data in overlapping
regions. A simple first order kinetic model is able to describe the oil
yield over the temperature range of both experiments.
Ensyn Engineering
Ensyn Engineering is a recently formed company whose principal
investigator, R. Graham has scaled up the University of Western Ontario
Ultrapyrolysis reactor by a factor of 20 to a 5-10 kg/hr capacity RTP
(Rapid Thermal Processor).
The reactor is designed to accept any
carbonaceous feed (solid, liquid, or gas) by injecting it into a turbulent
cloud of hot solids. The mixed feed plus solids is carried through a
tubular transport reactor to an inerial separator where vapour products
are removed. This project is co-sponsored by the private sector.
Work planned for 1989 involves thermal cracking and catalytic
treatment of pyrolysis oils and various lignin preparations including
steam exploded biomass derived lignin.
Laval University
Multi-stage vacuum pyrolysis was developed by C. Roy and co-workers,
initially at the Universit de Sherbrooke and, currently, at the
Universit Laval. The technology consists of a 40 kg/hr multiple hearth
vacuum pyrolysis process development unit located near the Universit
Laval. There is aleo an industrial cost-shared pilot demonstration of a
38
single-stage process at St-Amable, Quebec.
200 kg/hr and is designed for used tires.
The unit has a capacity of
Although the multiple hearth concept suffers from low heat transfer
relative to other pyrolysis processes, and, at first glance, is capital
cost intensive, it has a number of redeeming features that show commercial
promise as follows:
1. A high yield of pyrolysis oil (50% based on wood).
2. The production of co-product carboxylic acids and high value
chemicals.
3. Reactive charcoal at 25% of input wood.
4. The aqueous phase is recovered separately as vapour or liquid as an
integral part of the process leaving a low water content water-free
pyrolysis oil ready for upgrading.
5. The multiple hearth performs a product fractionation function that
could reduce extraction costs of high value chemicals.
Centralized Analysis
One final work of interest in Canada is a Centralized Analysis project
at B.C. Research. In 1984, a trial project was set-up whereby different
Canadian bio-oils could be compared in a standard manner.
The project
embraced a three-pronged approach. Under the guidance of J. Howard and J.
McKinley, B.C. Research performed and/or coordinated the centralized
analyses of optimized oils produced by each researcher. Individual
researchers also did some of their own analyses to obtain immediate
experimental feedback.
The second prong of the approach
provided with a standard wood sample,
Canada Corp.
The idea was that when
somewhat optimized, the researcher would
sample to the centralized analysis team.
was that all researchers were

Populus deltoides, by Forintek
each process development became
submit oil from the standard wood
The third prong was a computer communications network link called

CoSy, through the University of Guelph, to provide fast communication of
analytical data. It was also used to encourage multilateral and bilateral
collaboration and problem solving.
The centralized analysis project has entered Phase II. Learning from
the successes and pitfalls of the first two and one half years, the scope
of this project has changed somewhat. Phase II has two major tasks.
Task 1 is a set of analytical techniques along the same lines as the
initial project except the methods that were considered to be less
interesting to the entire group are not included. The basic analyses of
task 1 include the following:
-
Elemental Analysis
Water Content
Density
Carboxylic Acids
Gas Liquid Chromatography
Carbon-13 NMR
Gel Permeation Chromatography
39
Task 2 consists largely of special analytical projects to meet the
special needs of individual researchers, Energy, Mines and Resources
Bioenergy Development Program or groups of thermochemical conversion
researchers that may arise over the next two years.
4.
INTERNATIONAL VIEW - IEA
Under the International Energy Agency, eleven countries signed a three

year Bioenergy Agreement on Cooperative R&D, effective January 1, 1986 to
December 31, 1988.
This Agreement has since been extended by another
three years. Canada, USA, Sweden and Finland agreed to collaborate on a
project entitled Direct Biomass Liquefaction (DBL). A Working Group of
engineers
and
other
specialists
are
preparing
a
detailed
technical-economic assessment (TEA) at commercial size scale-up and
operation
of
the
most
promising
high
and
low
pressure
pyrolysis/liquefaction processes.
Both primary oil production and
upgrading are considered in the TEA.
The upgrading work on Canadian
atmospheric and vacuum pyrolysis oils has been conducted by D. Elliot at
Battelle Pacific Northwest Laboratories.
Yields of products in the
gasoline boiling range have so far reached 35% of primary oil by
hydrotreating. The Working Group is attempting two types of analyses, one
based on current state of the art and the second based on projected
improvements and developments in the technologies.
ACKNOWLEDGEMENTS
The author wishes to acknowledge the various researchers in North
America without whose ideas, open discussion, and dedication to research
in thermochemical conversion of biomass, this paper would not have been
possible.
Each has contributed to this paper, either directly or
indirectly.
The following list is not complete, but includes the
principal investigators in Canadian laboratories and other notable
international collaborators.
In alphabetical order, many thanks to
Narendra Bakhshi, Dave Beckman, Dave Boocock, Jean Bouchard, Maurice
Bergougnou, Michel Bertrand, Esteban Chornet, Maurice Charron, Helena
Chum, Jim Diebold, Allan Dolenko, Murray Douglas, Guy Drouin, Dick Eager,
Doug Elliot, Bob Graham, guy Gravel, Michele Heitz, Ed Hogan, John Howard,
Serge Kaliaguine, Bjrn Kjellstrom, Bill Lowe, Tom Milne, Hugh Menard, Jim
McKinley, Ralph Overend, Hooshang Pakdel, Jim Pepper, Jan Piskorz, Desmond
Radlein, Tom Reed, Joe Robert, Christian Roy, Tom Tidwell, Don Scott, and
their many colleagues, staff, and students.
REFERENCES
This paper contains technical contributions including progress reports
from all the Canadian and other workers mentioned here. The reader is
referred to these individuals or their published papers as primary
references.
1.
Brundtland, Gro Harlem. 1987 "Our Common Future".

on Environment and Development.
World Commission
40
RAPPORTEURS REPORT ON SESSION I

C.H. NELS
Federal Office for the Environment, Berlin
The following report covers the first session of the conference.

The papers delivered during this session dealt mainly with :
Activities and results of the demonstration program of the Commission
in the areas of gasification and pyrolysis as well as European
activities planned for the future.
International research and development in this area presented by the
United States, Canada and Japan.
Because of time constraints follow-up discussion was limited to the EC
papers. Topics included details for the forthcoming planned EC research
program, how technologies already proven in laboratory and bench scale could
be transferred/tested in the field, how many test plants currently exist in
the EC and when results will be ready for general use. Special interest was
given to problems of developing countries. Issues included how demands of
developing countries could be taken into consideration in future RSD
programs and whether direct or indirect help could be given by the EC to
strengthen their own efforts in this area. Environmentally related issues
were also discussed dealing with critical emissions caused by extended
agricultural production of biomass, its thermal or chemical conversion and
finally the question of its potential for use as a fuel or raw material.
The papers as well as the subsequent discussion led to the following
conclusions :
Any future research commitment should have long term orientation.
Since funding resources are limited research should be directed toward
those types of biomass "crops" which are most widely applicable.
Alongside biomass research there should always be an environmental
impact assessment.
Because of the global nature of the problem there are numerous biomass
research programs underway internationally. To avoid duplication and
enhance information transfer more conferences such as this one should
be organized to coordinate international efforts.
Efforts in international cooperation should begin at the earliest
stage while planning research programs such as that currently underway
in the EC.
Such exchanges also provide the missing link to developing countries
giving them vital information; the importance of such exchanges should
be recognized.
SESSION II
43
PRETREATMENT AND CHARACTERIZATION OF FEEDSTOCKS
C MITCHELL and A V BRIDGWATER
Forestry Department
Chemical Engineering Department
Aberdeen University
Aston University
Aberdeen AB9 2UD
Birmingham B4 7ET
UK
UK
SUMMARY
Feedstocks generally considered for thermochemical conversion are wood and wood
waste, energy crops, agricultural waste and refuse. The main technical criteria for
suitability for thermochemical processing is low moisture content, and ash content and
characteristics. The main economic criteria are cost which includes production,
collection and transport, and quantity which includes availability. Wood will be
available from processing residues, unmanaged woodlands, conventional forestry and
short rotation forest biomass plantations. Harvesting, processing and transport
systems for delivering wood fuel either already exist or are under development.
Delivered fuel costs will be between 28 - 36/dt from conventional forestry and in the
order of 41/dt from short rotation.
Agricultural wastes, such as cereal straw, can be delivered to the end-user for 22/dryt.
Domestic and commercial refuse is widely available and can attract disposal credits of
10 - 20/wet t which has a significant effect on the conversion economics.
INTRODUCTION
Feedstocks generally considered for thermochemical conversion are wood and wood
waste, energy crops such as short rotation forestry and sweet sorghum, agricultural waste and
refuse (1). The main technical criteria for suitability for thermochemical processing are low
moisture content, and ash content and characteristics. The main economic criteria are cost
which includes production, collection and transport, and quantity which includes availability.
There is also the question of competing uses such as pulp and board manufacture, combustion,
recycling or material recovery rather than energy recovery.
2
2.1
FEEDSTOC
K S
Wood
Wood will be potentially available as a feedstock from residues generated within the
wood processing industries, presently unmanaged woodland, conventional forestry and from
plantations specifically grown to produce raw material for the biomass industries.
Processing Residues
Residues are generated within the forest products industry itself. Processing residues
are produced primarily in sawmills; these consist of slabs and blocks of wood, chips and
sawdust. However, with the increasing demand for raw material in the pulp and board mills
much of these residues go to these industries and are therefore unlikely to be available in large
quantities to the energy industry.
Unmanaged Woodland
There are several million hectares of woodland within Europe which is currently not
managed and which could be brought into production for biomass. In France and Italy alone
there are some 5 million hectares of overmature coppice. The maquis systems in the
mediterranean region and several other categories of natural vegetation offer good prospects to
be brought into management for biomass production (2). In the UK, the potential for
production of fuelwood from presently unmanaged woodlands is around 0.15 million wet t/y
(3).
44
Conventional Forestry
Conventional forestry practice gives several opportunities for harvesting wood for fuel.
Firstly, under current harvesting practice only the merchantable stemwood is removed from the
forest. The tops and branches, roots and stumps are left in the forest. The roots and stumps
can be harvested but it is a costly operation and there are potentially severe environmental
problems which limit their use. However, the tops and branches, so-called forest residues are
available for harvest. Secondly, early thinnings can be harvested using whole tree harvesting
techniques. A third opportunity lies in adapting harvesting systems to remove both the
stemwood and the "energy component" at the same time. These integrated harvesting systems
are attracting a great deal of interest world-wide because the overall harvesting system costs are
reduced.
Modified conventional forestry management systems involve planting trees closer
together initially, taking heavy early thinnings using whole tree harvesting techniques, and
using integrated harvesting systems for later thinnings and clearfell.
For the UK alone by the year 2020 the total annual sustainable production of fuelwood
from conventional forestry could amount to some 4.8 million wet tonnes. In the longer term
modified conventional forestry could provide an additional 8 million wet tonnes per year (4).
Short Rotation Forest Biomass Plantations
Woody biomass can be purpose grown for energy in short rotation coppice biomass
plantations. These are intensively cultivated plantations using fast growing broadleaved trees
which coppice readily and are harvested every 3 to 5 years. The main species used are from
the genera Eucalyptus, Populus (Poplars) and Salix (Willows). Growth rates are high
giving productivities of around 10 to 15 dry tonnes per hectare and year (dt/ha/y) in commercial
operations. Coppice crops need to be grown on good fertile soils. Within Europe the
agricultural surpluses problem coupled with the revision of the CAP is leading to land being set
aside from agricultural production. Such land is well placed for coppice plantations. Of the 40
million hectares of land coming out of production in the CEC some 5 million hectares has been
conjectured to be available for energy plantations (2). In the UK, it has been estimated that if
0.82 million hectares of land currently in agricultural production were to change to short
rotation forestry then this would give an annual production of some 2.72 million wet tonnes
(4).
2.1.1 Harvesting of Wood Fuel
Conventional Forestry
The actual harvesting system chosen for conventional forestry is heavily dependent on
the crop, species, size, terrain and the requirements of the end-user. Most current harvesting
systems operating in Europe are designed to supply raw material to the pulp, board industries
and sawmills. Harvesting systems can be categorised into one and two pass systems. One
pass systems are applicable to whole tree operations in either integrated or whole tree
comminution, and two pass systems to residue collection and comminution following
conventional methods for harvesting the stem wood. The harvesting options available are
shown in Figure 1.
Two pass residue harvesting systems are perhaps those that are the most appropriate
with short wood harvesting systems. The residues can either be chipped in the stand with
mobile machines (terrain chipping) or the residues are collected and extracted to a central point
for chipping (landing chipping). Terrain chipping is appropriate to the dryer load bearing
mineral soils and landing chipping to the wetter organic soils.
Yields of fuel chips from terrain chipping will reflect the predominance of pine species
and are likely to be in the lower end of the range 50-100 wet tonnes per hectare (wt/ha).
Production costs for terrain chipping are in the range of 10 - 15/wet L
Yields of fuel chips from landing chipping systems reflect the higher potential of spruce
crops and are likely to be in the lower half of a range from 100 - 200 wet tonnes per hectare.
Production costs for extraction of residues to landing are estimated to be in the region of 3.00/
wet t and chipping costs in the region of 7.00/wet t
Whole tree comminution systems are appropriate to smaller tree sizes, either in early
thinnings or premature clearfell situations where the tree stem size is insufficient to warrant
45
conventional utilization or in clearance or cleaning operations in hardwoods. Chipping can take
place either at landing or at the stump (terrain chipping) and the choice of systems will be a
factor primarily of the suitability of the terrain and extraction distance.
In landing chipping systems the whole trees are extracted to landing. In the smaller
tree sizes appropriate to whole tree chipping, the use of forwarder extraction of whole trees or
tree sections, is favoured to reduce extraction costs. Whole tree chipping at landing requires the
use of larger chippers with infeeds capable of handling and feeding the whole tree by grapple.
Terrain chipping can be used where the ground conditions permit. Small scale
equipment such as small tractor mounted chippers can be used. A self propelled chipper and an
infeed at the front fed by a grapple crane can be used in line thinning operations with the chips
blown over the chipper into a chip bin at the rear.
Yields of fuel chips from whole tree comminution systems has been found to be in the
region of an additional 50 -100% expressed as a percentage of stem wood. Production costs
for fuel chips from whole tree comminution systems will vary on the scale of the operation,
and as for integrated systems, on the tree size and the terrain. Landing chipping costs will be
around 4.80/ wet t and 5.60/ wet t for terrain chipping.
In integrated harvesting systems the whole tree is extracted to landing for processing
and product separation. Landing processing, involving delimbing and crosscutting, can be a
manual system with the use of chain saws, or be partly or fully mechanised, the availability of
equipment and landing size being the factors taken into consideration when deciding the
method to be adopted. The residue material on the landing can be chipped in a continuous (hot)
system closely following the processing, or, can be allowed to accumulate on the landing for
chipping in a separate process (a cold system). The chipping equipment used will be primarily
decided by the scale of operation, the use of hand fed tractor mounted chippers will be
appropriate to only the smaller operations. Given a sufficient scale of operation, the use of
trailer mounted chippers feeding with a grapple crane will give higher outputs, particularly in
working a cold system where there are no limiting factors in the processing line. The chipped
material can be accumulated on the landing for later loading on to road transport, or, more
commonly the chips can be blown directly into containers or lorry trailers for road transport.
Yield of fuel chips from integrated harvesting systems has been found to be in the
region of an additional 30% expressed as a percentage of stem wood. Production costs for fuel
chips from integrated harvesting operations vary considerably with tree size, terrain and the
harvesting system used. On the assumption that integrated systems can produce the traditional
assortments as efficiently as comparable shortwood systems, the cost of fuel chips will reflect
the "free ride" that they get to landing. The cost of production then amounts to the chipping
element which can be as low as 5.10/wet tonne.
Short rotation forestry
Current harvesting technology for short rotation crops is limited. The two coppice
harvesters currently working are both prototypes; there are no machines commercially
available. The principle on which these machines work is for the coppice to be severed by
circular saw(s) and the cut coppice rods tied together in bundles before being ejected from the
machine. The Loughry coppice harvester produces 300 kg (wet) bundles, the Swedish
machine 2.5 wet tonne bundles. The rationale for this approach is to produce bundles which
can be left in the field to dry. Coppice willows and poplars are around 55% moisture content
(wet basis) at harvest. By stacking the bundles of cut material in the open or with a tarpaulin
cover there will be some natural drying. Once stored for 3 months or so the moisture content
will drop to around 40% and the bundles are then chipped.
2.1.2 Transport of Wood Fuel
The transport system of the raw material to the conversion plant is of utmost
importance. In many respects it is no different from any other wood delivery system to the pulp
and board industries which are designed to handle chips. In addition, delivery and reception
systems have been developed in Sweden for handling wood fuels to the mill and district
heating plants (5).
Converted pulp wagons, containers, tippers and curtainsiders can all be used for
transporting wood fuel. Converted pulp wagons show the most potential for use in the present
UK situation ie with a small wood fuel market and existing road transport legislation. These
46
allow self loading and unloading, a wide range of available loads and the ability to revert to
conventional pulp haulage.
Container systems are used in the UK for several commercial operations. Tippers and
curtainsiders showed potential for use in the future when demand for industrial fuelwood will
be high allowing full utilisation of independent loaders. It is not feasible to use lorry transport
of whole trees and forest residues over long distances without compaction equipment.
Transport costs amount to some 0.07/wet tonne/km.
2.1.3 Storage of Wood Fuel
Storage of wood fuel will be necessary to bridge the gap between supply and demand
with due allowance made for the time required for drying and pretreatment. The storage can be
done in the open, under cover to protect it from rain or an enclosed space such as silos and live
bottomed bins which have to be linked to the gasifier feeding system. The type of storage is
strongly influenced by scale of operation and climatic factors. The most common type of wood
fuel is chipped wood.
If storage is required then it has to be carefully considered. Whole tree chips, due to
their high moisture content and foliage content, decompose rapidly (1 - 5% per month) during
storage. Such materials also present a fire risk because of heating during decomposition. A
further problem associated with the storage of wood fuels in enclosed spaces is the
development of microfungi the spores of which represent a serious health hazard (6). From
experimental experience, drying during storage will give a moisture change from a delivered
55% to an outgoing 40%. Costs of storage have been calculated to be of the order of 5/wet
tonne (7) (Table 1).
2.1.4 Drying of Wood Fuel
Flash pyrolysis requires a feedstock at <5% moisture content and gasification <15%
but there is an optimisation to be carried out between moisture content and conversion
efficiency. The actual moisture content required for the conversion process will therefore vary
somewhat between conversion facilities. Biomass as received will have a moisture content
typically in the range 50 - 60% (wet basis).
Passive drying during summer storage can reduce this to perhaps 30%. Active silo
drying can reduce the moisture content down to 12% (8). Drying can be accomplished either
by very simple means such as near ambient/solar drying or by waste heat flows or by
specifically designed dryers operating on solid or hydrocarbon fuels. The selection of the most
appropriate system depends on the location, climate, level of sophistication required and scale
of operations. Commercial dryers are available in many forms and sizes but the most common
are the rotary kilns and shallow fluidized bed dryers.
2.1.5 Costs of Supply of Wood Fuel
The costs of supply of wood for fuel have been examined for UK conditions (3, 9).
Short rotation coppice crops biomass can be grown on a four year cutting cycle, harvested,
stored, chipped and delivered to the end-user at a cost of 40.83/ dry t (Table 1) for a farmer
operated system. In such a system the farmer carries out all the operations to do with growing
and tending the crop and uses contractors to carry out the harvesting and chipping operations
much as he may use contractors for other specialist farming operations.
Calculation of the costs of harvesting wood for fuel from conventional forestry is not
so simple as there are are conventional forest products produced along with the fuelwood
assortment. The costs of supply of wood fuel from forestry and the contribution of the
elements in the chain are illustrated for a number of options in Figure 1 and for the optimal
systems in Table 1. Delivered costs of wood fuel at 40% moisture content range from 28.17/
dry t for integrated harvesting systems in clearfell to 36.33/ dry t for a whole tree chipping
operation in an early thinning. Forest residue chips can be delivered for 34.33/ dry L
47
S H O R T ROTATION F O R E S T R Y
Stumpage
SYSTEM
COST
(3.60)
FELL/BUNDLE
XTRACT
(6.70)
(2.10)
CHIP
(2.60]
~*
TRANSPORT
(4.70)
STORAGE
24.50
(6.00)
RESIDUES
Stumpage
(1.00)
COLLECT
EXTRACT
(3.30)
CHIP
(6.30)
CHIP
(10.30)
WHOLE TREE
Stumpage
TRANSPORT
(4.70)
STORAGE
(6.30)
TRANSPORT
(4.70)
STORAGE
(6.40)
TRANSPORT
(4.70)
STORAGE
(6.60)
21.40
CHIPPING
(6.00)
FELL/BUNCH
EXTRACT
(4.30)
(1.60)
TERRAIN
INTEGRATED
CHIP
(4.80)
TRANSPORT
(4.70)
CHIP
(6.60)
STORAGE
(6.00)
(THINNING)
Stumpage - residue (1.00)

FELL
(1.20)
EXTRACT_
(3.30)
PROCESS^
CHIP
(6.10)
ROUNDWOOD
T R A N S P O R 1 _ STORAGE
(6.30)
(4.70)
20.60
INTEGRATED (CLEARFELL)
Stumpage - realduea (1.00)
FELL
(0.10)
EXTRACT
PROCESS^
ROUNDWOOD
(1.10)
CHIP
(6.10)
TRANSPORT.
(4.70)
STORAGE
(4.90)
Figure 1 Harvesting supply options and costs ( / w t ) .
16.90
48
Table 1
Total Cost of Wood Fuel,
Stumpage*
Felling
Extraction
Comminution
Transport
Storage
Total /wet t
/dryt
* raw material cost at stump
Assumptions:
1
2.
3
4
5
RF
Residues
/wett
/wett
3.50
6.70
2.10
2.50
4.70
5.00
24.50
40.83
1.00
5.00
1.50
10.30
4.70
5.30
20.60
34.33
5.60
4.70
5.00
21.80
36.33
Whole
tree chip
/wett
Integrated
clearfell
/wett
1.00
0.10
1.10
5.10
4.70
4.90
16.90
28.17
Moisture content of 55% (wet basis)

Transport distance of 70 km one-way
Covered storage at end user, moisture content reduction to 40%
Integrated systems costed on the residue component only.
Particle size of chips 5-35 mm.
AGRICULTURAL WASTE
Considerable quantities of agricultural waste, such as straw, bagasse, corn cobs, and
rice hulls, arise in agriculturally based economies where there may be no ready market for solid
fuels. In many cases this material is free and may even have a credit or negative cost of up to
-20/t because of the cost of disposal if it cannot be used. Particular features of agricultural
waste are that is is often already collected at one site and has often been subjected to extensive
pretreatment such as size reduction and drying. There will also usually be some storage and
material handling facilities. In addition such waste often creates a disposal problem with an
asociated cost. F or all these reasons, agricultural waste can be a very attractive feedstock for
conversion and upgrading, since the costs are low or even negative, i.e. attract a disposal
credit, and disposal problems can be solved. A summary of a variety of waste arisings in
several countries in Europe in given in Table 2.
In the UK, about 7 million t/y of surplus straw arise for which no ready market is
available, out of a total arising of about 14 million t/y. Comparable figures pertain to Europe.
Prices vary by location from 5 to 50/t, but representative costs have been estimated at about
17/t on-site or 22/t delivered [10].
The wide variety of materials suitable for processing precludes consideration of each
individually, and the range is indicated in Table 3.
4
4.1
REFUSE
Resources
Considerable quantities of domestic and commercial refuse are produced from any
society which require disposal at a significant cost. Processes that utilise this waste, therefore,
can often justify a credit from the disposal authority, as a result of saving the disposal cost.
Raw waste attracts the highest credit but requires the most preparation. There is again the
advantage of "free" collection as with agricultural wastes. The largest arisings of waste that
also attract the greatest disposal credit often occur close to the potential market for the energy
products. Estimated arisings for Europe are shown in Table 4.
49
Table 2
Estimated overall national arisings of potential energy from

principal agricultural residues, 1979 (11)
(millions of GJ/year unless otherwise stated)
Belgium & Luxemburg

Denmark
France
Italy
Holland
Ireland
UK
West Germany
Cereal.
Livestock
Maize & Rice Wastes
Residues
fa)
27.1
27.3
98.7
29.2
556.6
171.2
233.7
81.7
16.4
45.6
21.9
38.1
191.4
99.2
327.1
129.7
1 472.9
662.0
Green Plant Total

Matter
ibi
12.3
66.7
6.4
134.3
59.3
787.1
37.3
352.7
17.7
79.7
3.3
63.3
20.7
311.3
40.0
496.8
197.0
2 291.9
Total in
Mtoe
1.52
3.05
17.89
8.02
1.81
1.44
7.08
11.29
52.10
Notes
(a)
Presented as biogas available from pig, cattle and poultry by anaerobic digestion,
not as gross energy, animal bedding excluded.
(b)
Presented as biogas availabe by anaerobic digestion: other conversion routes are
available. No data are available for Greece, Spain and Portugal.
Table 3
Alfalfa straw
Barley straw
Coconut husk
Cotton gin stalks
Olive pits
Rice hulls
Tobacco dust
Table 4
Agricultural
Processed
Wastes
Almond shells
Bark
Coconut shells
Flax
Paper
Safflower straw
Vegetable fibre
that
have
been
Bagasse
Brazil nut husks
Coffee grounds
Ground nut shells
Peach pits
Straw
Walnut shells
Thermochemically
Bamboo
Cocoa husks
Cotton gin trash
Maize cobs
Prune pits
Sunflower husks
Estimated Arisings of Wastes in the EEC in 1982 (12)
Component
Household waste
Agricultural waste
Industrial waste
Sewage sludge
Waste from extractive industries
Demolition waste and debris
Consumer waste (used vehicles, tyres, etc.)
million tonnes/year
120
950
160
300
250
170
120
Some thermochemical processes have been devised that accept whole raw waste with
minimum pretreatment, such as the now abandoned Purox and Andco-Torrax processes.
Current thinking, however, is that some separation of inerts and pre-processing is necessary
for reliability and control in handling, feeding and conversion. Pretreatment of refuse to
50
produce a material acceptable for conversion would follow conventional refuse sorting
technologies, employing screening, shredding and classification. The products can range from
"fluff' (loose, low density material) through "crumb" (ie partially densified material) to pellets.
There are many proprietary systems on the market that have been proven for production of
refuse derived fuels.
Domestic refuse
In the UK, about 18 million t/y of domestic refuse are produced with a heating value of
about 9 GJ/t, and containing about 11 million t/y of combustibles, ie about 300 kg/head/y of
raw refuse or 150 kg/head/y daf waste. The average cost of disposal in the UK is claimed to
be about 6/t but these are believed to be very conservative with average costs of disposal
nearer 12/t, over a range of 5/t to as high as 40/t (13). In Europe, disposal costs are much
higher by a factor of up to 5, with typical figures at around 30/t. In some parts of the world,
disposal costs can exceed 70/t raw refuse. These figures will have a significant effect on
conversion economics if translated into credits. Further details of costs are given below.
Commercial refuse
In the UK, arisings of commercial solid waste have been estimated as 8 million t/y (dry
basis) with a heating value of around 16 GJ/t (dry basis) ie about 130 kg/head/y. The material
is generally cleaner and drier than domestic refuse with a higher proportion of packaging ie
paper, plastics, wood, etc. This is mostly handled by the private sector with a paucity of data
on quantity, quality and cost.
Industrial refuse
In the UK, combustible waste arisings from the UK industrial sector have been
estimated at 9 million t/y (dry basis) with a heating value of 16 GJ/t (dry basis), i.e. about 150
kg/head/y. This is also mostly handled by the private sector with a paucity of data on quantity,
quality and cost.
Other Wastes
Sewage sludge is another resource that is being investigated for thermochemical
processing. In the UK, sludge is generated at the rate of about 25 kg dry solids/head/y. A
disposal credit of up to 50/dry t is potentially available.
4.2
Refuse Processing
Most refuse processing or pretreatment processes are based on refuse separation for
RDF production in which the raw material is shredded to reduce particle size, screened to
separate inerts such as dust and glass, demetalled to remove cans, and classified as a refining
stage, giving a wet low bulk density (fluff) RDF product, although the sequence of these steps
can vary. The fluff can be dried, or pelleted then dried, and an intermediate step in the
production of pellets is a partially densified and dried material known as crumb. Each of these
operations has a cost associated with it which includes all capital and operating costs. This
permits the total cost of production of any RDF product to be estimated as shown below.
There will invariably be a residue after recovery of the fuel product which consists of nonfuel
materials and inerts, and which will have a much higher bulk density than the raw refuse. This
residue would normally be landfilled, and since the bulk density is so much higher, the cost of
this operation would be expected to be significantly less than for raw refuse due to the reduced
transport and handling costs.
4.3
Costs of Refuse Processing

The total cost of the unit operations encountered in refuse processing is summarised in
Table 5. Figure 2 shows a processing flowsheet and mass balance for various levels of
separation from which the cost of refuse derived fuels has been estimated in Table 6.
Refuse is normally disposed by landfill or incineration at a cost that reflects the
economic, social and environmental constraints. Disposal of residue, as explained above,
would be expected to be less than the disposal of raw refuse as costs are usually based on
51
volume rather than weight. It has been assumed that the disposal cost of the residue after
processing is half therawrefuse disposal cost.
From the methodology employed in the example in Tables 5 and 6, a general cost
model has been derived in Table 7 for the estimation of fuel costs for any raw refuse disposal
cost/disposal credit. This has been applied for a range of disposal credits in Table 8 to estimate
fuel costs at various levels of disposal cost/credit. This data is used in another paper at this
conference to estimate fuel gas and fuel oil costs from gasification and pyrolysis processes
(14).
Table 5
Cost of Refuse Processing Operations
Basis
Disposal cost
10/t raw refuse
Operations
Shredding
Demetalling
Screening
Air classification
Disposal of residue
Drying -fluffor pellets
Pelleting
Table 6
A
2.75/t
2/t
2.75/t
1.5/t
2.75/t
3/t
3/t
raw refuse
raw refuse
raw refuse
raw refuse
raw refuse
raw refuse
raw refuse
assumed
(self financing)
(50% disposal cost of raw refuse)
or
10/t product fuel
or
10/t pellets
Cost of Refuse Derived Fuel Products
Gross
The gross cost of products are as follows:

Wet "fluff' RDF (25% water)
9.75/t raw refuse
Dry "fluff' RDF (10% water)
12.75/t raw refuse
Pelleted RDF (10% water)
15.75/t raw refuse
or 24.40/t product
assuming 40% yield of
product (with demetalling
self-financing)
or 37.50/t product
assuming 34% yield of
product (with demetalling
self-financing)
or 46.30/t dried pellets
fuel
being
fuel
being
Nett
A disposal credit may be set against these costs, of, for example, 10/t raw refuse as used
above. This gives the following net costs:
Wet "fluff' RDF (25% water)
Dry "fluff (10% water)
Pelleted RDF (10% water)
-0.25/t raw refuse

2.75/t raw refuse
5.75/t raw refuse
or
or
or
-0.60/t product
8.10/t product
16.90/t dried pellets.
52
Raw refuse
d.a.f. RDF
0.25 te
ash
0.05 te
water
mme
waste, d.a.f.
0.34 te
ash
0.07 te
water
0-14 te
metal, d.a.f.
0.05 te
Total
1.00te
I
Shredding " " " 2.75
Demetalling
2.00
Screening
2.75
Air classification 1.50
Total
9.00
Metals 0.05 te
Credit 2.00
Waste 0.55 te
Disposal0.275 D
H20
To atmosphere
Wet "fluff"
d.a.f. RDF
ash
H20
Total
RDF
0.25 te
0.05 te
0.10te
0.40 te
JL
Drying
3.00
0.06 te
Dry "fluff' RDF

d.a.f. RDF
0.25 te
ash
0.05 te
H20
0.04 te
Total
0.34 te^
Pelletising
3.00
Pelleted RDF
d.a.f. RDF
0.25 te
ash
0.05 te
H20
0.04 te
Total
0.34 te
Note:
Figure 2
Raw refuse disposal cost

Processed refuse disposal cost
= D / te
= 0.5 / te
Refuse Processing Flowsheet, Mass Balance and Build-up of

Cost
53
Table 7
Product Cost as a Function of Disposal Cost

Example of build-up of processing costs.
Basis
Wet "fluff RDF (see Figure 2)
Assumptions
Assume disposal cost = D / te.
Assume disposal cost of residue after processing is half disposal credit value, as bulk density is
much higher thus reducing transport and handling costs, = 0.5 D/te
Cost Model
Cost of shredding, demetalling, screeening and air classification (Table 5)
Cost of waste disposal, 0.55 * 0.5 D
Credit from sale of metal
Disposal credit
Total cost per tonne of raw refuse
Cost per tonne of wet "fluff' RDF
Cost per tonne of wet "fluff RDF, d.a.f. basis
Cost of RDF
Wet "fluff RDF

Dry "fluff RDF
Pelleted RDF
Table 8
Product
(7.0-0.725D)/0.4
(7.0 - 0.725D) / 0.25
+9.00
+0.275 D
-2.00
-D
7.0 - 0.725 D
17.5- 1.81 D
28.0 - 2.9 D
/te raw refuse
/te product
/te product
daf basis
7.0 - 0.725 D
10.0 - 0.725 D
13.0 - 0.725 D
17.5- 1.81 D
29.4-2.13 D
38.2-2.13 D
28.0 - 2.9 D
40.0 - 2.9 D
52.0 - 2.9 D
Product Cost for Various Disposal Options

Costs derived from cost model in Table 7
Disposal
credit
Cost per tonne

raw refuse
Cost per tonne

product
Cost per tonne

d.a.f. product
Wet "fluff RDF
5
10
15
20
3.38
-0.25
-3.88
-7.50
8.45
-0.60
-9.63
-18.70
13.50
-1.00
-15.50
-30.00
Dry "fluff RDF
5
10
15
20
6.38
2.75
-0.88
-4.50
18.75
8.10
-2.55
-13.20
25.50
11.00
-3.50
-18.00
Pelleted RDF
5
10
15
20
9.38
5.75
2.13
-1.50
27.55
16.90
6.25
-4.40
37.50
23.00
8.50
-6.00
Note: All costs and credits are expressed as /tonne
54
CHARACTERISTICS
The basic characteristics of biomass are summarised in Tables 9 and 10. Particular features
are the fairly high moisture content, low bulk density and wide particle size range.
Typical Properties of Biomass
Table 9
Moisture content
(wet basis)
Mean particle size
(mm)
Size range 2-150
(mm)
Bulk density
(wet kg/m3)
Forest
residues
Processing
residues
Whole
trees
SRF
MW
(fluff)
Straw
30-60%
20-60%
40-60%
40-60%
15-40%
10-20%
5x20
5x2C1
5x20
5x20
50
5x200
2-75
2-100
2-50
up to 500 5-1000
300
350
300
350
Feedstock
Ultimate analysis
Mass %. drv basis
H
0
Ash
52.3
51.6
56.2
6.3
6.3
5.9
40.5
41.5
36.7
0.1
0.0
0.0
0.0
0.0
0.0
0.8
0.6
1.2
80.3
43.4
38.5
48.1
30.7
33.5
3.1
5.8
5.7
5.9
4.2
4.6
11.3
44.3
39.8
40.2
20.5
22.4
0.2
0.3
0.5
1.0
0.3
0.7
0.0 3.4
0.2 6.0
0.0 15.5
0.1 4.7
0.5 43.8
0.4 38.4
58.4
68.4
73.1
5.4
5.8
5.5
26.0
17.8
8.7
Douglas Fir
Beech
Douglas Fir bark
Wood shavings
Sawdust
Sander dust
Charcoal
Paper
Rice hulls
Straw
Refuse (UK)
Municipal solid waste (USA)
For comparison
Peat
Lignite
Bituminous coal
200
Analyses of Feedstocks
Table 10
Notes
100
Moisture
%,
wet basis
30-60
30-60
25-75
16-40
25-40
2-8
16-20
20-35
15-30
0.5 9.7
0.4 7.6
1.2 11.5
Ash includes metals, glass etc.
CONCLUSIONS
Wood, municipal solid waste and agricultural residues are all potential feedstocks.
Wood will be available from processing residues, unmanaged woodlands, conventional
forestry and short rotation forest biomass plantations. Harvesting, processing and transport
systems for delivering wood fuel either already exist or are under development. Delivered fuel
costs will be between 28 - 36/ dry t from conventional forestry and in the order of 41/ dry t
55
from short rotation. Agricultural wastes, such as cereal straw, can be delivered to the end-user
for 22/dry t. Domestic and commercial refuse is available and can attract disposal credits of up
to 20/wet t which has a significant effect on the conversion economics, even after extensive
processing to separate the fuel rich fraction. Once at the plant, conventional handling,
screening and sorting systems can be utilized for all feedstocks. All aspects of the supply chain
are under active research and development which should result in reduced feedstock costs.
7
ACKNOWLEDGEMENT
S
The work on wood as fuel (CPM) was supported by the UK Department of Energy and
the Biomass for Energy Programme of the CEC. The views expressed are those of this author
and not necessarily those of the sponsors.
Much of the data reported in this paper on refuse costs (AVB) were generated for the
Energy Technology Support Unit at the UKAEA, Harwell, UK, as an update of earlier work
(13). They are intended to be published in due course in a strategic review of thermochemical
conversion technologies for biomass and wastes (15). All opinions and statements are the
views of this author and in no way reflect any views of the UKAEA or the UK Department of
Energy.
8
1
REFERENCES
BRIDGWATER, A V and MITCHELL, C 1987. Interfacing biomass production and
biomass conversion. In 4th EC Energy from Biomass Conference. Ed Grassi et al.
Elsevier Applied Sci 1174 -1178.
2
MITCHELL, C 1987. European forest energy scene. In Proc 4th EC Energy from
Biomass Conference. Ed Grassi et al. Elsevier Applied Sci 54 - 58.
3
HARE, M; MARTINDALE, L and MITCHELL, C 1989. Supply and Use of
Wood Fuel in the UK. Energy Technology Support Unit, Harwell. In press.
4
MITCHELL, C ; TRANTER, R B; DOWNING, P; BRANDON, O; PEARCE, M L;
BUNCE, R G H; and BARR, C J 1987. Growing wood for energy in Great Britain.
ETSUB-1102.
5
DERLER, R 1988. Measurements of tree fuel at eleven district heating plants in
Sweden. IEA/BE Report 52.
6 JJ
IR IS, R 1988. Microfungi problem - health aspects. In Production, storage and
utilization of wood fuels. Proc IEA/BE Conference, Uppsala, Sweden Dec 6-7,1988.
2 Vols. Ed B O Danielsson and O Gislerud. Swedish University of Agricultural
Sciences, Department of Operational Efficiency. Research Notes No 133/134 1988.
163 - 167.
7
MITCHELL, C ; HUDSON, J B; GARDNER, D A and STORRY 1989. Storage
and drying of comminuted wood fuels. In Proc IEA Task VI Workshop "Wood
preparation, storage and drying". Lind, Denmark May 16 -18,1989. In press.
8
GUSTAFSSON, G 1988. Forced air drying of chips and chunkwood. In Production,
storage and utilization of wood fuels. Proc IEA/BE Conference, Uppsala, Sweden Dec
6 - 7, 1988. 2 Vols. Ed B O Danielsson and O Gislerud. Swedish University of
Agricultural Sciences, Department of Operational Efficiency. Research Notes No
133/134 1988. 150 -162.
9
MITCHELL, C ; MARTINDALE, L P; HARE, M; HUDSON, J B; GARDNER, D
A and STORRY 1988. The potential for harvesting fuelwood in the United
Kingdom: A systems approach. In Proc IEA Workshop "Economic evaluations of
biomass oriented systems for fuel". Ed G Lonner and A Tornqvist Swedish University
of Agricultural Sciences, Department of Forest Industry Market Studies, 211 - 217.
10
CLEGG, J M et al., The acquisition and utilisation of straw as fuel, Silsoe College,
Report to ETSU, 1985.
11
BUNGAY, H R, "Thermochemical Processes", in Energy: The Biomass Options,
(Wiley-Interscience Publication, New York, 1981).
12
BOURDE AU, P H and FERRER, G L, "Introduction and general presentation of the
R&D programme on recycling of urban and industrial waste", in Anaerobic digestion
and carbohydrate hydrolysis of waste; Eds. Ferrer, G L, Ferranti, and Naveau,
U, (Elsevier Applied Science, 1987).
56
13
14
15
BRI
D GWATER, A V; DOUBLE, J M and EARP, D M 1986. Technical and market
assessment of biomass gasification in the UK. Report to ETSU 1986.
BRI
D GWATER, A V, Economic and market opportunities for biomass derived fuels,
these proceedings.
BRI
D GWATER, A V and STRONACH, J, "A Review of Thermochemical
Conversion Technologies", Report to ETSU, Department of Energy, 1989.
57
PROCESSING OF URBAN WASTE TO PROVIDE FEEDSTOCK

FOR FUEL/ENERGY RECOVERY
J R Barton
Warren Spring Laboratory
Department of Trade and Industry
Summary
The UK has over ten years experience in the design, operation and
monitoring of Refuse Derived Fuel (RDF) production plants and
combustion of the products. Although most plants recover the fuel
in pelletised form for use on conventional industrial solid fuel
boilers, shredded fuels are also made and used. The paper reviews
the technology adopted
for
fuel recovery
and,
given
the
composition and processing characteristics of UK refuse, comments
on best practice based on the experience of commercial plants.
Brief comment is made on the combustion characteristics of RDF
based on laboratory research and practical experience in order to
highlight problem areas.
The paper concludes that much better
guidance can now be given to designers of thermal treatment
processes on the role waste pretreatment can play in developing
more effective energy from waste systems, whether these involve
direct
combustion
or
the
application
of
pyrolysis
or
gasification.
1. INTRODUCTION
Mechanical sorting systems, by separating, concentrating and
altering the physical nature of the waste, permit more effective
application of subsequent thermal, biological or other treatment and
recovery processes.
They also offer the opportunity for improved
control over the environmental problems associated with waste treatment
and disposal. However, experience of sorting plants for MSW has been
mixed and
full
scale
processes
have
generally
not
fulfilled
expectations. Often equipment capacity and availability has been lower
than expected and marketing problems have been experienced with the
products due to quality deficiencies, competition from alternatives or
the introduction of more stringent regulations governing use. Despite
these difficulties, significant progress has been made in terms of
achieving
reliable
plant
operation
and,
more
importantly,
in
understanding the limitations and potential inherent in the approach
to permit better matching of feedstock characteristics with process and
58
market requirements.
Warren Spring has been closely involved in
designing, commissioning and monitoring refuse derived fuel plants in
the UK and abroad and this paper summarises the key factors that need
to be considered when adopting a pretreatment stage prior to thermal
treatment.
Obviously sorting waste for fuel recovery results in
residues which must be disposed or further treated to recover values.
However, whilst effective treatment of these residues is an integral
part of the overall concept and influences process selection, it is a
subordinate consideration.
Fuel and energy recovery is the major
weight and volume reducing stage and if this is not effective,
extending recovery processes to residues can rarely be justified.
2. SEPARATION AND RECOVERY OF THE FUEL RICH COMPONENTS
2.1 Refuse composition and process selection
Table 1 gives a typical composition for UK refuse along with the
ash, moisture and calorific value of the components 'as received', ie
as delivered to a processing plant. This input data dictates the mass
yield, energy recovery and quality achievable by physical sorting
alone. Fig. 1 illustrates the effect of ideal separation (eg by hand
sorting) assuming categories are removed in order of increasing fuel
value eg starting at point A with raw refuse, removing glass, metals
and inert categories first (point ) , then
unsorted fines (10 mm)
(point C ) , next putrescibles (point D) and so forth.
The effect on
mass yield (x axis) energy loss (y axis) and fuel quality at any point
can be assessed.
Obviously mechanical sorting systems are not so
systematic nor are they 100% efficient at removing separate categories
but this graph,does provide target values for process designers and
a baseline against which to assess plant performance.
Theoretical
separation efficiences can be calculated at each point using accepted
efficiency formulae. The values given on Fig. 1 are calculated using
the following formula derived by Douglas'1':
Separation efficiency
where R
C
c
f
=
=
=
=
iooC
i00f
x 100%
% of available energy recovered in concentrate

weight % of concentrate
% assay of concentrate (in terms of calorific value)
% assay of feed (in terms of calorific value)
To obtain values for c and f, an arbitrary maximum calorific value

must be selected to represent 100% 'pure' fuel.
In this case the
average
calorific
value
of
the
combined
plastics
categories,
ie 28.5 MJ/kg, has been selected. The low values calculated using this
formula mainly reflect the unrealistically high target CV for 'pure'
fuel which, by
definition
cannot
be
reached
without
rejecting
categories such as paper. However, considering the relative changes,
these data show that whilst the separation efficiency gains from the
removal of non combustibles, fines and putrescibles reach a maximum
value and conform to expectations, selective recovery of the plastics
alone is equally efficient; this is because the formula used gives
equal weight to maximising fuel quality as it does to maximising fuel
59
Table 1.
As ree'd
assay
wtZ
Paper
Plastic film
Dense plastics
Textiles
Misc. combustibles
Misc. non-combs
Glass
Ferrous
Non-ferrous
Putrescibles
Fines -10 mm
TOTAL
Composition of UK refuse
Moisture
content
wtZ
Ash content
(as ree'd)
wtZ
33
4
4
4
5
5
8
6
1
20
10
30
25
15
25
25
15
20
15
10
65
40
8
9
6
8
12
85
90
85
90
8
40
100
33
28
Gross calorific
value (as ree'd)
MJ/Kg
12
27
30
15
13
6
4
9.1
20
40
60
80
100
YIELD OR WEIGHT OF FUEL AS A PERCENTAGE OF INPUT
FIG. 1 EFFECT OF 'IDEAL' SORTING OF REFUSE FOR FUEL RECOVERY
60
recovery. Obviously many other criteria, particularly options for the
residues, need to be taken into account when determining an optimal
solution but this assessment does highlight that, for refuse, a wide
range of fuel yields is compatible with maintaining a high separation
efficiency from a strict technical viewpoint.
Even from the fuel viewpoint alone the chemical composition,
particularly of elements which cause environmental problems in thermal
treatment (eg chlorine, heavy metals), has a significant effect on the
costs of converting the 'fuel' to usable energy.
Thus to select the
optimum fuel recovery and grade for a system and to determine how to
achieve it requires more detailed data.
Such information has become
available from testwork undertaken by WSL and other workers'^)").
For example, size distributions of each category have been measured at
10, 20, 40, 80, 160 and 320 mm and for each sized-category fraction (eg
-80+40 mm paper fraction) further analysis gives moisture, ash,
calorific value and chemical composition.
These data have proved
invaluable for optimising plant equipments and process flowlines. At
WSL the information is kept on database and manipulative software has
been written to permit selection and averaging of sample data and the
application of "process function" matrices which represent either real
separations achieved by specific process equipments or
'ideal'
separations. This work, along with the potential to develop mathematic
models of the processes, has been detailed previously^*'; for the
purposes of this paper it is sufficient to know that given a
specification or requirement based on the thermal treatment step, a
rapid assessment of whether this is achievable using sorting technology
alone can now be made.
2.2 Practical considerations
Many options can be selected for a process flowline but practical
considerations and experience have narrowed these down, particularly
during the early treatment steps. Thus whilst the simplified flowline
illustrated in Fig. 2 represents a good option for achieving fuel
qualities and yields close to the theoretical values given in Fig. 1,
variations on the theme, particularly in the latter stages for a more
refined fuel with controlled physical characteristics (eg pellets), are
entirely acceptable. For discussion purposes, the four stages selected
are (i) preliminary liberation and screening, (ii) magnetic separation
and coarse shredding, (iii) a refining separation stage and finally
(iv) processes to control the physical characteristics of the fuel.
The following sections are not intended to be a comprehensive review of
the requirements for each stage but to illustrate, with examples, why
certain processes are effective, where the major problems are and to
indicate where the balance between pretreatment and preparation costs
and the costs of the energy raising unit is likely to be in any given
circumstances.
2.2.1. Stage 1 liberation and screening
Experience in the U K ' ^ ) has clearly identified that screening
prior to size reduction has significant benefits in terms of process
reliability and fuel quality.
It can remove materials which
contaminate the fuel categories during shredding as well as problematic
items which adversely effect the performance of shredders.
The key
equipment item is a rotary screen or trommel and, whilst a separate
61
RAW WASTE
wt = 100%
cv = 9.1 MJ.Kg" 1 - - ENERGY = 100%
50mm FINES
STAGE 1
LIBERATION AND SCREENING

FINES REMOVAL (^50mm)
OVERSIZE REMOVAL (^500mm)
+500mm
OVERSIZE
wt =
cv =
ENERGY=
wt =
cv =
ENERGY=
32%
4M J. Kg"1
14%
2%
13 M J Kg"1
3%
wt = 66%
c v = 11.5 M J. K g " 1 * - - I
ENERGY= 83%
STAGE 2
MAGNETIC SEPARATION
AND
COARSE SHREDDING
-FERROUS METAL
w t = 6%
c v = 1 MJ.Kg"1
ENERGY= 1%
HEAVY AND
FINE REJECT
wt = 12%
cv = 9 MJ.Kg"1
ENERGY= 12%
wt = 60%
cv = 12.5 MJ.Kg"1-ENERGY = 82%
STAGE 3
REFINING (SEPARATIONS)
AIR/BALLISTIC
CLASSIFIERS
FINES REMOVAL (<10mm)
wt = 48%
cv = 13.4 MJ.Kg 1 '
ENERGY = 70%
STAGE 4
REFINING (PHYSICAL)
SHREDDING
DRYING
PELLETING
COOLING
MOISTURE
LOSS
wt
wt = 36%
cv = 18MJ.Kg- 1 -*-I
ENERGY = 70%
RDF PELLETS
FIG. 2 STAGES IN PRODUCTION AND REFINING OF REFUSEDERIVED FUELS
12%
62
liberation stage to open bags and release refuse component (eg at the
Byker plant) is advantageous, a trommel can be designed and operated in
a manner which ensures sufficient liberation and breakage of friable,
non-fuel components (such as glass) to achieve efflicient screening.
Effective design criteria for fine screening duties have been
developed*"', the equipment
is simple
and robust, designs for
feedrates up to 40 teh-* for a single unit are proven and scale up
for higher feedrates is possible. Running costs are low with specific
power consumptions below 1 kWh per tonne of raw waste processed.
For
UK refuse the aperture size selected for fine screening is normally
between 40 and 60 mm, a size which ensures minimal loss of identifiable
combustibles categories ( 5%) whilst achieving removal of over 65% of
the putrescible category, over 90% of the -10 mm fines and over 85% of
the glass. Most metal reports to the topsize, fuel rich fraction, but
items such as small batteries and foil from wine bottles tend to report
to the fines and this results in reduced heavy metal contamination of
the recovered fuel.
One action of a trommel which is detrimental to downstream
processes is the tendency to 'create' ragtails; these are sausage like
composites of wire, string, textiles and plastics up to several metres
in length. Such items, along with the bulky items which 'naturally'
occur in refuse (eg matresses, dustbins etc) are difficult to size
reduce effectively.
Some pulveriser designs, such as vertical shaft,
non gridded hammer mills are capable of coping with such materials but
the effect on gridded mills can be extremely damaging in terms of
throughput and availability.
Fortunately a coarse screen section
installed in the trommel can reject such items with minimal loss of
fuel values and is strongly recommended.
Table 2 shows the dramatic
improvement achieved at the RZR Herten plant by modifying the trommel
to scalp out items above approximately 500 mm in size. Close attention
needs to be given to the design of the screen plate to minimise
blinding and to ensure easy access to the external surface for cleaning
purposes. Experience suggests that downtime for cleaning can be kept
to below 10 minutes per 8 hour shift without adversely effecting
screening efficiency.
Removal of coarse materials also improves the
efficiency of subsequent magnetic separation when this is carried out
before shredding in Stage 2.
The importance of trommel screening as the first fuel-non fuel
separation process is now well established, even without magnetic
separation, screening alone proved effective in terms of increasing
energy output and boiler efficiency for a conventional mass burn
incinerator at Sheffield*''.
For UK waste, Stage 1 should result in a yield of 60% wt fuel rich
material, reporting a calorific value of approximately 11.5 MJ/Kg and
containing 83% of the original energy content.
63
Table 2.
RZR Plant, Herten - Effect of coarse aperture screening

on plant performance
Before coarse aperture
scalping
Steady state
throughput
22 teh
Plant
availability
72%
Hammer mill
specific power
consumption
*
-1
25 kWh/tonne
After scalping out

oversize at
approx. 500 mm*
27 teh"1
96%
18 kWh/tonne
weight of oversize removed was less than 2% of the refuse feed.
2.2.2. Stage 2 Magnetic Separation and Coarse Shredding

Assuming the fuel rich topsize has been scalped to remove coarse
items, the preferred magnetic extraction system is an overband unit
positioned at a head pulley in line with the refuse flow. Recoveries
of at least 90% are common but the magnetic product will contain up to
15% contrary materials (eg paper, plastics).
Cleaner products are
obtained if magnetic separation is delayed until after the shredding
operation; however prior metal removal can be considered a protective
measure, reducing the risk of explosion damage from volatiles (eg paint
thinners, butane) present
in cans, aerosols
and
gas bottles.
Irrespective of the sequence, shredders need to be sited in 'explosion
proof' housings and preferably fitted with an explosion suppression
system. Hammer mill designs are preferred for coarse shredding due to
their robust nature and, if scalping has been carried out, a gridded
design does assure topsize control for downstream operations is
maintained irrespective of hammer wear (hammer condition will still
need attention
for
maintaining
desired
size
distribution
and
throughputs). Specific power consumptions and flow rates will depend
on mill design and feed composition.
Values between
15 and
25 kWh/tonne are not untypical. A major pitfall to be avoided is to
believe that the size and power of a mill can be significantly reduced
by stream splitting. For example, when a trommel was installed before
the pulveriser at Byker, the weight throughput to the pulveriser
reduced
from
30
teh-^
to
20
teh-'due
to
removal
of
10 teh -1 of fines.
It can be seen from Table 3 that the effect on
power usage was minimal as the specific power requirement for the
remaining topsize increased from 12 to 17 kWh/tonne.
This is not
surprising, the volumetric flowrate was largely unaffected and the
weight of materials that actually required size reduction, ie the
paper, plastics and textiles had not been reduced. Similar experiences
at the secondary shredding stage have occurred when little benefit has
64
resulted from prior removal of materials already below the desired
shred output size.
From the fuel quality and yield data given on Fig. 2, it can be
seen that the bulk of the fuel-non fuel separation has been achieved by
the trommelling and magnetic separation stages.
Again, without
shredding, current testwork on a conventional mass burn unit (at the
Edmonton incinerator) is showing encouraging results and the shredded
product is similar (but of better quality) to the fuel used at
Courtaulds'"' in Grimsby on a large water tube chain grate boiler
and the fuel used
in the cement
kilns
at Westbury
by Blue
Circle'"'.
Restricting pre treatment to this stage and using
circulating
fluid bed
combustore
is also being
given
serious
consideration in the UK.
For UK waste, Stages 1 and 2 should result in a yield of 60% wt
fuel rich material, reporting a calorific value of approximately
12.5 MJ/Kg and containing 82% of the original energy content.
Table 3.
Effect of fines removal on hammer mill performance

Throughput
Wt.
Volume
teh
Raw refuse
Screened
refuse
(-50 mm fines
removed)
Size reduction
(d,, mm)
From
To
Hammer mill power

consumption
Total
Specific
kWh
kWh/te
30
165
80
11
355
11.8
20
155
150
24
335
16.8
2.2.3. Stage 3. Light-heavy separations and fine screening

The separations in Stage 3 are primarily to refine the fuel
product.
Useful improvements in terms of reducing ash and metal
contents can be achieved but residues often report relatively high
calorific values.
Of equal importance, Stage 3 separations protect
more vulnerable
downstream
equipment
such
as
knife
mills
and
pelletizers by removing
heavy
or dense
items
irrespective of
composition.
Light-heavy separations for refuse materials have been subject to
a number of detailed studies'"''' and many different designs have
been tested at full scale'"'.
Products other than fuel from refuse
have also been
recovered
(eg plastics, composts, paper).
The
separation characteristics of ballistic units are different from air
classifiers, for example in certain designs 'bounce' is a more
important characteristic than particle density and shape.
Such
differences can be worth exploiting, eg PVC bottles tend to 'bounce'
into the heavy reject for one ballistic design and this can reduce
chlorine levels in the fuel. On the other hand fuel quality and fuel
flow rates
tend
to be easier
to
control
in
air
classifiers
(particularly under variable feedrate or surge conditions) and this can
65
bring important benefits in terms of process efficiency of downstream
equipment.
Further fines removal is often carried out during this stage to
reduce ash content and screening can be incorporated into the
light-heavy separation unit or carried out separately.
Both trommels
and flat bed units have been used, but if a flat bed unit is selected,
vibration amplitude should be larger and frequency lower than is
normally adopted for screening minerals (eg coal, sand, gravels). To
prevent excessive loss of fuel values on aperture size of 10 mm or
below is usually selected.
Energy inputs for Stage 3 separations equipments
are not
particularly high and rarely exceed 10 kWh/tonne for most fuel recovery
applications.
Careful
consideration
should
be
given
to
the
requirements of downstream equipments and the thermal conversion
process when designing this section of the plant.
Specific problem
materials can be rejected and there is scope for more development in
the equipments but it must be recognised that in strict energy
efficiency terms the separations undertaken are in a regime of
diminishing returns.
For UK waste, Stages 1, 2 and 3 should result in a yield of
48% fuel rich material reporting a calorific value of approximately
13.4 MJ/Kg and containing 70% of the original energy value.
2.2.4. Stage 4 Processes to improve the physical properties of the
fuel
This stage is concerned entirely with tailoring the fuel to suit
the combustion or thermal treatment stage.
By further shredding,
drying and pelleting, the fuel storage, handling and combustion
properties are improved.
This stage also lends itself to blending in
additives specifically to enhance combustion properties.
In terms of
capital, maintenance and operating costs per tonne of material
processed, the processes in this stage tend to be the most expensive in
the plant.
Hence, high plant availability is essential and this
requires much improved monitoring and control of flowrates, feed
composition and equipment.
The shredding stage normally requires in
excess of 25 kWh/tonne to reduce a coarse shred (say approximately
100 mm) to below 25 mm (mean size approximately 10 mm).
The
evaporative heat
requirement
for successful
pelleting
(reducing
moisture levels from approximately 30% to below 12%) is approximately
700 MJ per tonne of fuel and as drying efficiencies are between 50 and
65%, a thermal input of over 1200 MJ per tonne is needed (ie +4/tonne
at natural gas prices or up to 10% of the plants fuel output if an RDF
fired combustor is used).
For good quality pellet production a
specific power consumption of +35 kWh/tonne for the pellet mill alone
is typical. Although no physical separation processes are undertaken
during Stage 4, moisture removal during drying, pelleting and cooling
increases calorific values to around 18 MJ/Kg and the bulk density from
approximately
100 Kg m~3
for coarse
shred
to over
600 Kg m--*
for pellets.
There are many views on the best equipment designs and of best
process sequence for the production of pellets.
There are certainly
advantages and disadvantages to all with different plant designers
preferring
knife mills to hammer mills, cascade dryers to pneumatic
66
dryers, fixed die pelletisers to rolling die machines, single stage
pelleting to two stage densification etc.
Suffice it to say all
systems initially developed failed to meet design objectives, flowrates
of half the anticipated levels were not unusual and dedicated effort to
modify and improve the process, often by the plant operators rather
than individual equipment manufacturers has been needed to achieve
satisfactory performance.
Today there is no excuse for installing
equipments which don't fulfill the process requirements but new plants
would be strongly recommended to buy proven systems rather than put
together separate units that haven't previously been tested in
sequence.
Quite simply "the art" in preparing and pelleting waste
fuels is as important as the scientific and engineering knowledge of
the individual unit processes.
An important consideration in the drying stage is abatement of
particulate emissions and odours from the dryer gas. This has caused
problems with existing UK plants whether the drying heat has been
provided by gas burning or burning RDF. Although satisfactory retrofit
solutions have been found (eg increasing chimney heights, increasing
efflux velocities, adding odour counteractants and oxydising chemicals
to scrub waters, adding additional particulate removal systems etc),
this is an area where further investigation is needed to define the
problems more closely and develop optimal solutions.
There is undoubtedly scope in Stage 4 processes for significant
improvements to be made.
The design of pelleting processes has been
based mainly on achieving similar handling, storage and feeding to
small coal.
This has proved expensive but as experience with using
waste fuels increases, user requirements will become more specific and
this should stimulate development of more cost effective Stage 4
systems.
For UK waste, Stages 1 to 4 should result in a yield of 36% by wt
fuel, reporting a calorific value of approximately
18 MJ/Kg and
containing 70% of the original energy content.
Electrical energy
inputs for the full plant are likely to be up to 70 kWh/tonne of refuse
input, approximately 200 kWh/tonne of pelletised fuel.
2.1.5. Other processing factors
Before
considering
fuel
characteristics
against
combustion
requirements, brief comment on storage and handling systems is
warranted. Within a production plant, short term storage systems have
advantages from a design viewpoint in smoothing out flows and matching
capacities in different sections of the circuit.
However they have
frequently resulted in more problems than they have solved. Blockages
and uneven discharge characteristics have been experienced with most
shred bunker designs, particularly push floor bunkers and bunkers with
screw discharge systems. The reasons for failure vary, hopper size and
shape is critical (it must diverge), push floor designs generally do
not provide sufficient positive motion to be effective if the depth of
shred exceeds 1 or 2 metres, the design of screws and discharge outlet
must avoid compressing the shred. Recent work at WSL on a multiscrew
discharge hopper proved blockages could be avoided by careful design,
but even with a fine sized ( 25 mm), relatively dry shred suited for
pelleting, fluctuations of 25% about the mean discharge flowrate still
occurred. Bunkers with screws that move position within the mass of
67
the shred (eg by traversing the bottom of the hopper or rotating
eccentrically within the hopper) largely overcome blockages and a novel
design based on a slow moving plate conveyor floor and a rotating rake
device to tear off the shred as the mass moved toward the .open
discharge side worked successfully at the Rolls Royce plant' 11 '.
Thus progress has been made but problems in this area are still a
frequent occurrence at sorting plants and for all new systems or
systems to feed shred to a combustion unit, particulary attention needs
to be paid to this aspect of plant design.
Handling, storage and feeding of pellets is less of a problem;
small amounts, kept in dry and well ventilated conditions, show little
sign of degradation after a year or more, but prolonged storage in deep
bunkers or piles would not be recommended. There are many examples of
localised heating, sweating and fungal growth leading to break up of
pellets in bulk storage and potential fire/health hazards. Whilst some
of these problems can be attributed to poor control of moisture content
during production, changes in climatic conditions (temperature and
humidity) also affect pellet stability.
Hence storage should be
limited to a few months. For undried RDF, a few days is preferable
although longer periods can be tolerated if the subsequent handling
system is designed to cope with 'lumpy' materials.
The above comments cover a few of the practical difficulties
experienced on UK plants.
Generally solutions have been found but
further progress and experimentation with plant design is still
required and to aid this, a few thoughts are given below based on over
10 years of problem solving on RDF plants.
.
.
.
.
.
Reliability is more important than technical efficiency

Reject problematic materials as soon as possible
Exploit the natural separation characteristics of the waste first
Delay energy intensive stages as long as possible
Ensure the basic processing and separation principles of the
equipments are understood
. Volume, not weight throughput tends to be the rate limiting
factor
. Once refuse stops moving, it needs a positive kick to start again
. Always remember it is waste until a marketable product is
recovered, irrespective of the degree of processing
3.
RDF and thermal treatment

Although this paper is primarily concerned with production of RDF,
UK experience with combustion of RDF (pellets in particular) is
beginning to feed back into the production process and consideration
can be given to whether problems are better tackled during feed
preparation or by developments in the thermal conversion stage.
Table 4 gives basic information on composition and properties of RDF
pellets and a typical UK bituminous coal but many of the comments made
below are based on more detailed characterisation studies undertaken by
WSlA").
Th e objectives to be realised for an effective energy
from waste plant are as follows:
1. Maximum heat release for minimum grate size.
2. Minimising clinker formation.
68
3. Minimising boiler fouling
4. Minimising emissions (acid gases and heavy metals in
particular).
Table 4.
Properties of RDF pellets and bituminous coal
RDF (Byker)
Gross calorific value MJ/kg
Coal
18.5
27
8
15
67
10
8
10
26
56
55
7
36
84
5
8
1.6
.1
1
Proximate analysis
Moisture content
Ash content
Volatile matter
Fixed carbon
Zwt
Zwt
Zwt
Zwt
Ultimate analysis (DAF)

Total carbon
H
0
Cl
S
Zwt
Zwt
Zwt
Zwt
Zwt
Zwt
Bulk density
Size of fuel
Kg m"
mm
.6
.9
.3
600
16 mm diameter
900
10 to 25 mm
Heat release
From Table 4 it can be calculated that almost twice the volumetric
throughput of pellets is required to match the same thermal input of
coal. This affects fuel handling and feeding equipment more than the
combustion appliance because the higher volatile content of RDF and the
higher reactivity of RDF char compared to coal greatly reduces the
residence time requirements within the combustor for complete burn out.
Pellet density, size and shape will affect this but, to date, it has
not proved necessary to exploit the ability to change these properties
to increase (or reduce) heat release rates.
It is pertinent
to note the difference
in heat
release
characteristics of RDF pellets compared to raw waste; the residence
time for pellets on a chain grate is approximately 15 minutes compared
to approximately 60 minutes for MSW on an incinerator grate.
As
pellets have approximately 7 times the energy content per unit volume
compared to raw waste this suggests a 30 fold advantage over raw waste
in terms of grate area required to achieve the same heat release
rates.
3.2 Minimising clinker formation
Although clinker formation was a problem experienced on a number
of stoker/grate
systems
during
early
firing
trials^^',
69
improvements in processing technology, particularly the use of front
end screens, have reduced ash contents in RDF and reduced clinker
formation.
At
Byker, for example, RDF ash contents reduced from
approximately 17Z to below 14% on a dry weight basis^) and much of
the reduction was due to removal of components with a low fusion
temperature such as glass. Most of the remaining ash is inherent in
the combustible categories; paper extracted from refuse for example
normally assays approximately 10% ash (dry wt basis) and the IDT
(initial deformation temperature) is between 1000'C and 1050C compared
with 1150C for coal. Hence RDF will always report lower ash fusion
points than coal but, given efficient processing, clinkering on most
commercial systems is not a problem.
For systems which still
experience problems (eg ram stokers), recent work at Warren Spring has
indicated that addition of chemical compounds can increase fusion
temperatures and hence offer a potential solution. Obviously for lower
temperature thermal processes, eg pyrolysis or gasification, the
possibility of clinker formation is much reduced.
3.3. Minimising boiler fouling
Severe fouling of boiler surfaces has been experienced with both
raw waste incineration and RDF combustion.
The deposits have a high
concentration of alkali metals, for example tube entry deposits on a
chain grate unit burning pellets assayed over 90% alkali sulphates.
The problem is more severe than coal simply because RDF contains ten
times more sodium and potassium and these metals are also present in a
more easily volatilised form. Alkali salts are added as fillers to all
forms of paper and there is no physical separation technique capable of
removing these deposit forming chemicals from the feedstock.
One
processing step that could contribute to some deposition control is the
addition of a chemical that reacts with the alkali to form a more
stable compound which will not
volatilise
at
the
temperature
experienced on the fuel bed.
Kaolin has been proved effective in
retaining alkalis as alumino silicates in the past'^' but is
unlikely to offer a complete or cost effective solution. In the longer
term, control of deposition will probably lie with the design and
operation of the combustion and boiler unit. Boiler fouling has been
substantially reduced on a chain grate by a combination of selecting
fuel bed depths and grate speeds to reduce the time of the high
temperature ash burn out phase (and hence reducing volatilisation),
reducing the temperature of the flue gas prior to the first boiler pass
(at the cost of reduced boiler efficiency) and use of soot blowers.
Again adoption of lower temperature gasification processes as opposed
to full combustion would make a significant impact on this problem by
retaining the alkalis in the fuel ash residues.
3.4 Minimising emissions
Coal combustion particulates are mainly coarse fly ash entrained
through the system and relatively easy to abate using conventional
basic units, ie grit arrestors. In RDF combustion a larger proportion
of the particulates are sub micron which can only be removed
efficiently by more expensive abatement units such as electrostatic
precipitators or bag filters.
Test work in chain grate stokers has
shown RDF particulate emissions are high in metallic chlorides (eg Na,
K, Pb, Cd and Zn). As mentioned, the alkali metals are constituents of
70
paper; lead, cadmium and zinc also appear in combustible categories.
For combustion
processes,
improved
abatement
equipment
is
the
established solution though again lower temperature thermal processes
should certainly reduce the emission of these metal chlorides.
For acid gas emissions, SO2 is not a problem compared with coal
combustion but HCl emission certainly is. In the UK, combustion of RDF
pellets typically gives rise to HCl concentrations of 800 to 1000 mg
Nm - 3 (9% CC-2).
Up to 60% of chlorine in RDF is present in
chlorinated plastics (PVC) and this is totally converted to HCl in all
forms of thermal treatment.
As discussed previously there is some scope for removing PVC
bottles during RDF production but this by itself is unlikely to make a
substantial reduction in emission levels.
Thus controlling HCl
emission from combustion processes requires the appropriate downstream
flue gas clean up technology (eg scrubbing). Lower temperature thermal
processes may offer more cost effective methods of retaining chlorine
within the system, for example gasification with injection of lime is
reported' " ' to retain approximately 90% of the fuel's chlorine.
5. Conclusions
Whilst burning waste and waste derived fuels for energy recovery
has and continues to be an effective waste treatment option, problems
with clinkering, boiler fouling and emissions still occur under full
combustion conditions.
Whilst some cost effective solutions are
available by improved production methods and improved combustion
control, other solutions will significantly increase the costs of using
RDF on conventional coal fired plant, particularly where stricter
emission limits are applied to RDF as compared to coal.
Lower
temperature processes such as gasification or pyrolysis are looking
increasingly attractive as a means of reducing these costs.
In terms of preparing waste for thermal treatment, full scale RDF
plants have proved the potential for significantly increasing calorific
value, energy density and the provision of fuels with consistent
handling, feeding and combustion properties.
These are all factors
which lead to substantial reductions in the cost of building and
running the thermal treatment plant compared to mass burn incineration.
The energy loss on converting raw refuse to an RDF can be restricted to
30% by effective plant design and for a range of RDF types there are
positive experiences to report on a variety of combustion plant.
Equipment requirements and processing costs for the various forms of
RDF are established in broad terms and matching fuel characteristics
with requirements for the thermal treatment stage is facilitated by the
availability of detailed analysis data and improved understanding of
the separation processes.
Raw refuse cannot be considered to be the optimum form or
composition for thermal treatment and energy recovery.
There may be
arguments as to the degree of separation and processing warranted for
the most effective overall system, but there is no doubt that
pretreatment offers excellent opportunities for improving the thermal
treatment stage as well as the opportunity to recover additional values
from the residues by more appropriate, non thermal processing methods.
71
REFERENCES
(1) DOUGLAS, E.
Derivation
of basic
efficiency
formula
for
concentration operations. Trans. Inst. Mining and Metallurgy 71
(1961-2), pp697-704.
(2) LORBER, K.E. Incineration of RDF and incineration of total waste
- comparison of emissions.
Paper to EC Seminar, Sorting of
household waste and thermal treatment of waste, Luxembourg,
Sept. 84. Applied Science, Elsevier 1985 pp208-225.
(3) VAN ROOSMALEN, G.R. et al. Heavy Metal Sources and Contamination
Mechanisms in Compost Production.
Paper to MER 3 Conference,
18-20 March 1986, Antwerp. Belgium.
(4) BARTON, J.R. et al. The Use of Database and Modelling Techniques
in Furthering Developments in Solid Haste Processing in the UK.
Paper to 23rd intersociety Energy
Conversion Engineering
Conference (ECEC), 31 July-5 August 1988. Denver, Colarado, USA.
(5) BARTON, J.R., WHEELER, P.A. The Benefits of Front End Trommelling
in Processing Municipal Solid Wastes. Trials at the Byker Plant June 1987. WSL Report LR661(MR)M, Sept. 1988, 39pp.
(6) WHEELER, P.A. et al.
An Empirical Approach to the Design of
Trommel Screens for Fine Screening of Domestic Refuse to be
published, Resource, Conservation and Recycling (1989).
(7) BARTON, J.R., POLL, A.J. Preparation and Incineration of Screened
Refuse: Preliminary Trial, Sheffield, November 1986. WSL Report
LR592(MR), March 1987, 49pp.
(8) BARTON, J.R., POLL, A.J., WEBB, M., WHALLEY, L. Waste Sorting and
RDF Production in Europe. A report prepared for the Commission of
the European Communities R and D programme - Recycling of Urban
and Industrial Waste, Barking, England. Elsevier Applied Science,
Publishers Ltd, 1985, 209pp.
(9) BARTON, J.R.
Development and Application of a Method for
Predicting and Assessing Performance of Operating Air Separators
in the Processing of Municipal Solid Wastes. Paper to EC Seminar
on Sorting of Household Waste and Thermal Treatment of Waste,
Luxembourg,
25-27 September
1984, London: Elsevier
Applied
Science, 1985 ppl09-119.
(10) ROSENBRAND et al.
The Separation Performance and Capacity of
Zig-Zag Air Classifiers.
Paper to EC Seminar, Sorting of
Household Waste and Thermal Treatment of Waste, Luxembourg,
September 1984. Elsevier Applied Science, 1985, pp208-225.
(11) ENERGY EFFICIENCY OFFICE. Combustion of Shredded Industrial and
Commercial Waste in a Circulating Fluid Bed. Project Profile 206,
Energy Technology Support Unit, Harwell Laboratory, May 1985.
(12) RAMPLING, T.W.A., HICKEY, T.J. The Laboratory Characterisation of
Refuse Derived Fuel. WSL Report LR643(MR), Dec. 1987, 186pp.
(13) BURNLEY, S.J. The ETSU/WSL Refuse Derived Fuel Combustion Trials
Programme: A Review
of Progress.
WSL Report
LR595(MR),
Sept. 1987, 33pp.
(14) BRINSMEAD, K.H. and REAR, R.W.
The Formation of Alkali-Bonded
Deposits. Laboratory Studies of the Behaviour of Sodium Chloride
during Combustion. BCURA Inf. Circular No. 134, Doc. No. C/4950.
(15) HOS, J.J. et al.
Gasification of Organic Solid Wastes in
Co-current Moving Bed Reactors. Energy from Biomass and Wastes
IV, Florida 1980.
72
CHARACTERIZATION OF CARBON CONTAINING MATERIALS WITH RESPECT
TO PYROLYSIS AND GASIFICATION
H.J. Mhlen, W. Wanzl, K.H. van Heek
BergbauForschung GmbH, Essen, FR of Germany
Summarv
From the broad use of thermochemical conversion of coal
and other solid fuels various methods have been estab
lished for their characterization with respect to pyro
lysis and gasification. The experimental techniques and
theoretical methods including those for reactor modeling
are reviewed, taking as examples those in use at Berg
bauForschung. Typical results achieved for coal and
lignites are shown, demonstrating how the experimental
devices and the theoretical background can be used to
characterize other carbonaceous materials like biomass
and wastes. The final aim is the design of new or the
optimization of existing processes with respect to the
feedstock available and the products desired.
1. INTRODUCTION
As it is expressed in the introduction to the programme
of this conference, thermochemical processing is most impor
tant amongst the available technologies for biomass conver
sion. Such processes like pyrolysis, gasification and also
combustion have been since ever the basis for industrial con
version of coal. Therefore the purpose of this contribution
will be to review the main techniques for the characteriza
tion of coal with respect to pyrolysis and gasification,
thereby showing their importance also for the treatment of
other feedstocks.
2. CONVERSION PROCESSES AND RELEVANT FEEDSTOCK PROPERTIES
First of all it has to be noticed that the term "conver
sion" is used differently in science and technology. As illu
strated in fig. 1, taking as an example gasification, it
stands in a narrow sense for the heterogeneous reactions of
carbon with gasifying agents such as ,, C0 2 , H 2 and 0 2 In
a broader meaning it denotes the gasification reactor, that
means, it includes additional processes such as heating up,
drying and pyrolysis. In some reactors, in which heat has to
be provided for conversion, also combustion may be enclosed.
Finally, conversion means the whole process, starting with
the storage of the feedstock, its preparation and ending up
with valuable products at the one hand and the disposal or
utilization of the undesired residues on the other /!/.
73
GASIFICATION PROCESS
Storage
Grinding
GASIFICATION REA CTOR

Pyrolysls
Feed
Propertles
GASIFICATION REA CTIONS
53
C H20
C CO2
C H2
Resultant
Char
and A sh
Properties
Combustion
Gas Cleaning
Residue Disposal
Fig. 1:
Different steps of a thermochemical conversion

process taking as an example g a s i f i c a t i o n
Table 1; Correlations between coal properties and t h e i r

changes in the s i n g l e process steps
PROCESS
STEPS
RELEVANT
PROPERTES
ro*
self onrtion
ODOQuOn
oging
reduction of size
reduction of swefing
ra*
~ bea hooung
release of hydrocarbon
oases aid carbon oxidei
reduction in V i l
changes in surface area
90s ond tor evolution

~ char formation
HHiMjtjtastictty
STORAGE
GRNDNG
mocera composition
mineral content
grnMtfty
PYROLYSS
mocera composition
~ demonta composition
GASFCATION
COMBUSTION
strfoce and porosKy

reactivity
minora composition
bum out
partial combustion
minera composition
seJubty of ash elements
eh/tion of traces
ra*
DISPOSAL
PACT ON
PROPERTES
P0SS8LE
EFFECTS
asmen tol composition

sirfoce and porosity
intrinsic reactivity
minora composition
shape
kitema) surface
reactivity
elomental composition
~ partial consvnption
~ ash enriched residue
changes minerals
reactivity
changes in physical structure
physical and chemical
constitution
Considering characterization of the feedstock i t has t o

be taken into account that although the properties of the s o
l i d s influence the reaction in the s i n g l e process s t e p s , they
themselves do undergo changes in them. Under t h i s aspect
74
table 1 tries to summarize the effects of the reactions du
ring storage, grinding, pyrolysis, gasification, combustion
and disposal, and the interactions with the relevant proper
ties of the in and outgoing solids. Without going into de
tails it can be stated, that there is a wide number of pro
perties to be considered as relevant to the different process
steps. Taking as an example pyrolysis these are rank, maceral
composition and elemental composition of the ingoing feed
stock. During the process condensable products (tars) gases
and char are formed. A lso thermoplasticity has to be taken
into account for a proper operation of the reactor. The con
ditions in the pyrolysis process influence shape, internal
surface, reactivity and elemental composition of the outgoing
char. In a similar way also the other process steps have to
be discussed.
To sum up: the solid feedstock must be characterized
with respect to every process step, in which generally diffe
rent properties are relevant. However, the following part
will mainly concentrate on the conversion step.
3. EXPERIMENTAL AND THEORETICAL METHODS
Course and product yields during pyrolysis and gasifica
tion of carbonaceous solids are mainly influenced by such pa
rameters as final temperature, residence time, rate of hea
ting, gas atmosphere and pressure. Most important is the
timetemperature history, which can be described by the rate
of heating. As it is shown in table 2 the technical reactor
types differ widely by the rates of heating applied.
Table 2: Classification of heating rates in coal conversion
Heating Rate
K/s
Heating Time to 1000C
* 20 min
dp = 100
Technical
Reactor Types
Coke Oven
slow
Fixed Bed Gasifier
medium
fast
5 100
10 s U min
500 100.000
10ms 2s
LRCarbonization
Entrained Phase
Fluidized Bed
flash
> 105
< 1ms
Plasmareactor
Relativly slow values of some K/s are achieved in cokeovens

or fixed bed gasifiers. There the reactions occur in hours.
Medium rates of heating are found in carbonizers like the
75
Lurgi/Ruhrgas (LR) type. Much faster heating rates are achie
ved in entrained phase and fluidized bed reactors, where the
reactions occur in less than one second. Plasma reactors ap
plying temperatures up to 3000 lead to very fast heating
rates.
In order to characterize the behaviour of the feedstocks
in thermochemical processes under these very different hea
ting rate conditions we operate three types of apparatus at
BergbauForschung as shown in table 3. In the thermobalance
apparatus a sample of about 1 g is heated up with several
degrees per minute to a final temperature of 1000 " C A s a
result from the continuous measurement of the weight loss and
gas analysis the formation of products like Ho, CO, CO,,
CJJHJJJ, BTX or tar is described, from which the kinetic
parameters can be determined as will be mentioned lateron.
For higher heating rates up to 1500 K/s the grid heater
technique is used. About 10 mg of the sample are heated on a
metallic wire net. Besides the determination of the product
formation and yields we use a high speed camera to study the
mechanical behaviour of the particles and other visible phe
nomena like ignition, duration of plasticity phases etc. Very
high rates of heating of 10.000 K/s at an adjustable final
temperature can be achieved using the Curiepointtechnique.
About 5 mg of the solid is housed in a metallic cylinder
which is heated up by electrical induction.
Table 3: Laboratory equipment for pyrolysis, hydropyrolysis
and gasification; pressure 0.1 30 MPa
thermobalance
wirenettechnique
Curiepointtechnique
dt t i f i
apparatus
Th
"t tilt t
Th
sample size
mg
1.500
heating rote
K/s
0.05
10.000
1.000
adjustable
isothermal experiments
final temperature
results
kinetics of
product formation
E.ko.n.Vo
for Hi.COx.CxH.
BIX and tar
product yield
kinetics of
particle swelling
from high speed
camera studies
kinetics of
product formation
E.ko.n.Vo
for H.COx.CxH.
BTX and tar
product yield
At its Curietemperature the metallic cylinder loses its

ferromagnetic properties and does not take up energy any
longer. Thus it stays at this temperature. From this
technique we get similar results as in the apparatus men
tioned above.
76
As a next step to scale-up we operate process development units (PDU) where the solids can be converted in kgscale. As given in table 4 these are: fluidized bed reactors
operating semi-continuously with a feed of solids between 100
g/hour and 1 kg/hour. Reactions can be performed at a
pressure of 1 to 40 bar in steam or air at maximum
temperatures up to 900'C. - For pyrolysis, gasification and
combustion entrained phase reactors operated as free-fallreactors have been built up for the same amount of coals.
With respect to hydropyrolysis the pressure goes up to 200
bar, other gasifying agents are steam and air. Also inert gas
like nitrogen can be used. The maximum temperature is 950C.
Finally, a plasma reactor is used for the conversion of
solids in the presence of hydrogen at 1 bar. The temperatures
are here extremely high up to 3000-C.
Table 4; Experimental methods applied at Bergbau-Forschung to
characterize solid feedstocks for pyrolysis and
gasifications processes
apparatus
mode of
operation
sample size
lappr.)
laboratory :
Curie-Point pyrolysis
batch
5 mg
0.1 - 200 bar (N 2 ,H 2 I

500 - 950 e C
ca. 5 > 10 4 K/s
grid heater
batch
10 mg
0.1 - 90 bar (N2,H2,air)

20 - 1000"C
ca. 103 K/s
TGA
batch
1000 mg
conditions
1.0 - 100 bar (N2,H2,H20,airl

20 - 1150eC
1 - 100 K/min
PDU :
fluidized bed
seml-contlnuous 100g/h - 1kg/h
1 - 40 bar IH 2 0,airl
600 - 900 e C
entrained phase
semi-continuous 100g/h - Ikg/h
1 - 200 bar (H 2 0,N 2 ,iirl

up to 950C
semi-continuous lOOg/h - Ikg/h
1 bar (H2I
up to 3000C
105 K/s
- pyrolysis
- gssification
combustion
plasma reactor
For the evaluation of the results in laboratory scale

isothermal and non-isothermal reaction kinetics are used
/2,3/. From the poduct formation as a function of time and
temperature kinetic data are established. Also the product
yield can be determined for pyrolysis and gasification. These
are the input data for reactor models at hand both for
fluidized bed or entrained phase reactors. The throughput and
degree of conversion calculated can be proven first in kgscale in the process development units and then be used for
the scale-up to industrial reactors.
77
4. RESULTS
The following examples for the results on coal characte
rization with respect to thermochemical conversion are mainly
taken from thermogravimetric measurements, which in combina
tion with product gas analysis has been proven to be a very
powerful method on laboratory scale. As an example for the
process development units a result from the plasma pyrolysis
reactor is shown lateron also.
4.1 PYROLYSIS
Fig. 2 presents results obtained during the pyrolysis of
a hard coal in the thermogravimetric analysis device /4/. As
can be seen from the upper diagram on the left the sample was
heated at 3 K/min from room temperature to approximately
1000'C within approx. 6 hours. The primary measuring curve
relates to the mass left in the reactor. The coke formation
per unit time can be derived from this by differentiation.
The curves of gaseous product formation are obtained by gas
chromatographic analysis performed simultaneously to the TGA
measurements. The release of higher hydrocarbon gases leads
to rather simple curves so that it may be assumed that only
one reaction is involved in their formation with possibly 3
reactions at the most in the case of CH 4 . Obviously several
reactions contribute to the generation of ,, CO and CO,.
The formation curve of tar is obtained by subtraction of the
gas formation rates from the loss of mass. Obviously tar is
formed mainly in one reaction.
moss ioss
dGimgl
tar
dllglj
CCI
water
gaseous HC
600 m
irci
io
200
too
sfa
rrci
Fia. 2; Product formation during pyrolysis of hard coal

(coal: 32 % V.M. daf; 3 K/min; 1.1 MPa, N 2 )
Fig. 3 shows how the formation of gases during pyrolysis
of coal varies with rank, ranging from anthracite to high vo
latile bituminous coal. In the cases of CH 4 , C 3 H g , CO and N 2
78
the gas formation is reduced when rank increases. Thereby the
beginning of the curves is shifted torwards higher temperatu
res indicating that during coalification functional groups
with weaker bonds are preferably reduced. H 2 0 and CO 2 show a
different behaviour: The H 2 0 curves indicate less gas forma
tion with rank. Thereby the comparison leads to the conclu
sion that all relevant groups had been reduced equally during
coalification. The CO2curves show no remarkable differences
with rank /3/.
5?Is >]
cmll
CHt
0.4
O.l
ftD
L V
1,
500
Coals :
a
700
WO
Temperature I'C I
/.V.M, maf
Heinrich
10.0
b Dickebank 19.5
Gustav
29.0
d Frst Leopold 39.5
Fia. 3; Formation of gases during pyrolysis of coal of

different rank
These gas formation curves can be fitted by a mathemati
cal model on the basis of nonisothermal reaction kinetics.
This is rather easily done if the curves are representing one
reaction e.g. in the case of C3H8. A good fit is also possi
ble if one has to assume more than one reaction. In the case
shown in fig. 4 the fitting of the measured CH4formation by
3 reactions of second order leads to the lowest least square
deviations /5/. In this way kinetic parameters for the
different products and for various solid feedstocks have been
determined. Table 5 gives as examples values describing the
kinetics of pyrolysis of a coal at 1 and 100 bar. For the
condensable products tar and benzene and the gases CH 4 , C2H6
and C 2 H 4 the values for the activation energy E, frequency
factor k o and order of the reaction are given. Without go
ing into details it can be said, that these can be well
interpreted by the mechanism of pyrolysis assuming as a first
step the thermal breaking of bonds between the aromatic
structural elements and in the case of = 2 a following
bimolecular radical reaction as rate controlling. Practical
use of these data is made in reactor modelling. Thereby the
sound physicochemical basis allows a high security for
79
extrapolation from the laboratory scale into the next higher
and, finally into the industrial one.
dV/dt
[cmV(gK|]
0.3
3 reactions 1. order
S = 0,01
3X
SOO
TOO
o measured
3 reactions 2.order
S = 0,003
single reaction 1
. . . .
i calculated
total
Westerholt
CH4
inert gas 10 MPa N2
S: standard deviation
Fig.
Different kinds of mathematical description of

measured CH 4 formation curves of a h.v. bit. coal
Table 5; Overview of kinetic parameters measured in the ther

mobalance at 3 K/min (Coal Zollverein, 32.9 %VM)
N2
pressure
10 MPa
0.1 MPa
E
tar
1)
2)
benzene
ko
8
n=1
138
7.6 10
n=1
140
2.1 10 11
n=2
142
ko
174
1.5 10 11
136
2.0 1011
6.0 10
115
2.0 10 6
149
8.0 6
214
7.8 1 0
141
5.3 10 5
3)
n=2
150
1.0 10
1)
2)
n=2
204
7.8 1 0 "
n=2
158
2.7 x 10
3)
n=2
257
1.8 10 11
C2H6
n=2
210
1.5 10 1 3
224
2.2 10 1 3
C2H4
n=2
205
2.7 10 1 3
218
7.1 10 1 3
CH 4
in kJ/mol
k0 for n = 1 in 1/min
k 0 for n = 2 in g / ( c m 3
min)
80
4.2 GA SIFICA TION
At first an example shall be shown, how temperature and
pressure influences the rate of the carbonH20reaction. The
diagram in fig. 5 is based on experimental results measured
in a TGA /6/ taking coal char. As to the influence of tempe
rature an exponential increase of the rate of reaction can be
noticed following the A rrheniuslaw. A s to the influence of
pressure the reaction rate increases in the range between 1
and 10 bar, afterwards the curves come into saturation. This
behaviour can be explained by the LangmuirHinshelwoodmecha
nism, which assumes an adsorption step in the overall reac
tion /7,8/.
Fig. 6 compares the reactivities of lignites, coals,
chars, metallurgical coke and pitch coke against steam at 40
bar depending on temperature. In all cases the rate of reac
tion is increasing with temperature as has been seen in the
previous figure. However, great differences are found for the
different solid fuels. The reactivity of the lignite is
highest, those of coals and chars have been found in a
relatively narrow range, whereby rank is not significant.
92
0
950
5
90
Fia. 5; Rate of CH20gasification depending on pressure and
temperature
Finally, coke and pitch coke, that means carbonaceous mate
rial which is treated at high temperature significantly exee
ding 1200'C, show lowest reactivity. As main factors influen
cing the scattering of reactivity, chemical structure, physi
cal structure and catalytic influence of the ash constituents
have to be taken into account. Especially the coke, treated
at high temperatures shows very low reactivity as the active
81
60
Fio.
650
6.; Chemical reactivity against H 2 0 (40 bar) depending

on coal rank and pyrolysis conditions
10" 2 g/gmin
30
10 bar, 10 /min
* Kosovo
20
Schwarze Pumpe
Rhenish
Kolubara
Spanish
10
temperature
Fia. 7: H,0reactivity of lignites depending on their earth

alkaline content
sites, i.e. the rand atoms of the microcristallite structu

res, their dislocations and the hetero atoms are annealed at
high temperature. Responsible for the high reactivities of
lignites are the catalytic active constituents of their
ashes. s Fig. 7 shows some correlation exists between the
reactivity of the different types of lignites and their con
tents of earthalcaline compounds. It is known, that these
82
are found finely dispersed in the raw samples as salts of hu
mic acids. This is a precondition for the catalytic activity
of these compounds /9/. It should be noticed, that reactivi
ties of other materials such as biomass generally are found
to be less than those of lignites. This is understandable as
catalytically active compounds are not generally found in
these materials.
4.3 PLA SMA PYROLYSIS
Plasma pyrolysis for solids has been developed in order
to produce acetylene from coal, which is thermodynamically
the only stable gas at temperatures exceeding 2500"C. Within
a project together with an industrial partner we have built a
laboratory scale plasma pyrolyser as shown in fig. 8. Between
cathode and anode an electric arc is produced. It rotates in
a field of a magnet and produces a hydrogen plasma at
temperatures up to 3000"C. Into this coal is injected and
pyrolysed. Fig. 9 summarizes some results for different
coals. The left handdiagramme shows that the acetylene yield
is rising with the specific energy input and goes up to 40 %
of the feed coal. Besides acetylene small amounts of ethylene
and CO are formed, also tar and char are obtained /10/.
Plasma pyrolysis is generally a simple technique to produce
directly acetylene from carbonaceous materials. A lso it
should be taken into account that it could be a tool to de
stroy organic compounds from e.g. liquid wastes, which are
not acceptable for environmental reasons.
cathode
w,
cool
0.1 - 1 bar
2000 - JO O O 'C
s 10 kg coal/h
s WmJH2A
s 30 MW
anode
A
magnetic coil
plasma generation
plasma pyrolysis
H20=i
quench
products
C2H2
Fia. 8; Laboratory reactor for the pyrolysis of solid
feedstock in a hydrogen plasma
83
acetylene yield
In w t - X of
feed cod (ar.)
50-1
coal: Cape Breton
Cape Breton^
(Canada)
40
3020
10-
/ / \S N Luisenthal
ffi\
(Saar)
Westerholt
(Ruhr)
1
4
1
1 6
8
4
specific energy input in kWi/tcg cool
Fia. 9: Results from laboratory experiments of plasma

pyrolysis for different coals
5. CONCLUSIONS
With respect to the aims of the Conference to improve
pyrolysis and gasification of biomass in the future the following may be concluded:
From the broad use of thermochemical conversion of coal
and other solid fuels experimental and theoretical methods
are established for their characterization with respect to
their use in pyrolysis and gasification processes. Especially
it is possible to determine the course of the formation of
different products with temperature and thereby to investigate the influence of the conditions in the reactor i.e.
pressure and kind of atmosphere and rate of heating on the
amount and composition of the product. Mathematical models
are available to improve the design of reactors and processes.
All these methods and results can be used to characterize other carbonaceous material like biomass and wastes for
the design of new or the optimization of existing processes,
with respect to the feedstock available and the products
desired.
REFERENCES
( 1)
VAN HEEK, K.H. and H.-J. MHLEN, Effect of Coal and

Char Properties on Gasification. Fuel Processing Technology, 15 (1987 ), p. 113/133
( 2) JNTGEN, H. and K.H. VAN HEEK, Reaktionsablufe unter
nicht-isothermen Bedingungen. Fortschritte der chemisehen Forschung 13 (1970), p. 601/99, Springer Verlag,
Berlin
( 3) JUNTGEN, H. and K.H. VAN HEEK, An update of German nonisothermal coal pyrolysis work. Fuel Processing Techno-
84
( 4)
( 5)
( 6)
( 7)
( 8)
( 9)
(10)
logy, 2 (1979), p. 261/93

ARENDT, P. and K.H. VAN HEEK, Comparative Investigations of Coal Pyrolysis under Inert Gas and H, at low
and high Heating Rates and Pressures up to 10 MPa. Fuel
60 (1981), p. 779/788
VAN HEEK, K.H., P. KASSLER and W. WANZL, bertragung
von Laborergebnissen zur Pyrolysekinetik von Kohlen auf
in situ-Reaktionen. Erdl, Erdgas, Kohle 102 (1986),
p. 200/205
MHLEN, H.-J. and A. SULIMMA, High temperature, High
Pressure Thermogravimetry of Coal Gasification - Apparatus, Data Acquisition and Numerical Evaluation. Thermochimica Acta 103 (1986), p. 163/168
MHLEN, H.-J., K.H. VAN HEEK and H. JNTGEN, Kinetic
Studies of Steam Gasification of Char in the Presence
of Hydrogen, Carbon Dioxide and Carbon Monoxide.
Fuel 64 (1985), p. 944/949
VAN HEEK, K.H., H.-J. MHLEN and H. JNTGEN, Progress
in the Kinetics of Coal and Char Gasification. Chem.
Eng. Technol. 10 (1987), p. 411/419
VAN HEEK, K.H. and H.-J. MHLEN, Effect of Coal and
Char Properties on Gasification. Fuel Processing Technology, 15 (1987), p. 113/133
BAUMANN, H., D. BITTNER, H.G. BEIERS, J. KLEIN and
H. JNTGEN, Pyrolysis of Coal in Hydrogen and Helium
Plasma. Fuel 67 (1988), p. 1120
85
ACTIVITIES IN THE FIELD OF BIOMASS PYROLYSIS

L. ANTONELLI
Vice President - Director of Alternative Energies Department
Kinetics Technology International SPA , Italy
Summary
Solid fuels use is becoming more and more difficult because of the
environmental problems connected with their handling and burning.
Strong efforts are carried on to develop suitable pretreatments to
overcome
handling,
combustion
and
pollution
problems.
Slurrification of fossil coal (coal-water mixture, CWM) is starting
to have a significant role in the industrial installations.
The
production of slurries based on charcoal from biomasses pyrolysis
shows specific difficulties and requires sophisticated technologies
and know-how.
The ^critical factors and the results obtained with
our production process are illustrated. The production of charcoal
slurries
on
semi-industrial
scale
and their physical and
rheological behaviour is discussed.
Evaluations
of
energy
consumption in slurry production and comparison with pit-coal
slurries is also analyzed.
1. GENERAL
Figure 1 shows the programs developed by KTI in fuels production
from biomasses pyrolysis. A ll the aspects of the production of these
alternative fuels was investigated including the ecological impact.
Figure 1 :
1. Pyrolysis process development
2. Charcoal and bio-oil utilization as fuels
3. Ecological impact (pyrolytic waters etc.)
4. Economics
In this paper the charcoal use as industrial fuel is presented.
2. CHARCOAL UP-GRADING
The use of solid fuels is becoming more and more difficult because
of the environmental problems connected with their handling, sulphur and
ashes content.
A system to overcome these drawbacks has been the up-grading of the
coal transforming it in a coal-water slurry (CWM). The advantage is to
transfer the coal in a liquid fuel eliminating the pollution problems
connected with the storage, transport and handling.
The pollution due to SOx and ashes require further treatments. The
advantages are significant and a number of large industrial plants have
successfully adopted this system of burning coal and many others are
considering this possibility.
With the target of the maximum flexibility in the use of the
pyrolysis fuels, we started a program to develop the same system of
using charcoal.
86
The difficulties of obtaining a char-slurry with acceptable solid
content are well known and are mainly due to:
- high porosity
- high surface area
- high oxygenated groups concentration on the surface area with
consequent hydrophilic characteristics
- low bulk density
On the contrary, there are interesting positive points due to the
absence of sulphur, to the relatively low ashes content and to the good
reactivity.
The program was developed in three phases:
2.1) Phase 1
Laboratory tests have been started using two different categories
of char produced in the Raiano pyrolysis plant from wood chips and olive
husks. The tests were oriented to investigate the following:
- grinding techniques
- granulometry distribution influence on
the
viscosity
and
stability
- dispersion and stabilization agent selection and dosing
- influence of the oxygen during char milling
- influence of the char pretreatment at high temperature.
The results of this first phase were:
a) The max. solid content of the char based CWM has been as high as
52% by weight, with a slurry viscosity below 1000 cP.
b) The bimodal size distribution curve of the pulverized char is
producing an unstable slurry.
c) By using a very finely ground char powder with a monomodal size
distribution, the same solid content and the same viscosity, as
for the bimodal distribution, was obtained but with
the
advantage of a very good slurry stability. Another advantage is
the simplicity of the process to obtain the monomodal slurry.
d) None of the programmed surface modifications of the char
(heating treatment, wetting, ash leaching) resulted successful
in increasing the solid content in the char-water slurry.
e) The grinding of char under controlled atmosphere of nitrogen
increases the solid content of the char based CWM by 5 to 10J
with respect to the grinding in presence of air.
It is worth noting the peculiar behaviour of the char slurries with
respect to the granulometrie distribution.
Monomodal is better than
bimodal which gives unstable mixtures.
This is due to the surface
physico-chemical characteristics which are not modified by the thermal
and chemical treatments tried during the tests.
Figures2 and 3 summarize the results obtained for four typical
mixtures prepared from wood chips char and olive husks char.
Figure 4 shows the Theological behaviour of char slurries compared
with pit-coal conventional slurries.
Figure 5 shows the Theological behaviour of two typical slurries
with micronized char. The sample containing olive husk char has a lower
viscosity.
Figure 6 shows the trend of viscosity against the temperature.
2.2) Phase 2
At this stage of the program, the experimental work was transferred
from laboratory to pilot plant. The main targets were:
- Reproduction of the best lab results;
87
Mixture type
Mixture no.1
Coarse particles/fine p.
Char theoretic content in
the final mixture (% weight)
Dispersing agent (J weight)
Char content in the final
mixture (% weight)
*
**
Mixture no.2
(*)
Mixture no.3
(")
60/40
60/40
60/40
44,9
0,7
46,7
0,7
49,7
0,7
46,9
48,8
51,9
grinding in air
grinding in nitrogen atmosphere
Fig. 2. Solid Content in the Different Aqueous Slurries

Obtained from Wood Chips Char
Mixture type
Mixture no.4
()
Coarse particles (wt) /fine p. (wt)

Char theoretic content in the final mixture (% weight)
Dispersing agent (% weight)
Char content in the final mixture (J weight)
*
60/40
46,7
0,7
48,7
grinding in nitrogen atmosphere
Fig. 3. Solid Content in the Olive Husks-Char Water Mixtures
2.0
1.8
1.6
\
TOTBWTUTC 20 ' c
1.4
^\
1.2
1.0
0.8
ArU53
- W R T W T " ^ m
, . .,
* * * * * * auwr w.tr saio
0.6
AQUEOUS SLURRT WITH OUR FRUI CLIVE HJSKS (48.TTC U.CF SOLIDI
0.4
0.2
n.n
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
9AR RATE 1/S
Fig. 4. Charcoal Based Aqueous Slurry and Pit-Coal Water Conventional Slurry
88
- Better understanding of the influence of the granulometry;
- Investigation of the influence of the milling equipment when
operating at a scale which can be correlated to the industrial
dimension;
- Acquisition of data related to the energy consumption for the
milling and mixing stages;
- Definition of the best conditions for increasing the solid
content above the limits reacted during the lab tests.
A campaign of tests was carried on using a wet milling in single
stage.
The simplicity of this scheme is very attractive for an
industrial application.
The investigation on the bimodal distribution can be done adding a
coarse fraction prepared separately. The additive is the same used in
lab tests. The milling is done in the presence of air. Characterization
of typical samples can be summarized as follows:
Solid content
Values higher than those on lab scale are obtained, concentration
around 55-56J can be produced with micronized char.
Slurries viscosity
The samples produced in the campaign have a viscosity in the range
600-2000 cP at 30 deg.C, compatible with the pumpability requirements.
Furthermore the behaviour is pseudoplastic with significant advantages
in industrial application.
Figures 5 and 6 show the Theological behaviour of some samples.
Figures 7 and 8 Show the granulometry distribution of the same
samples.
Slurries stability
A series of slurries produced during the tests have been stored in
drums and the tendency to solid dcantation and water separation checked
every 2/3 days. With the same frequency all samples have been roughly
mixed by hand. After forty days, the Judgement on the most significant
sets of samples can be summarized as follows:
E1 very good
E3 excellent
Ek very good
E5 good
E12 acceptable
In any case, th analysis of the results shows that all the
products can be used in an industrial plant if midly mixed with a daily
frequency as it is normally done in all the installations using CWM.
2.3) Phase 3
Since the max. content of solid obtained using only char was 5556J, even using micronized powder, another line of investigation was set
up trying to produce slurries with char and pit-coal.
The basic concepts at the basis of this approach are:
- The pit-coal can be used for CWM production having solid content
up to 65-70J.
- The combination of the two coals makes possible to reconsider the
utility of the bimodal distribution using the pit-coal only for
the coarse function.
- The dilution of the polluting components (sulphur) makes possible
89
2.0
TEM"ERATURE 20 ' c
SOLID CONTENT IN BOTH SLURRIES 52Z W.
1.8
1.6
1.4
MONOMODAL (FINE SIZE}
12
CHA R POVCER FROM WOOD CHIPS
1.0
0.8
0.6
ItICtCOAL
04
(FINE SIZE)
CHA R POWDER FROM OLIVE HUSKS
0.2
0.0
1
20
40
60
80
100 120 140 160 180 200 220 240 260 280 300
SHEAR RA TE 1/S
Fig. 5. WaterCharcoal Mixtures Viscosity
1.6
1.4
SHEAR RATE 100 m'
1.2
1.0
0.8
0.6
0.4
0.2
20
1
40
i
60
80
1
100
TEMPERATURE
Fig. 6. Viscosity Related to Temperature for WaterWood Chips Char Mixture
"c
90
the utilization of large quantities of piteoai remaining in the
limits imposed by the antipollution regulations.
The new system consists in incorporating a fossil charcoal having
an average granulometry of about 45 microns in a micronized pyrolytic
coal slurry (dm. 1216 microns). Such procedure will permit to obtain
the following advantages:
Higher solid content in comparison with the pyrolitic carbon
slurry only.
Lower energy consumption in comparison with the completely wet
procedure.
Better fluidity with the same concentration, due to the bimodal
distribution.
Lower sulphur and ash content in comparison with the two separate
components.
It is also possible to foresee advantages in the plants operations;
for example the char slurry production will be done in the pyrolytic
plants spread in the territory, the fossil carbon grinding and its
incorporation in the micronized char slurry will be centralized close to
the power station which uses the fuel.
The operative diagram of such production is the following:
PYROLYSIS PLANT
POWER STATION
Production of
micronized char
at 50*
Grinding of fossil
coal at 45 microns
^
>
Transport to the
power station
Mixer
High concentration
slurry
'
Burner
Experimental work
A first campaign of samples production was carried on obtaining
slurries with 60J of char and pitcoal. The ratio between the two coals
is 60 and 40?
char. The coarse pitcoal is added to the char slurry
(50). The behaviour is Newtonian, the resulting slurries have a LHV
of 4000 Kcal/kg and are usable as fuel in a burner.
A second campaign aiming to increase the solid content to 65J is
carried on with a ratio char/pitcoal 40/60; 50/50 and 54/46. Analysis
of the produced samples show increasing viscosities.
With small
adjustments on the additive quantity, which is increased to almost 1J
the slurries obtained are good and usable in a burner. The HV is higher
than 4500 Kcal/kg.
In conclusion, this second group of samples confirm the possibility
of producing mixed slurries with 65 solid and good viscosity stability
and comparable with the pitcoal slurries.
The final experiments tried to increase furtherly the solid content
above 65%. The result was that it is still possible to reach 69/70% but
the viscosity is high and at the limits of acceptability for industrial
applications.
91
3. ENERGY CONSUMPTION
The energy consumption registration shows that during all the tests
the
milling process was regular without big variation in power
absorption.
Indications were also obtained for the
consumptions
expected on industrial mills with capacity 10/100 times higher. Figure 7
summarizes the results obtained on pilot plant:
Figure 7
Run
Energy consumption
KW
Slurry flow
Kg/h
2,2
2,1
2,2
1,9
(35? di E1 + 65?
E1
E3
EU
E5
E12
Legend: pilot mill
a
b
A
B
=
=
=
=
Char flow
Kg/h
15,3
20,4
18,2
16,7
di E2)
7,81
10,52
10,51
10,75
consumptions
consumptions
consumptions
consumptions
referred
referred
referred
referred
Consumption KWh/t
a
b A
B
86
62
73
68
58
to
to
to
to
170
120
125
106
114
43
31
37
34
29
85
60
63
53
57
slurry
char
slurry
char
The experience matured on pitcoal allows to foresee a reduction of

4060? of the figures shown in A and B when using industrial scale
equipment.
A further reduction can be obtained using multisector ball mills
for which the above experimental results allow a forecast of 2540 KWh/t
of slurry which with a solid concentration of 56? gives a consumption of
only 4570 KWh/t of dry charcoal.
1500
E12
E2o
1000
E1,
*^^^_
* ^^*^^
500
E3.
50
150
200
250
100
Fig. 8. Different Samples Viscosity at 30C
92
4. CONCLUSIONS
The case of the process investigated in this program allows the
production of excellent slurries with a solid content of 65>. Higher
concentrations are technically possible but not usable in industrial
burning systems. The resulting slurries have roughly 50J char, 50 pitcoal with a LHV above 4000 Kcal/kg.
Figure 8 shows the Theological behaviour of some typical products.
Energetic consumption: taking into condlderation the products with
solid (char/pit-coal 50:50), the energy consumption is 35 KWh/t of
slurry or 54 KWh/t of solid including the milling stage. The same value
for slurries with only pit-coal is 70 KWh/t of slurry with 70J solid or
114 KWh/t of coal. This calculation are relative to a slurry production
of 20 t/h.
93
BIOMASS FUELS AND GASIFICATION
J. CARRE, L. LACROSSE, Y. SCHENKEL
Center for Agronomical Researches (CRA)
Unit."Biomasse"
5800 GEMBLOUX, Belgium
F. RURIHOSE
Universit Catholique de Louvain (UCL)
Unit "TERM"
1348 LOUVAIN-LA-NEUVE, Belgium
Summary
Fixed bed downdraft gasifiers have specific requirements on fuels .
This paper considers the different fuels characteristics that are necessary to obtain an optimal gasification : moisture, mineral and volatiles contents, size, bulk density,...
The densified products quality is also considered, particularly their
cohesion . Specific testing methods have been developped at the CRA .
They allow to fix quality limits for these products .
1. INTRODUCTION
Many important studies have been carried out on gas producers designs.
The gasified fuel has often been neglected . Indeed, a well-designed gasifier will never work with fuels that do not have a minimum quality .
This paper presents the quality limits that fuels must have to be successfully gasified in fined bed downdraft gasifier .
2. FIXED BED DOWNDRAFT GASIFIERS REQUIREMENTS ON FUELS
2.1. Moisture content
The fuel moisture content is of prime importance for the success of
the gasification process . The negative influence of water can be noticed
at different levels :
- the lower heating value (LHV) of lignocellulosic material decreases when
the moisture content increases .
Considering that ashfree dry biomass LHV is about 18.8 MJ/kg, the LHV of
wet biomass becomes :
THV
-IflS
100
LHV
1 8
100 + H
H -
LHV
2
2
(1)
100 + H
= wet biomass lower heating value (in MJ/kg)
H
= moisture content (% dry basis)
For instance, ashfree biomass containing 20% moisture content (dry basis)
would have a LHV :
LHV H = 18.8 y|g - 2.5 - ^ = 15.25 MJ/kg
94
water in excess induces the hearth cooling . The resulting temperature does
not allow the cracking of the heavy hydrocarbons coming from the pyroli
sis zone of the gasifier . Moreover, the water itself is not cracked and
will condense later in the cooling and cleaning system .
it must also be said that, thermodynamically, it is always more interes
ting to gasify as dry as possible fuels .
Indeed, the gas LHV and the gasification efficiency quasilinearly de
crease from 0 to 50% moisture content (see fig. 1) .
The hydrogen and methane gains in the gas do not compensate the carbon
monoxide losses (see fig. 2) .
100
40
o CO
35
90
CO,
30
80
Q 25
70
g 20
60
1 15
10
50
5
______**
40
10
20
30
40
50
MOISTURE CONTENT (%, d.b.)

Fi g . 1 : Gasification efficiency
and gas LHV as functions
of moisture content
10
20
30
40
50
MOISTURE CONTENT (%, d.b.)

Fig.2 : C0,H , CH4 and C0 2
contents in the gas as
functions of moisture
content
2.2. Mineral content

The fuel mineral content must be as low as possible . It also affects
the LHV . Introducing the mineral content in relation (1), it becomes :
LHV,,
18.8
100 MC
100 +
2.5
100 +
MC = mineral content (% dry basis)

For instance, biomass containing 20% moisture content and 10% ash con
tent, would have a LHV :
LHV = 18.8
100 10
120
20
2.5 y|^ = 13.68 MJ/kg
95
Moreover, the mineral content can make the gasification impossible .
Indeed, the temperatures that are reached in the hottest zone of fixed bed
downdraft gasifiers are often higher than the biomass ashes melting points.
When the mineral content is too high, clinkers will progressively appear
in the hearth . They will finally prevent the gas from passing through .
Usually, it is considered that higher than 5% mineral content, it is
nearly impossible to avoid clinkers formation . But it is dangerous to generalize : following the mineral composition, melting happens at more or
less high temperatures . For instance, the presence of alkali oxides can
induce eutectics formation at relatively low temperatures .
For exemple, the mineral content of rice husks is about 20-25% with
more than 90% silica (Si0) . The latter has a melting temperature of
about 1700C . If it was alone, the risks of melting would be very little.
Unfortunately, it is principally accompanied by kalium oxide (K.0) but also by Mg, Al, Ca, Fe, Na oxides . It results a much lower melting temperature .
2.3. Volatiles content
The biomass volatiles content may not be considered as a limiting
factor . Fixed bed downdraft gasifiers must actually be designed in order
to crack the tars and heavy hydrocarbons liberated in the pyrolises zone .
However, it must be noticed that thermodynamically, biomass must not
only be as dry as possible (cfr supra) but should also ideally undergo a
thermal treatment (torrfaction) .
The gasification efficiency is optimal for dry biomass having lost an
equivalent of 20% moisture content (see fig. 3) i.e. biomass with a formula of about C L . 0. , .
0.9 0.4
100
Gasification efficiency and gas LHV

evolutions as functions of moisture
content or pyrolisis level
96
2.4. Size
The optimal size for a fuel that has to be gasified depends on the
gasifier hearth dimensions . It must be such as to allow an optimum air/
fuel contact .
It is generally considered that the length of the fuel must be between
1/10 and 1/5 of the hearth diameter . Out of these values, problems of irregularities in the gasification process can occur :
- too long fuels can generate bridges preventing the fuel from flowing down
to the gasifier hearth . The gasification reaction can tend towards combustion by air excess .
- too small fuels cause high pressure drops by forming a kind of airproof
cake .
For small size fuels (sawdust, agricultural residues,...) densification
can be a solution but the densified products must be of prime quality
and answer some criteria (see below) .
2.5. Bulk density
The fuel bulk density directly influences the gasification velocity
and the residence time of the fuel in the gasifier hearth . If the bulk
density is too low, it is difficult to maintain gasification reactions .
The air excess also turns gasification into combustion .
2.6. Ultimate analysis and heating value
If the only organic material is considered, it may be said that the
different kinds of dry biomasses more of less have the same composition in
carbon, hydrogen and oxygen : C = - 50%
H = I 6%
0 = - 44%
It corresponds to a formula of CH. ,, 0. .. and a lower heating value
c U T
1.44 0.66
of 18.8 MJ/kg .
The latter mainly varies with the moisture and mineral contents (cfr
supra) .
2.7. Densified products quality
Densified products generally answer the above quality criteria .
Indeed, their moisture content is low (<10%) and their density is high .
Moreover, it can be possible to adapt their size to the gasifier hearth
dimension .
But another quality must absolutely be satisfied : cohesion
Researches carried out at the CRA allowed to develop testing methods
in order to determine this parameter .
This methods are described by Carr et al. (1984) .
The most important are the ones concerning the measurement of :
the density after different conditionings
the rate of volume change in immersion
the friability index after different conditionings
the elongation and swelling at 20"C 95% RH
Table 1 give the quality limits corresponding to these tests .
97
800
Density at 20C 65% RH (kg/m3)
3
Density at 20C 95% RH (kg/m )
1200
//
77
50
100
075
Rate of volume change in immersion (% min)
0-5
Friability index at 20C 65% RH
Friability index at 20C 95% RH
y/A0 3
.
10
10
25
WZ
Swelling at 20C 95% RH (% initial diameter)
Acceptable
25
VM
Elongation at 20C 95% RH (% initial length)
Bad //////
05
Good
Table 1 : technical prescriptions for densified

fuels to be gasified
3. CONCLUSIONS
When a gasification unit does not work properly, the gas producer,
i.e. the technology is more or less always suspected .
Actually, the operators are very often responsible for the problems
that occur . One of the reasons is that they are careless about the fuel
characteristics : the gasified biomass is too wet, or bad calibrated, or
contains too much inorganics .
They too often forget that downdraft fixed bed gasifiers require very
good quality fuels .
It may be said that the respect of the above prescriptions must allow
to avoid many important problems and to have a good working of the gasifi
cation installations.
REFERENCE
CARRE, J., HEBERT, J. and LACROSSE, L. (1984) Critical analysis of the
dry process improvement of ligneous materials for energyproducing pur
poses . Final report CEC (DG VIII)CRA, 245p.
98
USAGE OF CARBON BLACK AND ACTIVATED CA RBON

IN RELATION TO INPUT AND TECHNICAL ASPECTS
OF THE PYROLYSIS PROCESS
B. Bilitewski, G. Hrdtle, K. Marek
intecus
associated engineers for environmental protection technologies
Berlin
SUMMARY
A variety of pyrolysie char made of domestic waste, biomass, sewage
sludge, plastics, rubber etc., has been examined in regard to its
usage as combustible, carbon black and activated carbon (1).
Pyrolysis char made of plastics and waste tyres has a high content
of carbon and a low content of ash and thus it is very suitable as
carbon black to enrich low and medium rubber qualities

a colour pigment in printing ink, colour and plasticsindustry
activated carbon for waste water purification
But in spite of the different possibilities to be used pyrolysis

char still has not been produced and commercially sold. The
examination shows that the raw material cannot be sold without a
further treatment, for example the enlargement of the BETsurface.
1. INTRODUCTION
The degasification of waste tyres produces char with a greater or
lesser carbon content. It is essential to find a suitable method of re
utilizing this product if the pyrolysis process is to be applied
economically. Particularly the pyrolysis char obtainded from waste tyre
degasification appears to offer a number of interesting possibilities.
With a pyrolysis temperature of 700 C and a retention time of 50
minutes, we obtain a residual char content of more than 40 by weight,
with an upper heating value of approx. 31,400 KJ/kg and a carbon content
of approx. 87 by weight. Cocombustion trials of this char with
mineral coal have yielded positive results, although the high sulphur
content (2.8 by weight) constitutes a considerable problem. Orienting
tests to determine the suitability of the char for application as acti
vated carbon, as carbon black for vulcanistes, as pigment or in the
printing ink industry have shown that the pyrolysis char cannot be
satisfactorily reutilized without further treatment.
99
2. ACTIVATED CARBON AND ITS APPLICATION
Pyrolysed waste tyre char can be effectively activated with steam
in a temperature range of 750 C 950 C. Fig. 1 shows the internal
surface area of the different sorts of activated carbon as a function of
burnoff. By burnoff, we mean the gasified portion of the carbon in the
char, expressed as a percentage (1). The symbols used mean: A700, A700P
A waste tyres, 700 pyrolysis temperature (C), t 10 pyrolysed for
10 minutes, t max pyrolysed for 2 hours, where no retention time
given, pyrolysed for 50 minutes. in powder form, AH waste tyre
char from the fluidizedbed reaktor at the University of Hamburg, Prof.
Dr. V. Kaminsky, K sewage sludge, Sp paper mill waste.
tm^/g] infernal surface area

600
A70o',f=10
A700V
\ /
400
yv
A550
iÂ700P
A700.t= max
Sp700
200
TV^r
K 700
r\AH
20
40
60
80
1001%]
burnoff
Fig. 1 Internal surface area of the different sorts of activated carbon

as a function of burnoff (Nz isotherm) (1)
It is evident that neither sewage sludge nor paper mill waste are
suitable for the production of activated carbon. Other important factors
for the possibility to use char as activated carbon are temperatur,
reactor type and the retention time of the pyrolysis of waste tyre.
Temperatures around 700 C and retention times around 1015 minutes
during the pyrolysis process are advantageous for the production of
activated carbon. The fluidized bed reactor (AH) however produces char
which is not as suitable as the char in a rotation drum.
Our results show that the theoretical considerations borrowed from
coal gasification (2) are applicable to the partial gasification of
waste tyre char within the limits of permissible variation. This means
that the characteristics of the activated products can be calculated as
a function of burnoff, where the cavity structure of the feed char is
known. The correctness of the postulate can also be verified qualita
tively by the change in the pore distribution in the adsorption and
macro pore structure as a function of burnoff.
Fig. 2 shows the differential radius distribution of the adsorption
pore structure for activated carbon from waste tyre char with varying
burnoff characteristics.
To begin with, the char has narrow pores which expand to produce
larger pores in the course of partial gasification at higher burnoff
values. The maximum number of pores is reached at about 200 A.
Comparable samples of activated carbon from mineral coal have their
maximum number of pores at 100 A and less. For this reason, such
commercial activated carbon has a considerably greater internal (BET)
100
surface area (Hydraffin BS 12 - 1200 m z /g) with the same total pore
volume as activated carbon from waste.
radius [l
Fig. 2 Differential pore radius distribution for activated carbon from
waste tyres with varying burnoff characteristics
Activated carbon was contacted with the test substance phenol dissolved in water until an equilibrium condition was reached. As phenol
frequently occurs in waste water, it constitutes an interesting test
substance for waste water treatment. There are two standardized methods
for tests using phenol: the DIN standard test method 19 603, which
governs the determination of the isotherms using powdered activated
carbon in a mechanical shaker with an input concentration of 10 mg/1;
and the AWWA standard test method, according to which the phenol
adsorption of a layer of granulated activated carbon is determined when
subjected to a phenol solution flow.
The adsorption equilibrium was determined by contacting phenol dissolved in water at a fixed input concentration with a predetermined
quantity of activated carbon. If the carbon remains in equilibrium with
the solution for a sufficiently long period, and no further changes in
the adsorption behaviour are detectable, we speak of an equilibrium adsorption. The concentration corresponding to this state is known as the
equilibrium concentration. The equilibrium adsorption Q Q is defined as
the quantity of the test substance in mg that can be adsorbed from the
solution per g activated carbon:
101
(CA.
Ce)
(mg/g)
M
Qo
V
M
CA.
Ca
equilibrium adsorption (mg/g)

volume of solution (1)
quantity of carbon (g)
input concentration (mg/1)
equilibrium concentration (mg/1)
As adsrbate a phenol solution with an input concentration of 10

mg/1 and a bath volume of 10 litres was used. The char sample weighed 1
g and was subjected to a constant flow of phenol solution. The concen
trations of the solutions were measured continuously with an ultraviolet
spectrometer, and the adsorbed quantities calculated in accordance with
equation above. Generally speaking, phenol adsorption is increased by a
factor of 8 through an activation process (850 C and 30 minutes). By
way of comparison, the commercial activated carbon Hydraffin BS 12 was
also tested. The equilibrium adsorption condition is reached between 16
and 20 hours, whereas Hydraffin reaches an equilibrium condition after
only 6 hours.
The slope of the equilibrium isotherms, at the same input concen
tration and with a constant quantity of solution, is determined by
altering the weight of the samples of activated carbon and plotted in
terms of loglog coordinates (fig. 3 ) . Fig. 3 shows the phenol
adsorption capacity of activated carbon from waste tyre with different
burnoff characteristics as a function of the residual concentration.
lwt%) phenol adsorption
5.0
2.0
5,0
10 (mg/Il
residual concentration of phenol
Fig. 3 Representation of phenol adsorption as a function of the residual

concentration in terms of loglog coordinates
102
twt %] DCadsorption
5
:
A 700,til0
B12,
OW
3
Sjp*
fop
A700F
1
0,7
0,5
0,3
1
0,2
30
50
100
200 300
[mgDC/l]
Fig.4 Dissolved carbon adsorption from waste water as a function of the

residual concentration in terms of loglog coordinates
Taking, on the basis of this figure, the phenol adsorption capacity
(in 2 by weight) for a residual phenol concentration of 1.0 mg/1 as a
criterion for assessing the activated carbon, the high quality of the
waste tyre char is confirmed by increasing burnoff. The capacity of the
carbon increases with higher burnoff as the almost parallel moved slope
became steeper and the adsorption capacity went down.
The reference carbon samples Hydraffin 214 and BS 12 showed very
good results. With a residual phenol concentration of 1.0 mg/1, we ob
tain, a phenol adsorption capacity of 9.8 for Hydraffin 214 and 4.6
for Hydraffin BS 12. Because of a steep gradient both of these activated
carbon samples can only be applied successfully in a relatively narrow
concentration range.
Adsorption tests designed to demonstrate the characteristics of
activated carbon cannot be limited to the adsorption of suitable test
substances. An orienting study was therefore carried out in which
granular and powdery carbon samples were produced from waste tyres and
tested together with two commercial activated carbon samples. In a
laboratoryscale sewage treatment plant the carbon was added to the
activated sludge tank in accordance with the biocarbon process. First of
all, the isotherm was plotted on the basis of tests using a mechanical
shaker. Fig. 4 shows the adsorption isotherm for waste water which has
not been subjected to biological preclarification, when tested in con
junction with the four different carbon samples. The input concentration
of the waste water measured CA. 145.3 mg DC/1. The curves obtained are,
as far as the gradient is concerned, comparable with the results
obtained by Franke et.al. (3) for activated openhearth carbon and waste
water treatment carbon.
103
[%] reduction
100
IJ [%) reduction
100
90
A700P
80
70
... A 700,*10
214
,'
y~)
BS12 \
' .
o
2
* X ^
60
without carbon
y^
50
30O[mgO2/l]
BSB5input
Fig. 5 Percentage BOD reduction

plotted against BOD input with
and without carbon
1000
1500
2000
2500
3000 [mg/I]
K2&2O7input
Fig. 6 Percentage COD reduction

plotted against COD input with
and without carbon
On the basis of the gradient, it is possible to describe the be

haviour of the carbon in activated carbon filters. Gradients greater
than 1 result in separating factors of more than 1, and thus cause an
unfavourable equilibrium. In the case of isotherms such as those in fig.
4, complete removal of the substances in a filter is likely to prove
difficult owing to the unfavourable equilibrium. However, it is obvious
form the curve that the powdery activated carbon A700P from waste tyres
demonstrates the most favourable characteristics.
In fig. 5 and 6 the performance of the carbon sample A700P is con
firmed. Here the percentage BOD and COD reduction is plotted against the
BOD and COD input and compared with the biological
BOD and COD
reduction. With the help of the activated carbon, the biological BOD and
COD reduction can be increased by approx. 1025 depending on the type
of carbon tested.
3. CARBON BLACK AND ITS APPLICATION

The utilization of residues of the pyrolysis of waste tyre as a
filler in the rubber industry is very important. Their utilization as
industrial black carbon for low technical rubber articles is undeniable,
but the most important field of application would be the utilization of
residues as enrichment fillers in the production of tyres. We examined
the following possibilities at the TUBerlin:
black carbon from the pyrolysis process as halfenrichment
black carbon SRF or GPF
black carbon from the pyrolysis process as fullenrichment HAF
black carbon, as it is for example used for the top surface of
tyres
Fig. 7 shows the characteristics of black carbon of the pyrolysis
of waste tyres in comparison with normal black carbon as it is used for
the vulcanisation of tyres. The mechanicaltechnological results are re
presented as a function of the temperature. The statement can be made
104
that the property of all used black carbon don't correspond to the
standard. The same results have been achieved in Japan by Kobe Steel,
Ltd. (4).
But in case of lower temperatures the black carbon quality
generally became better.
Another field of application which we examined concerns the black
carbon pigment in the production of printing inks. In a company for
printing ink in Berlin we examined the possibilities of utilization of
black carbon from the pyrolysis process of waste tyres for book,
offset, newspaper rotary and heliogravureink. Only one examined black
carbon met the requirements for the newspaper rotary print. The particle
size distribution, the adsorption capacity of oil, the set behaviour and
the swelling time corresponded the usual commercial requirements. The
ink proved to be slightly more blue than normal printing ink. The
intensity of ink of black carbon usually becomes better the smaller the
particle size granulation is and can be improved by a corresponding
treatment.
tear strength
abrasion
[ N/m]
[ mm ]
HAF
QPF
HAF
>
500
600
700
800
BOO
C]
900
elongation
600
700
900
C]
tensile strength
[ ]
[ M * N/m]
15,
HAF
GPF
500
eoo
700
eoo
eoo
I* C]
Fig. 7 Impact of pyrolysis temperatur on the physical property of vul

canisation products in comparison with two commercial(HAF, GPF) carbon
blacks.
105
REFERENCES
1. Bilitewski, .: Gezielte Herstellung von Adsorptionskoksen aus Abfl
len fr die Abwasserreinigung, Dissertation, TUBerlin, 1980
2. Juntgen, H.: Gezielte Herstellung von Adsorptionskoksen fr die Was
ser und Luftreinigung, Habilitationsschrift, Universitt Heidelberg,
1966
3. Franke, F. H., Motadi, M., Bohnke, B.: Forschungsbericht des Landes
NordrheinWestfalen, Nr. 2678, Westdeutscher Verlag, 23 pp.
4. Kawakami, S. ; Inone.K.; Tanaka.H.: Pyrolysis Process for Scrap Times
in American Chronical Society 1980
106
RAPPORTEURS REPORT ON SESSION II

Catherine Esnouf
Cemagref
B.P. 121
92164 Antony Cedex
France
PRESENTATIONS
Introduction
This session was concerned with feedstock variety and its adaptation to
thermochemical processes; two very different examples of charcoal valorization
were also presented.
Feedstock Characteristics
The diversity of feedstock was emphasised as being the most important
point, as the feedstock determines the process used and the products obtained.
This was clearly shown throughout the conference.
Feedstock diversity
Not only do different raw materials have to be considered, such as
agricultural waste, wood, refuse etc., but also the different characteristics of those
raw materials. Wood, for instance, is affected by the type of forestry it comes from,
the parts of the tree that are collected, and the harvesting techniques, giving rise to
as many products as there are processing lines.
This gives very different costs: wood from 48 ECU/dry t to 70 ECU/dry t;
agricultural waste 25 ECU/dry t; and municipal solid waste from 34 ECU/dry t (wet
fluff) to 53 ECU/dry t (dry fluff) and 65 ECU/dry t (pellets:RDF) without considering
disposal credits.
Feedstock influence on thermochemical processes
A detailed study has been conducted on coal, showing the influence of
chemical and physical structure, as well as mineral matter content. Experimental
and theoretical methods have been developed to link feedstock composition to
process, and the use of such methods has been proposed for biomass and wastes.
The main parameters influencing biomass gasification were presented, for
example moisture and mineral content, size and bulk density, volatile content, and
their effects on gasification were emphasised.
Pretreatment
Feedstocks may need pretreatment to improve the subsequent process, but
it must be remembered that it involves additional cost. With regard to biomass, a
critical study on densification for gasification was presented, showing that good
and bad methods exist. The minimum cost of pelletisation is US$100/t.
107
Municipal solid wastes (MSW
Pretreatment of municipal solid wastes (MSW) should include as few steps
as possible as set by the feedstock and the required output of the plant. In this
respect, several critical steps are recommended for any plant recovering energy:
liberation and screening; magnetic separation; and coarse shredding - these
operations give separation of the fines, oversize putrescibles and ferrous materials.
These are steps with high mass and energy efficiency which provide better plant
performance and improved energy recovery. Their viability is due to the low cost of
implementation.
The manufacture of refuse derived fuels (RDF), however, is often much more
questionable: it entails a high cost and complex process and a market for the
products has to be found.
Charcoal valorisation
Two different strategies for charcoal valorisation were reported:
(i) A large scale biomass project was presented in which charcoal-coal-water
slurries have been manufactured for burning in power stations. Compared to
coal slurries, the reduced energy needs and absence of sulphur are
advantages. The production cost was reported as US$25/t.
(ii) A project using wastes as feedstock for the specific markets of carbon black and
activated carbon was also presented. The effect of products specifications on
pyrolysis conditions and the importance of the feedstock were reported as major
considerations. An acceptable activated carbon was obtained in a three-step
process, but the carbon black produced was not of an acceptable standard so
that new markets had to be sought for the product.
Strategies of the latter type are more short-term as they provide answers to
environmental concerns and could therefore quickly prove profitable. Short-term
opportunities for pyrolysis and gasification mean, therefore, that diversification is
necessary such as looking for feedstocks that could match market needs through
appropriate processes.
DISCUSSION
Feedstock characteristics
A discussion took place on moisture content relating to the presentation by
Dr Lacrosse:
what is the influence of water?
Is it the same on every process?
Is it right to suggest zero moisture content as the optimum?
It was agreed that it depended on the process: gasification uses water for the
shift reaction and the performance improvement versus cost of removal of the last
remaining moisture is disputable. For pyrolysis, with water being produced in the
reaction, the less moisture content in the feed the better. On the optimum
gasification efficiency presented for partially carbonised (torrified) wood, Dr
Lacrosse said that it was the result of a theoretical computation, no experiments
having been performed. Mr Bonino stated that this was confirmed by his own
experiments.
108
Pretreatment
The discussion focussed on the briquetting technology for gasification where
it was asked what technologies had produced "good" and "bad" briquettes. Dr
Lacrosse replied it was very difficult to give a general answer, the methods being
as important as the equipment used. Generally screw extruders gave the best
results, but a small number of tests in a piston extruder in carefully controlled
conditions proved to be better on one occasion. It was suggested that a good
characterisation method for pellets was the measurement of mechanical strength at
high temperature.
Questions were asked on the cost of such pretreatment. Dr Lacrosse replied
that it depended greatly on the feedstocks, whether it had to be dried and/or ground
before compression. Whichever method was used, a minimum cost of US$100/t
was incurred reaching up to US$150-200/t.
Charcoal Characteristics
Questions were asked on lignite behaviour and whether the evolution of
reaction rate as a function of temperature and pressure were the same as those
presented for coal char? Mr van Heek replied that no systematic study had yet
been conducted, but that one has to be very cautious on extrapolations from one
feedstock to another. For instance in the case of ash content, carbonate formation
in the case of lignite leads to a reaction rate decrease with pressure increase.
With reference to the specific uses of carbon as higher value products,
questions were put forward concerning the value of the carbon black. Mr Bilitewski
stated that for an acceptable carbon black to be obtained, specific reaction
conditions had to be used in tire pyrolysis. The cost of making good carbon black
was 200-350 DM/t (1985 figures). For activated carbon, the process is more
complex and results in a production cost of 1200-1400 DM/t. Dr Roy, from the
University of Laval, indicated that in his process of vacuum pyrolysis, the resulting
char from tires had a better homogeneity but that the steel should be eliminated in
order to avoid catalytic formation of pyrolytic carbon.
Examples were requested of large scale uses of char-water slurries as well
as information on the economics of the process. Mr Antonelli stated that current
slurry usage concerned coal slurries; two large scale boilers in the petrochemical
industry presently use these slurries in Italy. Huge projects for coal slurry use exist
in the USSR, as slurries allowing the transport of coal in pipelines. As for the
economics, the last evaluation indicates a total production cost of 30-40 Lit/kg, i.e.
US$25/t; with the cost approximately equally distributed into operating cost, capital
cost amortization and energy cost. It was emphasised that charcoal use in
combination with coal in slurries permits a reduction in sulphur content.
Economics
In conclusion, the chairman asked Dr Bridgwater whether he could give a
breakdown of the biomass costs presented into labour, capital, and energy costs,
so that this could be extrapolated for developing countries as very high costs in
Europe compromise short-term energy uses through pyrolysis and gasification. It
was explained that the major costs are labour and capital and therefore
extrapolation must be carried out cautiously because if labour is expected to be a
lower cost, equipment could cost more or even be unavailable, even without
considering maintenance problems.
SESSION III
PYROLYSIS, GASIFICATION AND LIQUEFACTION TECHNOLOGIES
Ill
BIOMASS GASIFICATION:
PAST EXPERIENCES AND FUTURE PROSPECTS
IN DEVELOPING COUNTRIES
Matthew S. Mendis
Industry and Energy Department
The World Bank
Summary
This paper presents an overview of the history, technology and use of
small-scale biomass gasification systems in developing countries. The
experiences to date have been mostly disappointing due to several
reasons including: inappropriate technology and standards for developing
countries; use of unacceptable biomass fuels; lack of trained operators
and infrastructure support; lack of adequate user incentives; and
finally, marginal economics.
Recent developments in utilizing
ferrocement instead of metal to fabricate biomass gasifiers have led to
drastic reductions in the cost of production and significant increases
in reactor service life.
The resulting economics present a more
favorable picture for the future of small-scale gasification systems.
1. HISTORY
The basic principles of biomass gasification have been known since
the late 18 th century and commercial applications of the principles were
first recorded in 1830. By 1850, large parts of London had gas lights and
there was an established gas industry manufacturing "producer gas" from
coal and biomass fuels.
The use of producer gas to run an internal
combustion engine was first tried around 1881. By the 1920s, producer gas
systems were being used to operate trucks and tractors in Europe. While
it was demonstrated that it was possible to operate engines with producer
gas, it was not convenient or reliable and producer gas systems for
operating mobile or stationary engines did not gain wide acceptability.1
Biomass gasification systems reappeared with a force in Europe,
Asia, Latin America and Australia during World War II as a result of the
scarcity of petroleum fuels. In Europe alone, almost one million gasifierpowered vehicles helped keep basic transport systems running during the
War.
In most cases, the gasified biomass fuels were either wood or
charcoal. Gasifier systems were generally abandoned with the reemergence
of relatively inexpensive liquid fuels after the War.
The "energy crisis" of the 1970s sparked a renewed interest in
biomass gasification systems. The technology was perceived as a relatively
cheap indigenous alternative for small-scale industrial and utility power
generation in those developing countries that suffered from high world
market petroleum prices and had sufficient sustainable biomass resources.
By the early 1980s over 15 (mainly European and North American)
manufacturers were offering small-scale wood and charcoal gasifier power
plants (up to approximately 250 kWe).
In addition, at least four
developing countries (Philippines, Brazil, Indonesia and India) had started
gasifier implementation programmes based on locally developed technologies.
As a result of developing country interests and the possibilities for
export earnings, a large number of biomass gasification systems were
112
installed in several developing countries for testing and demonstration
mostly through donor financed projects.
In some cases such as Brazil,
China, India and Thailand, the technology was even developed and promoted
by local entrepreneurs.
At present, biomass gasification systems have
found only limited commercial applications in several developing countries
including Brazil, China, India and Thailand.
2. TECHNOLOGY
Chemistry.
Biomass gasification is the process of conversion
through thermal decomposition of a solid biomass feed material to
combustible gas. Gasification is achieved in the presence of heat and a
limited supply (less than stoichiometric) of oxygen resulting in incomplete
combustion of the feed material. The result is a combustible gas. When
air (as opposed to pure oxygen) is used as the gasifying agent, the product
gas mainly consists of carbon monoxide (CO), nitrogen (N 2 ), hydrogen (H 2 ),
small amounts of methane (CH4) and other higher hydrocarbon gases. Due to
the nitrogen dilution, the product gas has a low energy or calorific value
in the range of 3.8 to 5.6 MJ/m3 as compared to natural gas which is the
range of 38 MJ/m3. Thus, producer gas from air gasification is suitable
for combustion in adjacent internal combustion (IC) engines, boilers or
kilns but is too dilute for economic transport in pipelines over long
distances.
Equipment. Biomass gasification systems consists of four principal
components :
(a) Fuel preparation, handling and feed system;
(b) Gasification reactor vessel;
(c) Gas cleaning, cooling and mixing system; and
(d) Energy conversion system (e.g., IC engine with generator or pump
set or gas burner coupled to a boiler or kiln).
Power Gasifiers.
Gasification systems that are coupled to IC
engines to produce shaft power are called power gasifiers. When the gas
is to be used in an IC engine it is important that it is cleaned of all
particulate, tars and moisture and cooled to near ambient conditions to
ensure reliable and efficient operation of the engine. As such, power
gasifiers require elaborate gas cleaning, cooling and mixing systems and
in general have stricter fuel quality and reactor design criteria.
An
example of a typical power gasifier system is shown in Figure 1.
Heat Gasifiers.
Gasification systems that are used to fuel
external burners such as those found in boilers, kilns or driers are
referred to as heat gasifiers. Heat gasifiers differ from power gasifiers
in one important aspect. Heat gasifiers generally don't require elaborate
gas cleaning and cooling systems because the producer gas is usually
combusted externally in close proximity to the gasifier. Heat gasifiers
are also more energy efficient because they tend to utilize the sensible
heat and tars in the producer gas. As a result of the less critical gas
quality requirements, heat gasifiers, in general, are simpler to design,
construct and operate than power gasifiers and are more versatile in the
fuels they can utilize.
Figure 2 illustrates a typical heat gasifier
system.
Reactor Designs. The vessel or reactor used to convert biomass
fuels to gaseous fuels are called "gasifiers". These gasifiers are usually
characterized by the design of the "fuel bed" and the method in which the
biomass fuels are brought into contact with air and heat for the process
113
of gasification. Three principal fuel bed designs can be identified: fixed
bed; fluidized bed; and entrained bed. Fluidized bed and entrained bed
biomass
t
air *~
GASIFIER
gas
cooler/
cleaner
'
'
ash
Fig.
dust
engine
power
condensate
Typical power gasif ier system
biomass
GASIFIER
process
heat
ash
Fig. 2
Typical heat gasifier system
114
designs, while more robust and versatile in their operation are generally
more difficult to design , build and operate, are more expensive and are
presently not considered appropriate for small scale (less than 1 MWe) ,
developing country applications. As such, fluidized and entrained bed
gasifiers are not considered in this study.
Fixed Bed Gasifiers. The most common type of gasifier reactors
used in developing countries are the fixed bed type because of their
relative simplicity of design, low cost of fabrication and ease of
operation.
Fixed bed gasifiers can be further characterized by the
direction of the flow of biomass fuel and gasification air within the
reactor. The principal fixed bed gasifier types are:
(a) Down-draft or co-current;
(b) Up-draft or counter-current;
(c) Cross-draft or cross-current; and
(d) Open-core.
Several variations exists within the four principal fixed bed
gasifier types. The exact choice of gasifier design is more a function of
the type of fuel to be gasified and the end use of the producer gas (for
power or heat).
For example, power gasifiers fueled with unprocessed
biomass tend to be of the down draft design because of the ability of down
draft gasifiers to produce low tar gas. Heat gasifiers tend to be more of
the up draft or cross draft design.
Charcoal fueled gasifiers can be
either up draft, down draft or cross draft. Open-core gasifiers are
designed for gasification of rice husks.
Simplified block diagrams
illustrating the main types of biomass gasifiers considered in this study
are presented in Figure 3.
Fuel Characteristics.
Given the state-of-the-art of commercially
available fixed bed gasifier systems and based on data obtained from the
UNDP/World Bank Biomass Gasifier Monitoring Program, at present, only wood,
charcoal, rice husks and coconut shells are considered suitable biomass
fuels for gasification. Biomass fuels such as wood wastes, coconut shells
and rice husks can generally be used with minor processing such as drying,
sizing and screening. The typical characteristics of these bioraass fuels
are presented in Table 1.
In order to ensure reliable and efficient operation, biomass fuels
for gasification must meet certain specifications. All gasifier types have
fairly strict fuel requirements with respect to size, moisture content and
ash content.
Inadequate fuel preparation is an important and frequent
cause of technical problems associated with gasification and therefore a
strict organization and control of fuel preparation procedures is of utmost
importance.
Table 2.2 presents a generalized overview of the most
important fuel requirements for the different types of gasifiers considered
in this study.
115
fuel
air
fuel
qas
updraft
fuel
opencore
Figure
Main types of biomass gasifiers
116
Table 1:
Moisture
Content
% Wet
Biomass
Fuel
Charcoal
TYPICAL CHARACTERISTICS OF BIOMASS FUELS
Ash
Content
% Dry
Volatile
Matter
% Dry
2 - 5
5 - 30
200 - 300
30
70 - 80
600 - 800
20
100
15
2 - 10
Wood
Rice husks
20 - 40
0.1 - 1.0
3 - 5
15 - 25
60
0.8
79
Coconut
shells
25
Table 2:
Bulk
Density
kg/m3
Average
Higher
Heating
Value
MJAg
dry basis
20
FUEL REQUIREMENTS FOR DIFFERENT GASIFIER TYPES
Gasifier type:
Fuel:
Up-draft
(Wood)
Down-draft
(Wood)
Size (mm)
Moisture (%db)
Ash (% db)
20 - 100
< 25
< 6
5 - 100
< 60
< 25
"Open Core"
(Rice Husks)
1 - 3
< 12
approx. 20
Cross Draft
(Charcoal)
40
80
< 7
< 6
Producer Gas Utilization Systems

IC Engines. One of the most attractive uses of producer gas is its
use in internal combustion engines for the production of shaft power which
in turn can be used for generating electricity, pumping water, milling
rice, running compressors, motive power, etc. Although producer gas can
be combusted in gas turbines, its application in this area has not been
adequately demonstrated to warrant serious consideration in this study.
Producer gas has been widely used in reciprocating IC Diesel (compression
ignition) and Otto (spark ignition) engines.
However, several issues
regarding the resulting engine performance, efficiency, output, and life
need to be closely evaluated to determine the trade-offs of utilizing the
relatively low quality producer gas in engines that are essentially
designed to operate on high quality liquid fuels.
Spark ignition engines can be run entirely on gas. The maximum
power output of an Otto engine on producer gas depends on the gas heating
value, the setting of ignition timing and specific engine characteristics
and is normally considerably less then the equivalent value on petrol or
natural gas. Diesel engines can only be partly operated on producer gas
117
(dual fuel operation) and therefore always consume a certain amount of
diesel fuel. The maximum power output of such an engine depends on the gas
heating value, the injected diesel fuel amounts and specific engine
characteristics.
Direct Combustion Burners.
Producer gas can also be directly
combusted in external combustion systems such as boilers, kilns, driers,
ovens, etc.
In most cases little or no modification to the existing
equipment is necessary especially if the system is designed to burn a
gaseous or atomized liquid fuel. As in the case of IC engines, a close
evaluation of system performance, efficiency, output and life as a result
of the use of producer gas needs to be accounted for. However, given the
fact that direct combustion systems generally involve no internal moving
parts, the impacts of producer gas on these systems is usually minimal.
Safety and Environmental Aspects
Operation of gasification systems may give rise to the following
types of hazards :
(a) Toxic gaseous emissions;
(b) Fire and explosion hazards; and
(c) Toxic liquid effluent.
However, with care and proper safety precautions, biomass
gasification
systems can be made to operate without incident.
This requires full
recognition of the potential dangers associated with the system and
operation by only trained personnel.
Toxic Gases. An important constituent of producer gas is carbon
monoxide (CO), which is an extremely toxic and dangerous gas because of its
tendency to combine with blood haemoglobin and rob the body of normal
oxygen intake. Fortunately, normal power gasification systems work under
suction, so that even in case a gas leak occurs in the system, no dangerous
gas will escape from the equipment during actual operation.
If CO
emissions do occur, they are only of concern in the immediate vicinity of
the gasifier plant as the CO will quickly react with ambient 0 2 to form
The situation is different during start-up and shut-down of the
installation.
During start-up the gas is generally vented and it is
necessary to ensure that the vented gases cannot be trapped in an enclosed
room. As a rule a suitable chimney will provide sufficient safety. During
shut-down of the installation a pressure build-up will occur in the
gasifier, caused by the remaining hot and pyrolysing fuel. As a result, for
a short period (approximately 15 minutes) carbon monoxide containing gases
will be released. Therefore gasifier systems should always be installed
in well ventilated buildings, or, if possible, installed externally covered
only by suitable roofing.
Fire and Explosions. Fire hazards may result from high surface
temperature of equipment; risks of sparks during refueling; and flames
emerging from gasifier air inlets.
In most cases, burn risks can be
eliminated by relatively simple safety measures such as insulation of hot
parts, installation of double valve fuel feeding system, installation of
back-fire valve in gasifier inlet, etc.
Gas explosions may occur in case the hot gas is mixed with a
sufficient amount of air to trigger spontaneous combustion. Air leakage
into the system will generally not give rise to explosions, but will lead
to local zones of gas combustion resulting in higher gas temperatures and
lower gas quality. Pyrolytic gases in the bunker section when mixed with
118
air (as may happen during refueling) may form an explosive mixture. It is
not unusual for this to burn in a relatively harmless manner, especially
when the fuel level in the bunker is low. Risks to the operator can be
obviated by burning-off the gases in the bunker through introduction of a
piece of burning paper or the like. Also double sluice fuel feeding systems
prevent this type of risks. The major explosion risk lies in the lighting
of an un-vented cold gasifier. An explosive mixture may still be present
in the equipment and be ignited. Therefore cold systems should always be
carefully vented before ignition.
Toxic Effluent. A biomass gasification system produces ashes and
tar/phenol containing condensates.
Ashes do not constitute
an
environmental hazard and can be disposed of in the normal way. Condensates
amounts from down-draft gasifiers are normally small and also tar/phenol
contamination is relatively minor. The situation is different with the
large quantities of heavily contaminated condensates from up-draft and
"open-core" systems.
Although no hard data are as yet available on
biodegradation of phenolic and tarry constituents from condensates of such
systems, it is clear that untreated disposal of such condensates is
environmentally unacceptable and can result in contamination of drinking
water, fish kills and other related effects. Therefore, this disposal
problem needs careful study before introduction of gasifier systems that
produce large quantities of condensate are considered.
Positive Impacts.
The primary positive impact of biomass
gasification systems is the possibility of effectively utilizing a waste
biomass material such as wood residues, rice husks, coconut shells, etc.,
which could otherwise pose disposal problems and create localized fire
hazards, insect infestation, vermin breeding or odor during the decay
process.
Air emissions from IC engines fueled with producer gas are
marginally cleaner than emissions with petroleum fuels.
The main
advantages are the absence of lead and sulphur emissions with producer gas.
Additionally, gasification systems, by virtue of utilizing a biomass fuels,
do not contribute to the net increase of C0 2 in the environment as would
liquid fossil fuels.
3. CURRENT COMMERCIAL STATUS
Commercialized Power Gasifiers. There are a small number of strictly
commercial power gasifiers currently operating globally.
No accurate
inventory is available, but rough estimates would be in the range of one
to three thousand.
However, the vast majority of these would be small
charcoal gasifiers located in Latin America, primarily Brazil.
It is
estimated that less than one hundred commercial non-charcoal
power
gasifiers are currently in operation globally.
Of the commercial noncharcoal gasifiers, most are either fueled with wood or rice husks.
Down-draft Charcoal Gasifiers.
Several hundred commercially
operating down-draft charcoal gasifiers are reported in operation
throughout the globe.
Most are located in Brazil. About a dozen are
located in the Philippines as a result of a major government program to
promote the technology in the early and mid 1980s. It should be noted,
however, that of nearly one thousand down-draft charcoal gasifiers
disseminated through a government subsidy program, none are presently in
operation.
The gasifiers that are in operation were purchased by the
private sector without government subsidy and, in many cases, were modified
to meet the users needs. The technical performance of most down-draft
charcoal gasifiers have been satisfactory, especially where operator
119
training and maintenance support have been provided.
However, rising
charcoal prices and lower petroleum prices have resulted in the
decommissioning of many of these units.
Down-draft Wood Gasifiers.
A few commercial down-draft wood
gasifiers are reported to be operating in India and Latin America. The
units in India are small scale (5 hp - 100 kW) units used primarily for
water pumping and isolated power generation. The seemingly most successful
commercial down-draft wood gasifiers are located in the Mennonite community
of Loma Plata, Paraguay. The gasifiers are part of a power plant used to
supply electricity to the Loma Plata community. It is reported that there
are three gasifier units each coupled to a 420 kWe gas engine/generator
set.
The wood gasifiers are used to meet the base load demands while
stand-by diesels are used to meet peak loads. The first unit was installed
in 1983.
After initial technical problems and after extensive
modifications of the gas cleaning section, the system is now reported to
function to the satisfaction of the user.
At least one gasifier manufacturer (in France) can point to a small
number of commercial projects presently operating in developed countries
(primarily Europe).
Most of these gasifier systems are situated at
isolated sawmill sites. However, operational and financial details with
respect to these plants are not available.
Up-draft Gasifiers. A few commercial up-draft wood gasifiers are
known to be operating primarily in Latin America.
The situation was
completely different in the 1940s and 1950s when both in Europe and
elsewhere a considerable number of systems were functioning on a diversity
of fuels including wood residues and agricultural wastes.
The last
European updraft power gasifier (in Germany) operating on sawdust was
closed down recently for environmental reasons (water pollution resulting
from disposal of tarry effluent). Up-draft gasifier plants currently in
operation perform technically satisfactory on fuels of a fairly wide range
of specifications.
However, as explained earlier, updraft gasifiers
produce large quantities of tar, with potentially serious health and
environmental hazards. As such, their commercial applications have not
been aggressively pursued.
Cross-draft Gasifiers.
A large number of cross-draft charcoal
gasifiers have been in commercial operation in Brazil and other Latin
American countries. Two such installations were systematically monitored
under the UNDP/World Bank BGMP.2 The results indicated that the units
experienced
considerable
operational
problems
primarily
due
to
inexperienced operators, sensitivity to fuel quality, operation of the
gasifier below minimum loads and inconsistent maintenance of the plant and
equipment.
In cases where these issues were addressed and where plant
utilization factors were high, the charcoal cross-draft gasifiers were
commercially attractive.
Open-core Gasifiers. A number (at least twenty) commercial open
core rice husk gasification plants have been in operation in the Peoples
Republic of China (PRC) for decades.
Since 1967 identical units were
installed at a rice mill in Dogofiri, Mali. The performance of these units
were monitored under the UNDP/World Bank BGMP.3
It was concluded that
plants operate technically satisfactorily and, at given locations are able
to produce electricity at marginally lower financial cost than equivalent
diesel engines. As a result of the general success of these units in Mali,
it was recently (1986) decided to install an additional unit in Mali.
120
However, it should be borne in mind that the units, as presently designed,
produce considerable amounts of potentially harmful tars which are a
problem to dispose in an environmentally acceptable manner.
Over the past five years a number of locally designed and
manufactured open core gasifiers have been commercially installed at rice
mills in Thailand.
No performance data, other than that the systems
generally work to the satisfaction of the users, are available on the
Chinese and Thai rich husk gasifiers.
Commercialized Heat Gasifiers.
By
far
the
most
successful
commercialization of gasification technology has been with heat gasifiers
of varying capacities, designs and applications.
Most of the heat
gasifiers currently on the market have output capacities in the range of
0.1 to 10 MWt.
Heat gasifiers operating on fuels of widely differing
specifications have been used commercially to produce process heat for use
in kilns; ovens; driers; boilers; heaters; etc.
Heat gasifiers have been manufactured and applied in Europe and
North America
as well as several developing countries of the Pacific,
South-East Asia and South America. During the mid-1980s, Brazil had over
dozen active heat gasifier manufacturers and over 50 known commercially
operating heat gasifier installations.*
Heat gasifiers have also been
locally manufactured and commercially adopted in Malaysia, the Philippines,
Indonesia and India as well as several other Asian and Latin American
countries.
New Zealand manufactured heat gasifiers are reported to be
commercially operating in significant numbers in Papua New Guinea and
several other Pacific Island countries. Attempts are now being made to
promote similar heat gasifier technology in several African countries.
There appears to be no significant technical problems associated
with heat gasifiers. Unlike power gasifiers, the gas produced by heat
gasifiers is combusted externally, generally in close proximity if not
directly adjacent to the gas outlet of the gasifier.
Therefore, heat
gasifiers usually do not require elaborate gas cleaning systems, are more
efficient because they utilize the sensible heat and condensible tars in
the gas and do not produce any toxic effluent. An exception are heat
gasifiers applied in situations where the gas has to be transmitted long
distances or a clean flame is required as is the case in food drying or
baking or ceramic production.
4. RESEARCH. DEVELOPMENT AND DEMONSTRATION PROJECTS

Donor Financed Proprams.
Over the past decade there have been numerous
donor organizations that have financed biomass gasification research,
development and demonstration (RD&D) projects in developing countries. It
is beyond the scope of this report to outline the extent or results of
these efforts. However, a few key points can be summarized. Most donors
have concentrated on demonstrating down-draft power gasifier systems for
applications in isolated power generation, irrigation, water pumping or
rural industries.
In a majority of the cases, the gasifiers being
demonstrated were designed and manufactured in the donor countries and
exported to the developing countries. In many cases, a wide variety of
fuels were experimented with, however, positive results were achieved
primarily with the well established fuels of charcoal, wood, coconut shells
and rice husks. In all cases, the donor financed projects are important
121
to review as their history and experience are usually much better
documented than the strictly commercial operations.
The donor projects were, for the most part, designed on the assumption
that the technology would work in the developing country context and
therefore had the objective of demonstrating economic and social viability
while simultaneously promoting the technology for wider use. In reality,
most of these demonstration projects failed to achieve normal, reliable
operation due to several diverse reasons including those listed below:
(a) Use of biomass residues that were unacceptable for down-draft power
gasification systems;
(b) Use of equipment that was previously untested in developing country
environments ;
(c) Mismatching of gasifier system capacity to energy demand profiles
resulting
in systems operating at turn-down ratios below
specification or systems being made to respond to rapid and wide
load changes ;
(d) Insufficient training of operators and provision of competent
technical back-up resulting in initial operating errors and damage
to equipment;
(e) Lack of sufficient incentives to motivate operators to accurately
perform additional, and usually time consuming, laborious and dirty
tasks, associated with gasification systems;
(f) Poor system design including mismatching of imported and local
system components, inattention to local operator skills and biases
and little or no documentation or operation manuals; and
(g) Finally, disappointing economics due to poor system performance,
accounted costs or simply disregard for economic criteria at the
outset of project design.
Nationally Financed Programs.
In addition to the donor financed gasifier
demonstration projects, there have been several nationally initiated
efforts over the past decade. The most notable in the developing countries
include: The Philippines; Brazil; India; Thailand; and Indonesia. Brief
highlights of the key points associated with each program are presented
below.
The Philippines. A government backed and United States Agency for
International Development (USAID) supported program to commercialize
locally designed and manufactured charcoal gasifiers was initiated in the
early 1980s.
The program was aimed at providing options for rural
irrigation water pumping, rural electrification and motive power for
jeepneys and bancas (trucks and boats).
Nearly one thousand charcoal
gasifiers were manufactured under the program. The program, terminated in
1986, was a failure for several reasons including poor design and quality
of the gasifier systems, no control on input fuel specifications,
inadequate operator training, no manufacturer technical and maintenance
back-up, and, perhaps most importantly, disregard for the normal economic
incentives necessary to assure success.
The Philippine program was
subsidized. Gasifiers were essentially given away by the government to
local farmer cooperatives without instilling adequate economic incentives
to ensure commitment by the farm cooperatives to the overall success of the
systems. It is interesting to note that of the few gasifier systems that
did succeed in the Philippines, almost all were purchased and operated by
the private sector without any subsidy or other form of government
assistance.
122
Brazil. Unlike the Philippines, the Brazilian government program
to promote gasifiers was essentially passive and relied on demand side
incentives rather than on the supply side subsidies.
In addition to
instituting phased in quotas of petroleum consumption for certain
industries and thereby creating a demand for alternative technologies, the
Brazilian government also sponsored a few select research efforts to help
develop appropriate gasification systems for Brazilian needs. However, no
subsidies or direct government assistance were provided for the promotion
of gasification systems. The results were dramatic. By 1985 there were
between 15 to 20 commercial gasifier manufacturers and well over a thousand
power and heat gasifiers that were privately purchased and in operation.5
While gasification activity in Brazil has declined somewhat recently, this
has been primarily in reaction to easing of petroleum quotas and prevailing
lower petroleum prices.
India. Recently (1987) a government-backed commercial down-draft
wood gasification programme was started in India, based on locally
developed and manufactured technology and aimed at small-scale irrigation
applications. To date a total of 2.5 MWs of capacity, mainly in 5 kW size
units (i.e., approximately 500), has been installed.
The programme is
heavily subsidized. A recent evaluation concludes that approximately 60 %
of the units are not in regular operation for technical, organizational and
financial reasons. A
more detailed evaluation quantifying the above
factors is presently underway.
Thailand. Relatively independently from several donor and private
sector efforts to promote gasification in Thailand, the Thai Ministry of
Interior, through its Department of Public Works (DPW) has, for the past
few years, undertaken a program to promote rural electrification using
biomass gasification technology. With a budget of approximately 25 million
Bhats (one million US) , the DPW has installed 143 - 15 kW charcoal
gasifiers throughout Thailand. DPW's objective were to install 4000 units
by 1991.6 Like the Philippine government's program, the Thai DPW program
has run into several difficulties including technical problems with the
design of their gasifier system as well as economic, social and
institutional issues that have hampered the program.
Indonesia.
The potential for biomass fuelled gasifiers to
substitute petroleum consumption has attracted much attention in Indonesia.
In 1987, the President of the Republic of Indonesia (ROI) mandated that 10
Indonesian manufactured biomass gasifiers be placed in field operations,
to help demonstrate the technical and economic viability of such systems.
Over the past decade several donor financed activities in Indonesia have
also promoted gasification systems. A s a result of these activities, there
are at present over 20 power gasifiers and several heat gasifiers installed
in Indonesia.
The power gasifiers, all for demonstration and testing
purposes, are widely spread over the different provinces of Indonesia.
Three units are fueled with rice husks while the rest are fired with
different types of wood. Most projects aim at demonstration and/or testing
of the technology. To date no truly commercial power gasification systems
are in operation in Indonesia. Most of the heat gasifiers are situated in
Java or Sumatra and operate on coconut shells or other similar types of
residues. These units represent the only truly commercial applications of
biomass gasification technology in Indonesia to date.
5.
ECONOMICS
The economics of small scale power gasifiers hinges on the savings
that can be realized by switching from high-cost liquid fuels (i.e.,
diesel) to low-cost biomass fuels.
These fuel cost savings must be
measured against the additional capital costs of the gasifier, the increase
in operation and maintenance costs, and the reduced reliability of the
123
system.
One way to evaluate the tradeoff between capital costs and
operating and maintenance costs is to compare the levelized costs of
electricity generated by each system. This has been done in a study based
on data collected under the UNDP/World Bank Biomass Gasifier Monitoring
Program (BGMP).7 The study compared generic wood and charcoal gasifiers to
diesel stand-alone systems from 5 kWe to 1 MWe.
The study evaluated commercially available power gasifiers in the
following ranges:
o
Manual feed charcoal gasifiers from 5 - 200 kWe;
o
Manual feed wood gasifiers from 5 - 200 kWe;
o
Automatic feed wood gasifiers from 100 kwe - 1 MWe.
Figure 4 presents some of the principal findings of the study.
The
analysis indicates that power gasifier economics is most strongly affected
by system size and by the relative cost of petroleum and biomass fuels.
Under the baseline economic price of diesel at US$ 0.20/1, charcoal
at US$80/t and fuelwood at US$20/t, none of the gasifiers evaluated in the
BGMP were economic. However, if economic price of diesel were assumed to
rise to US$ 0.40/1, as is the case in many isolated rural areas of
developing countries, then the manual feed charcoal gasifiers and wood
gasifiers above 30 kW become competitive. With the current low economic
prices of petroleum fuels, it is clear that power gasifiers will have a
niche only in remote applications where the economic cost of diesel is high
(due to transport costs and unreliable supplies) and the cost of biomass
fuels is low (due to surplus availability).
6.
RECENT BREAKTHROUGH
Recent work at the Asian Institute of Technology (AIT) in Bangkok
has resulted in a radical departure from conventional gasifier systems.
Due to the high costs of metal, fabrication of a 10 kWe charcoal gasifiers,
even when locally manufactured, is in the range of US$500/kW. As such, the
economics of gasification are marginal given current petroleum prices.
Under the leadership of Dr. Bob Reines, the AIT has developed a 10 kWe
"ferrocement" open-core charcoal gasifier with the resultant costs of only
$50/kW for the gasifier. The reactor is lined with refractory brick to
manage the normally high temperatures encountered in this zone.
The
ferrocement components are water cooled which provides a relatively uniform
temperature gradient over the ferrocement surface minimizing thermal
stress. The water also serves as heat transfer fluid for gas cooling. As
a result, the ferrocement approach solves many of the material (thermal
stress and corrosion) as well as economic constraints associated with
conventional metal gasifiers. To date, ferrocement gasifiers have only
been demonstrated for small (less than 18 kWe maximum output) charcoal
gasifiers.
New Economics
The ferrocement gasifier presents the possibility of a ten fold
decrease in the capital costs of a gasifier. A brief comparison of the
economics of a diesel generator set, conventional charcoal gasifier system
and a ferrocement gasifier system is presented to illustrate the impact of
this new approach.
Table 3 outlines the basic assumptions used in the
analysis. Figure 5 shows the resulting levelized electricity costs (in
cents/kWh) of the three systems. At the current economic price of diesel
of US$0.25/1 and charcoal at US$40/t, the conventional gasifier is not
economic with a diesel system.
However, the ferrocement gasifier has
levelized electricity about 11% lower than the diesel system. Figures 6
to 8 show a sensitivity analysis on charcoal and diesel prices, installed
124
Costs of Electricity Production

Small Stand-Alone Systems
Electricity Costs ($/kWh)
1000
INSTALLED CAPACITY (kW)
Diesel I 40c/l
-- Woodgas/m $2Q/mt
POWER SOURCE
Diesel 20c/l
-*- Clmrgns $BD7mt
Woodgas/a $20/mt
m = manual / a = automatic
Figure 4:
Electricity Costs: Diesel vs. Gasifier Systems
capital costs (ICC) and annual operating hours. In all cases, the $50/kW
ferrocement gasifier significantly increase the range in which the
technology is economically competitive with diesel systems
7.
SUMMARY
Based on the above discussion, the current status of biomass
gasification technology can be broadly summarized as follows:
(a)
Commercially proven power and heat biomass gasifiers are available

especially when the fuels are charcoal, wood, coconut shells and
rice husks. Heat gasifiers are more tolerant of other types of
biomass fuels.
However, only limited experience with "nonconventional" biomass fuels is available for small-scale power
gasifiers.
(b)
The economics of biomass gasification, at present, are at best

marginal. When compared to the counterpart petroleum system, the
economics of heat gasifiers are more favorable at present than
conventional power gasifiers.
(c)
The recent developments in ferrocast charcoal gasifiers could help

change the negative picture for biomass power gasifiers. However,
further testing especially in field applications are necessary to
confirm the viability of this technology.
125
Table 3: BASIC MODEL OF THE ANALYSIS
Diesel Price
Charcoal Price
ICC Diesel/Gas
Ann.Op. Hours
(c/1)
(cAg)
($AW)
(hrs)
PARAMETER
25.00
4.00
600.00
3000.00
LHV (MJ/unit) Energy Cost (c/MJ)

36.00
0.69
30.00
0.13
500.00
50.00
DIESEL
SYSTEM
CONV. CHAR
GASIFIER
FEROCEMENT
CHAR GASIF
Capacity
(kW)
(hrs)
Ann. Op. Hours
Avg. Op. Load
(%)
Annual Output (;kWh/yr)
10.00
3000.00
0.80
24000.00
10.00
3000.00
0.80
24000.00
10.00
3000.00
0.80
24000.00
Installed Capital Cost

Eng/Gnenset
($)
Gasifier
($)
6000.00
7500.00
5000.00
7500.00
500.00
6000.00
6.00
10.00
1377.64
5.74
600.00
12500.00
4.00
10.00
3943.39
16.43
1250.00
8000.00
4.00
10.00
2523.77
10.52
800.00
(%)
20.00
3000.00
12.50
15.00
768.00
3.20
15.00
768.00
3.20
($/mo)
50.00
1.0
600.00
2.50
0.015
360.00
1.50
3960.00
16.50
50.00
1.5
900.00
3.75
0.025
600.00
2.50
2268.00
9.45
50.00
1.5
900.00
3.75
0.025
600.00
2.50
2268.00
9.45
22.24
25.88
19.97
Total ICC
Expected Lif
Discount Rat
Annual ICC
ICC/kWh
ICC A
ANNUAL O&M
Fuel
System Eff.
Annual
Unit Costs
Labor
Monthly Wage
Operators
Labor Costs
Unit Costs
Maintenance
Maint. Costs
Unit Costs
Total Ann. O&M
Tot Ann. O&MA
COST/KWH
($)
(yr)
(%)
($/yr)
(cents)
($)
($/yr)
(cAWh)
($/yr)
(c/kWh)
($AWh)
($/yO
(cAWh)
($/yr)
(c)
126
cents/kWh
25.881
19.966
I Sytten
/kW Qatifier
60/kW Qasifier
15
2.5
12.5
5.74
2.5
3.75
3.2
16.431
2.5
3.75
3.2
10.516
Maint Costa/kWh
Labor Costa/kWh
Fuel Coata/kWh
Cap. Coata/kWh
> Cap. Costs/kWh
22
EZ] Labor Costs/kWh
! S i Maint. Costs/kWh
Figure 5.
Fuel Costs/kWh
E l e c t r i c i t y C o s t Components
Cost of Electricity
vs. Charcoal Price
Coat of Electricity (c/kWh)
Charcoal Price (c/kg)

$eo/kW
200/kW
Diesel 20 e/l
Diesel 40 c/l
Figure 6.
600/kw
Sensitivity to Charcoal Price
10
127
COST OF ELECTRICITY
vs. ICC of Gasifier System
35
[c/kWh]
100
200
300
400
500
600
700
BOO
ICC of Gasifier System ($/kW)

25 c/l Diesel
40 c/1 diesel
S40/t Charcoal
380ft Charcoal
Figure 7:
S20/t Charcoal
Sensitivity to Installed Capital Costs
Cost of Electricity
vs. Operating Hours
Cost of Electricity ( c / k W h )
130
1000 1500 2000 2500 3000 3500 40GG 450G 5000 5500 6000
Annual Operating Hours

^ D i e s e l System
Figure 8:
50/feW Gasifier
* 1500/kW Gasifier
Sensitivity to Operating Hours
128
1.
Reed, T.B., Biomass Gasification:

Principles
Data Corporation, Park Ridge, NJ, 1981.
and Technology. Noyes
2.
Furtado, P. et.al.,
Biomass Gasifier Monitoring Proiect in
Brazil.
Final Report, prepared by Cetec under World Bank/UNDP contract,
January 1987.
3.
S tassen, H., et.al.,

Biomass Gasifier Monitoring Project in
Report prepared by Twente University of Technology, Biomass
Technology Group, under World Bank/UNDP contract,
1987.
4.
Mendis, M.S., "Biomass Heat Gasifiers:

Status and
Potential",
Internal Working Paper, New and Renewable Energy Unit, The World
Bank, Washington, DC, May 17, 1984.
5.
Furtado, P. and Antunes, R. , "Commercial Applications of Biomass

Gasifiers in Brazil", Presented at the Second
International
Producer Gas Confernece. Bandung and Jakarta, Indonesia, March 19
-23, 1985.
6.
Coovattanachai, N., "Final Report on the Assessment of the

Performance and Identification
of Technical Problems of DPW's
Gasification
System", Prince of Songkala University,
Haadyai,
Thailand, January 28, 1988.
7.
Terrado, E., Mendis, M. and Fitzgerald,

., "Impacts of L ower Oil
Prices on Renewable Energy Technologies", Energy Series Paper
No.5. World Bank, Washington, DC, 1988.
Hali.
129
GASIFICATION AND PYROLYSIS OF BIOMASS IN EUROPE

A A C M Beenackers
Department of Chemical Engineering
University of Groningen
Nijenborogh 16
9747 AG Groningen
The Netherlands
A V Bridgwater
Chemical Engineering Department
Aston University
Aston Triangle
Birmingham B4 7ET
UK
ABSTRACT
Biomass, as the only renewable source of fixed carbon, has attracted
considerable attention as a renewable energy resource after the oil crises of the last 15
years. Thermochemical processing has attracted considerable attention from the variety
of technologies available for converting biomass into more useful and valuable energy
products. As pyrolysis, gasification or liquefaction, this technology has been
researched and developed for the economic production of fuel products that may be
readily integrated into the energy infrastructures of both industrialised and developing
countries.
The characteristics of the generic types of thermochemical conversion gasification, pyrolysis and liquefaction - are described in this paper. The range of
products derivable from each system are discussed and related to each technology, and
the applications that have been researched to date are reviewed.
Current interest lies in relatively simple conversion technology to produce low
Joule gas and basic liquid fuels. Longer term possibilities include gaseous and liquid
hydrocarbon fuels, petrochemicals, bulk organics such as methanol and ammonia, and
chemical specialities.
INTRODUCTION
The potential offered by biomass and solid wastes for solving some of the world's
energy problems is widely recognised. The energy in biomass may be realised either by direct
use as in combustion, or by upgrading into a more valuable and usable fuel such as fuel gas or
fuel oil or higher value products for the chemical industry. This upgrading may be by
physical, biological, chemical or thermal methods to give a solid, liquid or gaseous fuel. This
paper is concerned with thermochemical conversion, and it reviews the state-of-the-art in
gasification, pyrolysis and liquefaction of biomass.
2
THERMOCHEMICAL TECHNOLOGY
Except for direct combustion which is outside the scope of this paper, there are three
thermochemical methods of converting biomassrgasification, pyrolysis and liquefaction. Each
gives a different range of products and employs different equipment configurations operating in
different modes. These are summarised below in Table 1, and the characteristics of the
technologies are described in Table 2. The basis of a fuel or chemical production system is that
the feedstock is converted to a useful primary energy product in a sequence of operations:
pretreatment, conversion, and primary upgrading by simple physical processing such as gas
scrubbing. Secondary higher value products may be produced by additional processing as
shown overall in Figure 1.
130
Table 1
Thermochemical Conversion Technologies and Products
Primary Product
gas
liquid
solid char
liquid mostly
solid char mostly
Application
fuel gas
Liquefaction
liquid
Gasification
gas
fuel gas
Combustion
heat
heating
Technology
Pyrolysis generally
Flash Pyrolysis
Slow Pyrolysis
Table 2
Characteristics of Thermochemical Conversion Technologies
Figures quoted are typical, and can vary considerably according to technology and operating
conditions
Pvrolvsis
Flash
Slow
Liquefaction Gasification
FEEDSTOCK
Feed size
Moisture content
any
low
small
very low
small
very low
mixed-large
50% max
PARAMETERS
Temperature, C
Pressure, bar
Maximum throughput, t/h,
achieved so far
500-700
0.1-1
5
500-900
1
0.05
250-350
100-200
0.1
800-1500
up to 30
20
up to 40
5-10
up to 30
22
30
30
up to 70
10-20
up to 70
22
up to 20
30
20
2-6
up to 50
27
up to 25
30
100-250
5-15
up to 5
22
nil (ash)
-
PRODUCTS
Gas
yield, %wt on dry feed
heating value, MJ/Nm3
Liquid
heating value, MJ/kg
Solid
heating value, MJ/kg
Feedstocks generally considered for thermochemical conversion are agricultural waste,

wood and wood waste, energy crops, and refuse (MSW). The main technical criteria for
feedstocks in terms of their suitability for thermochemical processing are low moisture content
and low ash content The main economic criteria are cost and quantity available, both of which
have a considerable influence on costs.
3
3.1
PRODUCTS
Introduction
The possible primary products and their processing origins are summarised in Table 3.
This primary product can be used directly, or it may be subjected to further chemical
processing to give a higher quality fuel or chemical product as shown in Figure 1. The
131
technologies for upgrading and likely viable size ranges are summarised in the relevant sections
below.
CONVERSION
TECHNOLOGY
/'/' ' PRIMARY

'\,\<
SSS PRODUCTS
S
V A . V WATER ^ . V >
Figure 1
Primary and Secondary Products from Thermochemical Biomass Processing
Table 3
Primary Thermochemical Conversion Products and Technologies
Product
Form
Components
Source
Fuel gas
LHV
MHV
CO, H2, C02, CH4, N2

CO, H2, C02, CH4,
higher hydrocarbons
Pyrolysis, Air gasification

Pyrolysis, 02 gasification
Liquid
OU
Water insoluble
oxygenates of high
boiling point
Charcoal and oil
Charcoal, water and
stabiliser
Pyrolysis, Liquefaction
Char-oil slurry
Char-water slurry
Pyrolysis
Pyrolysis
Aqueous
Waste water
Solid
Charcoal
Pyrolysis
Heat
Hot gas
Combustion
water soluble
} Pyrolysis
oxygenates of low boiling j Liquefaction
point.eg acetic acid
} Gasification
132
3.2
Primary products
The primary products can be gas, liquid, and/or solid char depending on conversion
technology employed. Much of the present interest in thermochemical conversion centres on
liquid products due to their high energy density and potential for premium liquid fuel
substitution.
The gas is a low to medium heating value fuel gas that may be used as such, or
physically and chemically upgraded to higher value products, including liquid products such as
gasoline. This is depicted in Figure 1 above.
The liquid, when formed, approximates to biomass in elemental composition, and is
composed of a very complex mixture of oxygenated hydrocarbons. The complexity arises
from the degradation of lignin, and the broad spectrum of phenolic compounds that result from
uncontrolled degradation. The liquid is often referred to as "oil" or "bio-oil", but is more like
tar. This also can be upgraded to liquid hydrocarbon fuels. Utilisation of this material is
discussed later.
The solid product from pyrolysis processes is char, which has limited application in
developed countries for metallurgical and leisure industries. Water is also produced from
moisture in the biomass feed and as a reaction product from pyrolysis. An alternative approach
to a liquid product lies in grinding the char and slurrying it with water with a stabiliser as in
coal-water mixtures. A slurry can also be made from the bio-oil and char The significance of
the energy density is shown in Table 4 below.
3.3
Secondary Products
These include power, fuels and chemicals and are summarised in Table 4.
Table 4
Secondary Products and Sources
Secondary product
Source
Oxygenate Fuels
Methanol
Fuel alcohol
Gasification
Gasification
Hydrocarbon Fuels
Gasoline
Diesel
Fuel oil
Power
Power
Chemicals
Ammonia
Speciality chemicals
Process
Synthesis
Synthesis
Pyrolysis
Pyrolysis
Liquefaction
Gasification via Methanol
Pyrolysis
Pyrolysis
Liquefaction
Gasification via Methanol
Pyrolysis
Liquefaction
Hydrotreating
Zeolites
Hydro-treating
MTG
Hydrotreating
Zeolite + MOGD
Hydrotreating
MOGD
Stabilisation
Stabilisation
Pyrolysis
Gasification
Turbine
Engine or turbine
Gasification
Pyrolysis
Liquefaction
Synthesis
133
4
GASIFICATION
Of the conversion technologies discussed in this paper, biomass gasification by now is
the most widely applied technology, except for charcoal production. However, relative to the
already significant contribution of biomass combustion to energy generation, the impact of
gasification of biomass for energy generation is still fairly limited. The main reason for this is
probably that the technology still has not reached full maturity. However, research efforts to
develop improved biomass gasification technologies have been impressive during the last 15
years. This is likely t result in an increasing number of successful commercial biomass
gasification applications in the future and justifies a review of recent developments including
low joule and medium joule gasification and the role of catalysis in gasification.
4.1
Low Joule Gasification

If air is used as the gasifying agent, a so called low joule gas or producer gas is
obtained having a heating value of typically 5MJ/Nm3.
Wood based gasifiers for heat applications have operated successfully for many years.
Both updraft moving bed gasifiers and (fast) fluidised bed gasifiers have been installed.
European plants have been described by Bierback et al. [1] McKeough et al. [2] and Salo [3].
New American plants were listed annually in the reviews of Klass [4, 5] but are no longer
published. A thermochemical biomass conversion database has been established through the
IEA Bioenergy Agreement which includes over 300 gasification activities around the world in a
total database of 650 thermochemical activities [6].
Recent progress at 150 kg/h dry biomass has been realised by Framatome with high
carbon conversion. Carbon to gas efficiencies as high as 96% have been obtained by
introducing secondary air above the bed and recycling char to the bed from the first cyclone (of
a set of two). In this way the char content in the ash collected from the second cyclone could
be as low as 0.7%.
Gasification of wood wastes followed by power generation via a steam cycle has been
investigated by the Florida Power Corporation at a scale of 2 MWe in an updraft moving bed
gasifier [7]. Some problems were encountered with handling the condensibles which were
separated from the wood gas on its way to the boiler by centrifugation. Initial problems to
combust the liquids in the burner could be solved. The project confirmed that adapting a
gasifier to an existing boiler can be accomplished with only minor effort. The economic breakeven point of the facility was determined at $16 per ton of raw fuel with actual fuel wood prices
at the time varying between $13 and $25/ dry tonne.
Figure 2 gives an overview of the capacities of the units constructed in the
industrialised world during the last five years and implemented in both the industrialised world
and in developing countries. As can be seen, typical capacities in Europe and North America
nowadays are in the range of 80 to 300 kW whilst for developing countries these are slightly
smaller typically from 40 to 200 kW. Further, the maximum capacity presently is in the range
of 1 to 5 MW. Despite the commercial availability of the technology, only limited operating
experience is available from the open literature. There is no doubt, however, that significant
scope still exists to improve the available technology. To show this in more detail, a diagram
of these systems is presented in Figure 3.
Although some counter current moving bed gasifiers have been installed, nearly all
modern systems for power generation are of the downdraft moving bed type. This is because
of the cleaner gas produced by downdraft gasifiers resulting in a relatively less complicated
cleaning process and less environmental problems with respect to waste water. However,
downdraft gasifiers show little flexibility with respect to feedstock moisture content (15-20%)
and feedstock size. Well defined chips or pellets with a moisture content not exceeding 25%
are necessary to produce a gas that has a really low tar content. Most commercial systems
operate on wood chips while maize cops and coconut shells can be successfully gasified too.
Loose materials such as straw, rice hulls and MSW are difficult to gasify at a small
scale. Pelletisation has been successfully applied but increases costs of the feedstock to $25
per tonne. A potentially very large market exists for small scale rice hull gasification. Initial
efforts by Kaupp to gasify it continuously at a scale of 30-60 kWe in a downdraft gasifier were
unsuccessful [8]. The main problems are:
134
poor flow due to low density and swelling in the pyrolysis zone
poor oxygen distribution due to small particle size
sintering arising from poor oxygen distribution
lack of a well designed continuous ash removal system.
Figure 2
Typical Distribution of Gasification Based Electrical Power Generation Units
Manufactured in the Industrialized World.
I - operating in industrialized world
II - operating in developing countries
III = I + II
Air
Biomass
Air-
Hot,
dirty
product
gas
Tar,
ash,
soot,
water
Cool
clean
gas
(Pilot diesel)
Exhaust
Electricity
Figure 3
Gasifier-Reciprocating Engine Systems
A = Gasifier C = Gas-air mixer
= C leaning and cooling section
D = Engine-generator set
135
Recently Manurung and Beenackers succeeded in solving all these problems by
developing a new type of gasifier optimally designed for rice hulls [9]. The system is shown
in Figure 4. Smooth flow of rice hulls is obtained by eliminating the throat of conventional
down draft gasifiers. Hot spots, causing ash sintering, is avoided by eliminating the
conventional local air inlets. Air is sucked into the gasifier over the whole cross section of the
surface of the bed resulting in a uniform combustion zone over the cross section close to the
top of the bed. Finally, a scraper slowly rotating over a grate effectively continuously removes
the ash from the gasifier.
GASIFIER
ASH FLUSHING
VESSEL
WATER SEAL
Figure 4
Small Scale UT/ITB Downdraft Rice Husk Gasifier with Ash Removal System
[9]
Such a device is essential because the rice hulls keep their original shape after
gasification. After successful trials both at Twente University, The Netherlands and the
Institute of Technology, Bandung, Indonesia, the first field unit of 10 kWe was installed at a
rice mill in an Indonesian village in 1986. It is operated by trained but otherwise unskilled
people. Now, after more than a year of successful operation the conclusion is that this
technology is promising and the Indonesian government has decided to start an implementation
programme.
On a larger scale, at 1-10 MWe, gasification of loose waste materials with relatively
high ash contents such as straw and rice hulls may be successfully gasified in fluidised beds.
For rice hulls van den Aarsen et al. have demonstrated this on a pilot scale [10]. Two methods
136
of gas cleaning are available: dry and wet. Dry dust removal can be carried out, for example,
by two cyclones in series followed by an impingement separator, filtration with high
temperature resistant fabrics and a cooler-condenser for tar and water removal [11]. The wet
method also uses cyclones followed by a wet scrubber, either of conventional or venturi type
design [12].
4.2
Low Joule Fuel Gas Utilisation

Gasification is a method to transfer the heating value of solid biomass into the heating
value of a combustible gas (and some sensible heat) while in combustion the heating value of
the solids is completely transferred into sensible heat. In principle, gasification offers some
advantages over combustion. Firstly, a gas has better burning properties relative to a solid.
The burning process is easier to control, it needs less excess air, it allows for simpler burner
construction, it causes no particle emissions, less air pollution and less fouling of the heat
exchange equipment. Further, gases can be burned in internal combustion engines (gas
turbines or reciprocating engines) and can be applied easily in combined cycles. Basically,
there are three main routes for combustion of the fuel gas produced (see Figure 5):
A)
external combustion for heating or drying purposes or for electricity
generation with a steam cycle
B)
combustion in a gas turbine
C)
internal combustion in either a diesel engine or a spark ignition engine, both
for shaft power and electricity generation.
ELECTRICITY
STEAM
CENERATOI!
ELECTRICITY
GAS TURBINE
DUST
COOLING
+
TAR CLEANING
DIESEL
ENGINE
. ELECTRICITY
ELECTRICITY
Figure 5
Low Joule Gas Production and Power Applications
4.2.1
External Combustion of Producer Gas

The direct use of the gas in a furnace (route A in Figure 5) is the simplest application
and this generally requires little or no gas treatment except for dust removal. For efficiency
reasons it is important to preserve the sensible heat of the product gas which requires close
coupling of the gasifier and the furnace. In many cases it is possible to convert an existing
natural gas or fuel oil fired facility to biomass firing by adding a gasifier. This requires some
137
repiping and change of burners etc., but not necessarily a derating of the facility. If a
completely new installation has to be constructed the situation is somewhat different and clearly
direct combustion is a competing alternative.
It should be realised that in many wood combustion installations some gasification
occurs, and complete combustion is realised by the introduction of secondary air. Thus, two
stage gasification with combustion and direct combustion systems are essentially the same.
There remains, however, a difference in controllability, especially under varying load
conditions. Generally it can be said that in gasification units combustion of the product fuel
gas can be expected to have less impact on the environment than in direct combustion. In
retrofitting an existing unit special attention must be paid to the burner. In most cases natural
gas or fuel oil will be replaced by a hot dirty gas of low heating value. The characteristics of an
ideal burner to cope with such a gas were defined recently as follows [13]:
the burner should maintain stable combustion over a wide range of gas compositions and
gas energy content and should be adjustable without modification to accommodate different
gas types
it should have low pollutant characteristics
the burner should be able to handle dirty gas without clogging or frequent servicing
the burner should be able to operate at low gas pressures
if possible, the burner should be able to simulate the heat release patterns of a natural gas
burner so that retrofit modifications could be attempted.
Many types of commercially available burners for low Joule gases have been tested by
the Canadian Gas Research Institute but none were found entirely satisfactory, mainly because
of susceptibility to clogging or erosion/corrosion with dirty tar laden gases [13]. Therefore,
the Canadian Gas Research Institute has developed a modified two stage burner which,
reportedly, meets the characteristics described above. It can handle a gas with a calorific value
as low 3 MJ/Nm' standard cubic meter which is heavily laden with dust and tar as results from
counter-current updraft moving bed gasification systems.
4.2 2
Combustion in a Gas Turbine.

This is shown as route in Figure 5. The favourable properties of gas turbines such as
long running periods between overhaul, low cost of maintenance, potential high inlet
temperatures favouring high thermodynamic efficiencies and the possibility of using the
exhaust gas in a steam generation cycle (combined cycle), make turbines potentially very
attractive for use in combination with a gasifier. F urther developments in turbine technology
are probably needed such as in prevention of corrosion by alkaline metal vapours, improved
tolerance to trace amounts of dust, and in control technology of the gasifier-engine system.
For an optimally integrated system the gasifier has to be pressurized [14-16]. F or an air blown
gasifier the optimum pressure will be in the range of 10-30 bar. Operation under pressure
increases the complexity of both the gasifier, the reeding and the ash removal system and can
probably only be done economically for relatively large capacities. Efficient filtering,
preferably at high temperature, will be required to protect the gas turbine.
4.2.3
Internal Combustion in Engines.

A gasifier/engine system is currently the most attractive way of generating shaft power
or electricity from biomass in the power range from a few kilowatts to several megawatts.
This option is made attractive by the simple arrangement of a gasifier/engine system with the
relatively high overall efficiency in producing shaft power at different loads (with diesel
engines up to 30%), and the possibility of immediate use of other fuels. The technology is
already relatively old, having started in the 1890's. The wide spread application in the second
world war was caused by a shortage of liquid fuels and its moderate revival in the last two
decades was stimulated by sharply increased crude oil prices. Re-introduction of this
technology for traction will probably remain a curiosity in the industrialised world, unless a
dramatic shortage of liquid fuels arises. F or stationary applications, however, particularly for
electricity generation, the R&D work of the last 15 years has resulted in a commercially
successful technology which now is being implemented, especially in the developing countries.
A major problem is that minimum gas quality requirements for engines are still unclear.
138
For dust, values vary from <0.5 to <20 mg/m^ whilst for tar a maximum value of 100 rng/m^
is quoted. There is much uncertainty on the efficiency of the gas cleaning methods. On dust
filtration some results have been published recently [17]. Primary cyclones were found to be
not effective for particles below 5 micrometer, Barrel filters not effective for diameters in the
range 0.3-3 micrometer and bag house filters not efficient for particles between 0.3 and 1.0
micrometer. However, two stage or two sleeve fibre glass filters were found to be effective for
any particle size. Tar removal seems to remain the major problem, particularly at the small scale
below several MWe where secondary gasification is not economical. Under specific, but
poorly understood conditions, particularly with respect to specifications on fuel size,
downdraft gasifiers can produce a relatively tar free gas. However, with irregular solids or
with no-throat gasifiers as developed for rice hulls, tar removal still requires further additional
R&D.
Control devices for optimizing the fuel/air ratio to the engine under varying loads are
proven technology, as are the engines [18]. Whether to choose for a diesel engine or a spark
ignition engine will vary from application to application. For a discussion on this topic see
Kohan [19] for example.
For biomass based power stations of capacities of 10 MWe and higher, direct
combustion of biomass is technically proven and an economically feasible technology in some
applications [20]. It follows that there is still a need to develop biomass based power
generating systems in the capacity range of 1-10 MWe. It is here that gasification in fluidised
beds and/or in fast circulating fluidised beds may have potential. Both atmospheric gasification
and pressurised gasification may be considered, with the latter option probably in combination
with route B of Figure 5 (power generation by gas turbines).
For biomass based power generation in engines Fritz Werner has sold units up to 1
MWe [21] and Ahlstrom Oy in Finland has developed units for combined heat and power in the
range of 2-28 MWe + 3-35 MWt [2]. European operating experience both with a countercurrent Smaus system and a two-stage Michel Kim (Easimod) gasifier each at a capacity of 500
KWe have been collected by Friedrich Wahl GmbH. [22]. For operating experience in
developing countries, reference should be made to the reports of the World bank [23].
4.2.4
Gasification for Ammonia Production

A pressurised high temperature Winkler fluidised bed gasifier is operated in Finland for
ammonia production [24]. The feed is 23 ton peat per hour and the pressure is up to 4 bar.
The longest uninterrupted operation time so far has been 31 days.
4.3
Medium Joule Gasification

Medium Joule gas can be produced if oxygen instead of air is used as the gasifying
agent. Alternatively, steam can also be used as the gasifying agent but then some provision
should be made to supply sufficient heat to the gasifier because steam gasification is an
endothermic process. Various options are available as indicated in Table 5. The so called
Oxygen Donor Gasification process may lead to a Medium Joule Gas using air as the gasifying
agent. For a review of the various process principles and technologies, see Beenackers and
van Swaaij [25, 26].
Although none of these medium Joule processes are commercial yet, much
development work has been done during the past decade, particularly in the European
Community under the second E C Biomass Development Programme "Methanol from Wood".
An overview of the companies involved in medium joule gasification and of the process types
they selected to develop is presented in Table 5 above. Under the E C programme four pilot
plants were operated at design capacities ranging from 4.8 to 12 tons dry wood/day. An
overview of the results is presented in Table 6; a more comprehensive analysis of the results of
this programme has been published elsewhere [27]. The main result of this programme is that
atmospheric gasification with oxygen both in a classical fluid bed (Framatome) and in a fast
circulating fluid bed (Lurgi) are technically proven.
139
Table 5
Principle Gasification Routes for Medium Joule Gas from Biomass
Gasifying Agent Process Types
Processes
Downdraft
Updraft
Oxygen
Cross flow
Huid bed
Circulating fluid bed

Entrained bed
With heat carrier (doublefluidbed)
Steam
With indirect heat supply (fluid bed)

With recycle of synthesis gas (fluid bed)
With heat and oxygen carrier
(double fluid bed)
Air
SERI
SFW-Funk
Purox
Simplex
Foster Wheeler
Framatome*
IGT
Omnifuel
Lurgi*
Texaco
Baillie
Battelle
TNEE Compiegne*
AVSA*
C02 Acceptor
ALI 'bN/ltaienergie*
John Brown/Wellman*
* Sponsored by the Commission for the European Communities.
Table 6
Main Characteristics of Pilot Plant Projects for EC Methanol from Wood
Programme
Organisarion
Press:. Capacity Reactor

bars kg dry
yS
wood/h
Gasifying
agent
Duration H'carbon Reagent

of test
in svngas. use. kg/
run
vol %
kg wood
Framatome 1
350
fluid bed+ 2
empty tube
gasifier
0 2 & H 2 0 24 hrs
for 1 & 2
gasifier
0.6
02:0.57
H20:0.08
Lurgi
200
circulating
(fluid) bed
02&H20
36 hrs
6.5
02:0.453
H20:0.02
John Brown 1
/Wellman
400
double fluid
bed + chemically
active solids
Air
9.5 hrs
12.5
Air only
Italenergie
/AGIP
500
1 fluid bed steam H20 for 1 100 hrs

gasifier heated
gasifier, 02
through wall + 2 for 2 gasifier
fluid bed
12.4
N/A
140
Progress on circulating fluidised beds has been realised with both the AVSA process
[28] (G4) and the TNEE-Compiegne [29] (G5) dual fluidised bed. Due to significant
improvements in the slot designs of the former, the early problems of excessive gas-leakage
between the compartments have been largely eliminated.
The EC programme aimed to develop the large scale methanol from biomass
technology. With present oil prices below US$20/bbl this technology is not economically
feasible. However, application for power generation is already a viable option, depending on
site specific conditions. Prospectives for large scale power generation via pressurised
gasification of coal using low cost oxygen enrichment techniques such as membrane
technology, means that medium joule gas might also be viable from biomass. If so, there is an
extra incentive for pressurisation of the gasifier because of the increased flow ratiorproduct
gas/gasifying agent, in oxygen gasification relative to air gasification. This conclusion holds
for either methanol synthesis or power generation. In the latter technology the use of gas
turbines seems to be particularly attractive because of efficiency considerations. Although this
route is not commercially available yet, significant development work on pressurised medium
joule gasification is in progress; particularly in fluidised beds (see Table 7).
The Framatome project [30] (Gl, Gil) is the only pressurised pilot plant within the
EC. Operating results will probably become available from 1990 onwards. In parallel,
fundamental research is carried out by Gelus et al, on the kinetics of gasification under pressure
[31] (G10). This is considered to be essential research for pressurised units because hardly
any information is available on the influence of pressure on pyrolysis and gasification but for
the fact that such an influence exists.
Table 7
Pressurised Oxygen-Wood Fluid Bed Gasification Projects [30, 32-35]
Company
Framatome
MINO
Biosyn/Omnifuel
IGT
4.4
Pressure
bar
5-30
10-30
14
20
CaDacitv
kg drv wood/hr
Moisture
wt%
Temperature
2500
300
1400
400
15-40
50
5-45
800-1000
700-850
Catalysis in Medium Joule Gasification

Results obtained outside the E C have shown that a potential exists for catalysis both in
enhancing gasification rates in double fluidised bed processes and in improving the synthesis
gas quality, reviewed in [26]. A major conclusion of the Venice Workshop on thermochemical
conversion routes in 1985 [36] was that also the E C should take up fundamental research in
this area. As a result, the third C E C . R&D subprogramme Energy from Biomass, which
started in 1986 included several topics such as the project of TNEE on the improvement of the
dual fluidised bed wood fast pyrolysis/gasification process by use of catalysts [37] (G5). The
project consists of:
fundamental studies on the catalytic activity of dolomite;

development of a catalyst with favourable characteristics under operating conditions in a
double fluidised bed (sintering, erosion, poisoning);
solids circulation studies on a fluidised bed gasifier - fast circulating combustor system;
pilot unit tests at a capacity of 10-20 kg/hr.

A special feature of the TNEE process is a counter-current gas-solids trickle flow
contacting device above the fluid bed. Here pyrolysis gases are heated with the hot solids from
the combustor raining down into the bed over a packing. The main challenge of the project is
in finding suitable catalysts for product gas composition improvements and/or reduction of the
solids circulation flow rate. The main problems here will be catalyst deactivation, particle
attrition and catalyst effectivity to produce a hydrocarbon free gas. As far as the project
concentrates on alkali carbonates as catalysts still much work remains to be done at the
141
fundamental level on a small scale.
A second project is at the University of Zaragoza [38] on catalyst steam gasification,
which includes testing catalysts on activity, selectivity, deactivation rates and attrition risks.
Results obtained with a single fluid bed are reported at this conference [39]. Future work will
be directed towards a circulating multi-solids fluid bed such as developed by Battelle Columbus
[40].
4.5
Hydrogen From Producer Gas

Traditionally, the E C "Energy from Biomass" Programmes have also supported the
exploration of speculative new ideas on a laboratory scale to explore long-term potential. An
example is the recovery of pure hydrogen from low joule producer gas by a slurry of
hydridable metal alloys. Under the previous programme very reactive metal alloy slurries have
been developed [41] (G3).
The objective now is to select suitable reactors to apply the technology at a continuous
scale, and to evaluate the design rules for scaling-up and to optimise the process conditions.
Opportunities are in synthesis gas production from simple single bed air gasification, in
providing the hydrogen both for pyrolysis oil upgrading and direct hydro-liquefaction of
biomass, and, who knows, in cold fusion if it ever becomes practical.
5
5.1
PYROLYSIS
What is Pyrolysis?
Pyrolysis is thermal degradation either in the complete absence of oxidising agent, or
with such a limited supply that gasification does not occur to an appreciable extent which may
be described as partial gasification. Relatively low temperatures are employed of 500-800C,
compared to 800 to 1100C in gasification. Three products are usually produced: gas, liquid
and char, the relative proportions of which depend very much on the pyrolysis method and
reaction parameters. Fast or flash pyrolysis is used to maximise either gas or liquid products
according to the temperature employed.
5.2
Why is Pyrolysis Interesting?

Pyrolysis is attractive because solid biomass and wastes which are difficult and costly
to manage, can be readily converted to liquid products. These liquids, as crude bio-oil or
slurry of char and water or char, have advantages in transport, storage, combustion, retrofitting
andflexibilityin production and marketing. The energy density advantages are summarised in
Table 8.
Table 8
Energy and Density Characteristics of Biomass and Derived Products
Feed
Bulk
density
kp/m3
Straw
Woodchips
Pyrolysis liquid
Char
Char-water slurry (50/50)
Char-oil slurry (20/80)
-100
-400
-1200
-300
-1000
-1150
Heatine value
drv basis
GJ/t
Enerev
densitv
GJ/m3
20
20
25
30
15
23
2
8
30
9
15
26
The crude pyrolysis liquid is a black fluid which is often referred to as bio-oil,
pyrolysis oil, or just "oil". The other main liquid product is a slurry which can be made from
water and ground charcoal with chemicals added to stabilise the suspension. Stable and mobile
concentrations of up to 60% wt charcoal have been reported. Slurries can also be made from
the oil and char.
In pilot plant work to date the gas is usually flared but in a commercial process it would
142
be used to drive the process or use it as a fuel gas for fuel drying or power generation [42].
In transport bulk density is important, and some estimated values are given in Table 8
above. Oil and slurry mixtures have a clear advantage over woodchips and straw in transport
bulk densities and notably in energy density. For longer distances this difference may be a
decisive factor.
Storage and handling may be important because of seasonal variations in production
and demand and some storage will always be required [43]. Apart from the bulk density and
energy density considerations, it is important to appreciate that crude biomass (such as wood
chips and straw) will deteriorate during storage due to biological degradation processes. Char,
however, is very stable and will not deteriorate. Another important factor is handling, in which
liquids have significant advantages over solids.
Potential disadvantages can arise from the chemical and physical instability of bio-oil,
bio-slurries and mixtures, although there are mixed reports on such problems. These are
discussed later, but unless the properties of these fluids can be completely controlled, the
advantages of liquid fuels cannot be fully realised.
Combustion, retrofitting, market flexibility. Generally liquid (or gaseous) products are
easier to handle in the combustion process and this is important in retrofitting existing
equipment. Existing oil fired burners cannot be fuelled directly with solid biomass without
major reconstruction of the unit, which may not be attractive in uncertain fuel markets.
However bio-oils, char-oil slurries and char-water slurries are likely to require only relatively
minor modifications of the equipment or even none in some cases [44]. Powdered coal fired
furnaces can relatively easily accept charcoal as a partial fuel replacement, as long as the volatile
content is compatible with the furnace design.
It is likely that gas turbines can be readily fired with bio-oil and slurry fuels although
care is needed with the alkali ash residue in the char content of the slurry [45]. Modified diesel
engines may also be modified to accept upgraded char/water slurries or related products, but
there is little recent practical experience as yet. In most countries there is a small market for
charcoal lumps and briquettes for leisure and industrial applications and small regional markets
for firewood, usually as logs. There is reported to be a growing demand for charcoal for
specialist steel and non-ferrous metal production [46].
5.3
Pyrolysis Technologies
The heat required for pyrolysis can be added indirectly in a variety of ways such as
indirect firing, hot gas, or hot liquid such as metal or molten salt [47](PI2), or directly by
partial gasification with limited addition of oxidising agent such as air to give direct heating
[48KP5).
Pyrolysis has been practiced for centuries for production of charcoal. This requires
relatively slow reaction at low temperatures to maximise solid char yield (P6). More recently,
studies into the mechanisms of pyrolysis have suggested ways of substantially changing the
proportions of the gas, liquid and solid product. This is achieved by changing the rate of
heating, and the final temperature (P7).
High heating rates, of up to a claimed 1000C/s or even 10 000C/s, at temperatures
below about 650C and with rapid quenching, causes the liquid intermediate products of
pyrolysis to condense before further reaction breaks down higher molecular weight species into
gaseous products. These high reaction rates also minimise char formation, and under some
conditions no char is apparently formed. At higher maximum temperatures the major product is
gas. Pyrolysis at these high heating rates is is known as fast, flash, or ultra pyrolysis
according to the heating rate and residence time, although the distinctions are blurred. Other
work has attempted to exploit the complex degradation mechanisms by carrying out pyrolysis
in unusual environments. The variations are summarised in Table 9.
A wide range of processes based on flash pyrolysis have been researched and
developed in these various modes in the last few years either to produce liquid bio-oil in high
yield, or to produce chemicals. In a few cases a reactive environment has been included to
influence the type of products. Examples of the main technologies and reactor configurations
employed are listed in Table 10, which is not intended to be exhaustive but indicative of the
variety of processes under development [50].
143
Table 9
Characteristics of Pyrolysis Technologies [49]
Slow pyrolysis
Carbonisation
Conventional
Fast pyrolysis
Fast
Flash - liquid
Flash - gas
Ultra
Vacuum
Reactive pyrolysis
Hydropyrolysis
Methanopyrolysis
Temp.
Cmax
Maior
product
very low
low
400
600
solid
gas,, liquid & solid
0.5-5 s
<1 s
<1 s
<0.5 s
2-30s
fairly high
high
high
very high
medium
650
<650
>650
1000
400
liquid
liquid
gas
gas
liquid
<10s
high
<500
liquid
Residence
time
Heating
rate
hrs-days
5-30 m
Table 10
Examples of Pyrolysis Technologies [50]
Pvrolvsis technology andI main product(s) Reactor
Organisation. Country
Liquids
Conventional for liquids
Cyclonic for liquids and gases
Fast entrained flow for liquids
Vacuum for liquid fuels and chemicals
Ablative for liquids and chemicals
Low temperature for liquids & charcoal
Flash fluid bed for liquids
Stirred bed
Alten (KTI + Italenergie), Italy
Cyclone
Ensyn Engineering, Canada
Entrained upflow
Georgia Inst Tech., USA
Multiple hearth
Laval University, Canada
Vortex
Solar Energy Research Inst., USA
Auger
Tbingen University, West Germany
Fluid bed
Waterloo University, Canada
Solids
Conventional for charcoal & liquids
Downdraft
Gases
Molten salt
Methanopyrolysis for gases & chemicals
Hydropyrolysis for gases & hydrocarbons
Twin fluid bed fast pyrolysis
Fluid bed
Aston University, UK
Batch
Entrained flow Brookhaven National Lab., USA
Autoclave
Toronto University, Canada
Twin fluid bed
TNEE, France
Fluid bed
University of Zaragoza, Spain
Chemicals
Vacuum for liquid fuels & chemicals
Ablative for liquids & chemicals
Molten salt for gases & chemicals
Methanopyrolysis for gases & chemicals
Hydropyrolysis for gases & hydrocarbons
Multiple hearth
Laval University, Canada
Vortex
Solar Energy Research Inst., USA
Batch
Entrained flow Brookhaven National Lab., USA
Autoclave
Toronto University, Canada
Bio-Alternative SA, Switzerland
One of the more innovative processes being developed is based on the principle of
ablative pyrolysis in which biomass "liquifies" if it is pressed onto a hot moving surface at
below about 650C [51]. At these temperatures the liquid vapourises and if it is removed
sufficiently rapidly from the high temperature zone and quenched, high liquid yields with very
144
low char yields result The most advanced research of this type is being earned out at the Solar
Energy Research Institute [52] and a diagram of the equipment is shown in Figure 6. Other
processes based on a range of technologies are also well advanced [50] and await a suitable
opportunity for larger scale demonstration [53].
To liquid condensation
train and collection
Biomass pins
Char
cyclone
Screw feeder
400 to 750 C
Steam
Steam
ejector
Vortex
reactor
Char
receiver
Figure 6
Vortex Ablative Pyrolyser at SERI [52]
5.4
Pyrolysis Products
5.4.1
Liquid Product
The process of pyrolysis is complex, but a recent theory is that primary vapours are
first produced, the characteristics of which are most influenced by heating rate. These primary
vapours then further degrade to secondary tars and gases, the proportions and characteristics of
which are a function of temperature and time [54]. Yields of liquids from pyrolysis can thus
be influenced by the rate of reaction, with fast or flash pyrolysis at lower temperatures of
typically 450-650C giving the highest liquid yields.
This liquid product may be readily bumed [44] and has been employed for this purpose
[55]. There are, however, some precautions which have to be taken in handling, storage and
combustion due to the water and high oxygen content (P6). For these reasons, pyrolysis
liquids cannot be directly assimilated into a conventional fuel marketing infrastructure and some
conversion or upgrading is necessary to give a product that is compatible with conventional
fuels. Upgrading technology is not well developed with most attention being paid to either
hydrotreating or zeolite decarboxylation to give synthetic gasoline and other hydrocarbons.
Characteristics and Utilisation
The liquid product is a highly oxygenated hydrocarbon with an appreciable proportion
of water from both the original moisture and reaction product. Solid char may also be present
Raiano). These properties can make it relatively unstable in both chemical and physical terms
and have been reported to cause some problems in utilisation and upgrading. It is readily
combustible, but care has to be taken in storage, handling and atomisation. Some of the other
characteristics are discussed below [56].
Water content is important as it has several effects: it reduces the heating value, affects
the pH, reduces the viscosity, influences both chemical and physical stability, reduces potential
pollution problems from waste water disposal and could affect subsequent upgrading processes
[57]. The interactions are poorly understood. The water is difficult to measure and remove,
since evaporation or distillation at normal temperatures of around 100C can cause significant
145
and potentially deleterious physical and chemical changes in the liquid. Lower temperature
drying is not successful due to the nature of the relationship between water and the organic
component in which the water seems to be chemically combined, analogous to water of
hydration. This phenomenum makes claims of water content and consequently oxygen content
of liquids on a dry basis subject to some uncertainty. Water appears to be completely miscible
up to 20% by weight of total liquid, but above which an aqueous layer separates. Any water
that does separate must be carefully managed and this is discussed further below. Utilisation
and consideration of oil on a "wet" basis therefore seems to be more sensible. A much more
attractive approach appears to be to not condense the water by maintaining the pyrolysis
vapours above the dew point of water i.e. above about 110C. The principle has been tried by
Roy in his vacuum multiple hearth pyrolyser [58] and successfully practiced by Bio-Altemative
[59].
Particulate levels may be high from char and ash carry-over. Separation of solids and
liquids is poorly understood with reliance placed on primary separation in the vapour phase
downstream of the reactor before condensation. Efficient separation inevitably causes some
condensation or precipitation and careful design is essential. Solid separation in the liquid
phase is not believed to have been studied, but is very likely to be troublesome. However, it is
clear that a fairly high level of charcoal can be assimilated in the liquid product, for example
Alten reported up to 15% [48] although some lumpiness was evident in the bio-oil. Both char
particle size and proportions will influence the liquid product quality. This is why research into
char-oil mixtures could prove valuable.
Oxygen content of the pyrolysis liquid is very high, at up to 40% wt. When produced
from dry or low moisture content feeds it typically has a heating value a little above that of the
biomass feed in the range 20 - 25 MJ/kg, which has caused it to be referred to as "liquid
biomass". The oxygen content arises from oxygenated compounds including phenols and
polyphenols, which can be recoveered as a valuable chemical fraction [60].
Low pH arises from the organic acid content (e.g. acetic and formic acids), and is
therefore corrosive. Mild steel is not suitable for handling or storage. Polypropylene piping
has been used to overcome this problem.
Polymerisation or deterioration of the liquid can be caused by temperatures above
around 100C which adversely affect physical properties such as viscosity, phase separation,
and deposition of a bitumen-like substance. Heating the liquid to reduce viscosity for pumping
or atomisation needs to be considered carefully and thoroughly tested. Exposure to air also
causes deterioration, but at a slower rate than temperature increase. Maintenance in a sealed
enclosure has been claimed to cause substantial pressure increases, so some minimal venting is
necessary to avoid pressure build-up, but minimise exposure to oxygen. Pyrolysis liquid has
been stored in this way in a useable form for up to two years without problems (P6). Liquids
produced from refuse/MSW appear to be much more unstable [52, 61, 62].
Health hazards associated with pyrolysis liquids are also poorly understood. It has
been claimed that these are no worse than coal tar or crude oil [63].
Compatibility with conventional fuels is variously reported as immiscible but
compatible (P4). Pyrolysis liquids cannot be expected to be assimilated into a conventional
fuel marketing infrastructure without some conversion or upgrading to give a product that is
compatible with conventional fuels. One alternative is to feed to crude pyrolysis liquid into a
refinery for upgrading in orthodox refinery operations, utilising the hydrogen availability and
blending opportunities [64]. The alternative is to create a discrete pyrolysis liquids storage,
distribution and utilisation system, that is managed by experts who understand the special
problems of this fuel.
Some properties that have been reported are summarised and compared in Table 11.
Stabilisation
The crude liquid product can be used directly if in a single phase. If more than about
20% water is present, it can be processed to overcome some of the above problems by
emulsification with the water content if this separates (at typically above 20%wt water).. This
controls the stability of the liquid to a certain extent, and also enables the contaminated water to
be effectively disposed of, but at the expense of a lower heating value product. The cost is
relatively high with additives costing about half the value of the product as fuel [46,48].
146
Table 11
Comparison of Pyrolysis Technologies - Typical Data [1]
Temperature, C
Products, yield on daf feed
% wt gas
% wt liquid (dry)
% wt water
% wt char
Liquid characteristics
oxygen (raw product), % wt
oxygen (dry product), % wt
water, % wt
viscosity, cps@40C
pour point, C
density, g/cm^
pH
HHV, MJ/kg raw product
HHV, MJ/kg dry product
Elemental analysis, dry product
Cwt %
Hwt %
Owt %
H:C molar ratio
0:C molar ratio
Char content, % wt
*
(P5).
Conventional
Alten *
500
Fast
GIT
480
68
21
26
21
51
29
20
15
14.6
300
27
1.195
2
26.3
61.9
6.0
14.9
1.16
0.18
9.2
53
42
17
220
-23
1.26
Flash
Waterloo
510
10
66
10
14
18.3
22.1
39
18
40
1.19
2.4
16.3
-
52.2
6.3
41.5
1.45
0.60
54.7
6.4
38.9
1.40
0.53
Upgrading
Upgrading technology is based either on orthodox hydrognation technology to
produce successively lower oxygen content hydrocarbons, or the evolving zeolite technology
to produce hydrocarbon fuels directly.
Hydrotreating is based on technology that is established in the petroleum industry and
is in principle readily adaptable to reducing or removing the oxygen content of the bio-oil.
Preliminary results indicate that conventional hydrotreating processes may be readily adapted to
pyrolysis liquids [65](P8) and [66]. An alternative approach is to send the crude bio-oil to a
conventional refinery for upgrading with fossil oil. This has not yet been examined.
Zeolite based synthesis of hydrocarbons has been extensively demonstrated for alcohol
feeds. Some experience has been gained on upgrading products of cellulose pyrolysis by
decarboxylation [52, 67, 68], but there is concern over the problems of coking which would
require aregenerativeprocess. No reliable results are yet available.
Neither technology is yet available commercially, nor have robust mass balance and
performance data been produced, although a comprehensive technoeconomic assessment
suggests that atmospheric flash pyrolysis gives gasoline costs approximately double that of
conventional fuels with the potential to reduce this considerably in the medium term [69]. The
zeolite decarboxylation route gives potentially higher quality products due to preservation of the
aromatic structures resulting in high levels of benzene, toluene and xylene.
An alternative approach is to reduce the oxygen content to a sufficiently low level that it
may be satisfactorily blended with conventional fuels. This might be achieved by less complete
hydrognation, or by simple distillation over activated clay such as bentonite which is claimed
to give a stable and storable product in one low cost step. No work on blending requirements
is known to have been carried out, but has been considered as a possible route to utilisation
[64].
147
5.4.2
Gas product
The gaseous product from pyrolysis is usually a MHV fuel gas around 15-22 MJ/Nm3,
or a LHV fuel gas of around 4-8 MJ/Nm3 from partial gasification depending on feed and
processing parameters. It has a high level of hydrocarbons, particularly methane, and saturated
and unsaturated hydrocarbons from the complex thermal dgradation processes. The heating
value is enhanced if the gas is used and kept hot, from the sensible heat, and the relatively high
tar content. The gas may be used to drive the pyrolysis process if an indirectly heated process
is used, or it can be employed to dry the feed, or generate power.
5-4.3
Solid product
When pyrolysis is optimised for charcoal production, yields of up to 30 or 40% wt on
dry feed are obtained. This occurs in slow pyrolysis with reaction times of hours or days.
Partial carbonisation gives the higher yields, when the product contains a high level of
volatiles, and this is also referred to as torrified wood. At the very high heating rates
encountered in fast and flash pyrolysis, very low char yields result, and have been reported as
approaching zero under some process conditions. This avoids the marketing and design
problems of a multiple product process, since the associated byproduct - gas in the case of
liquid production for example - can be used as process heat [46, 53](P5). Char yields can be
optimised for production of material for char-water slurries, although an integrated approach is
necesary for maximum energy recovery.
5.4.4
Slurries
A possible outlet for the char is slurrying with the oil, or with water, or with both oil
and water. Only a limited amount of char can be introduced into oil as unacceptably high
viscosities result from a char concentration higher than about 30% wt [46] (P4, PIO). The
maximum concentration of char in water that can be handled is about 60% to retain mobility
[42]. Costs of the additive are significant at about 1/3 of the slurry preparation cost [46].
Three phase slurries of bio-oil, char and water or waste-water are not feasible.
Coal-water slurries are increasingly used in large boilers and these slurries can be
simply and/or partially replaced by char-water slurries. The char/water slurry cannot,
however, be an outlet for pyrolytic waste water as unstable sludge formation results. The ash
content of the char is an important consideration in developing liquid fuels, and de-ashing
processes are being examined [70] (P6).
Although in principle it seems to be attractive to remix all products of pyrolysis process
into one single liquid biomass derived fuel, this does not currendy seem possible.
5.4.5
Chemicals
Several hundred chemical constituents have been identified to date, and increasing
attention is being paid to recovery of individual compounds or families of chemicals [52, 58,
71] (P7). The potentially much higher value of speciality chemicals compared to fuels could
make recovery of even small concentrations viable. An integrated approach to chemicals and
fuels production offers interesting possibilities for shorter.term economic implementation.
5.4.6
Water
A key feature of the pyrolysis process is that water is produced in significant quantities
of typically between 20 and 40% wt on the feed, depending on feed moisture content. The
water phase is highly contaminated with dissolved and suspended organics, with a COD of
typically 150 000. This therefore represents a major problem of disposal or utilisation. In the
selection of the primary pyrolysis products this waste water must be considered (PIO). If
biological treatment is not appropriate or too expensive, part of the heat of combustion of the
products will be required for incineration of this heavily contaminated water fraction. The
pyrolysis gas should primarily be used for this purpose but this may not be enough in cases
where the primary feedstock has a high water content and the gas is required for feed drying.
A potentially more attractive alternative route than incineration is oil condensation above
the dew point of water, i.e. about 110-120C. The water then stays in the vapour phase and
can be burned with the product gas [59].
148
5.4.7
Secondary Products
The range of secondary products derivable from pyrolytic oil and char is summarised in
Table 12. The secondary products obtainable from the gas are not different from those
obtained by gasification (see Section 4).
Table 12
Secondary Products from Pyrolytic Oil and Char
Primarv
product
Process
Secondary
product
Process
Market
Size ranee
\Jh input
LHVgas
Engine
Turbine
Conversion
Power
Power
Ammonia
Conversion
Fuel gas
Electricity
CHP
Fertilisers
0.1-5
0.1-5
1-10
2-20+
MHVgas
_
Engine
Turbine
Conversion
Conversion
Conversion
Conversion
_
Power
Power
Methane
Methanol
Methanol
Hydrocarbons
.
Refine
Conversion
Refine
Fuel gas
Electricity
CHP
SNG
Methanol
Gasoline
Gasoline,
diesel, fuel oil
1-5
1-5
1-10
10+
10+
10+
10+
Liquid
Hydrognation Intermediate
Refine
Gasoline,
diesel, fuel oil
Gasoline,
diesel, fuel oil
5-20+
Zeolites
Hydrocarbons Refine
Char
(briquetting) Solid fuel
5-20+
0.2-5
Notes: + upper size limited by feed supply

5.5
Pyrolysis Implementation
Bio-oil is claimed to be a relatively easy fuel to use, provided the viscosity is not too
high. Preheating to reduce viscosity is not usually favourable due to thermal degradation of the
bio-oil. The water content can be considered an advantage both for the combustion process
and because it reduces the viscosity of the liquid. Therefore the oil can be considered an outlet
or disposal route for some of the pyrolysis water. Phase separation is likely to occur at water
concentrations greater than 20% which could only be counteracted by costly emulsifiers.
Moreover the water could render the oil more unstable and more corrosive. Methanol has been
suggested as a possible additive [42].
An alternative to upgrading bio-oils on a relatively small scale is to introduce them into
some sector of mineral oil refining operations [64]. Bio-oil has a relatively large oxygen
content however, and oxygen is not easy to remove, being placed in this respect between
nitrogen and sulphur contaminants in oil. In a refinery biomass oil would profit from the
economics of large scale processing used in mineral oil refining as well as the ready availability
of low cost hydrogen. Research is planned in this area. One problem is that the resultant value
attributed to the bio-oil by the refinery may be too low to justify implementation.
5.6
Pyrolysis Status in Europe and North America

A demonstration plant of 500 kg/h is currently operating in Italy for liquid bio-oil
production with plans for a series of small commercial units there, in Spain and in Greece. A
number of demonstration plants for flash pyrolysis for bio-oil production are operating in
149
North America at a scale of up to 25 kg/h with plans for several commercial developments
ranging up to 20 t/h, including a commercial installation planned for California based on the
SERI ablative pyrolyser [72]. In addition to conventional and well established units for
charcoal production, a number of new carbonisation processes have become available for
production of slurry fuels from the charcoal and also recovery of the oil as a liquid fuel [73,
74]. These are, however, slow pyrolysis processes that give a low liquid yield. Examples of
current activities are listed in Table 13, all of which are orientated to liquid or slurry fuels
production.
Table 13
Examples of Pyrolysis Processes
Status
Pilot
Demonstration
Commercial
Example, (country')
Reactor type
Ensyn (Canada)
Cyclonic reactor
SERI (USA)
Cyclonic reactor
GIT (USA)
Entrained flow
Waterloo (Canada)
Fluid bed
Laval (Canada)
Multiple hearth
Waste Water Treatment Centre (Canada)
Auger kiln
Cemagref (France)
Fixed bed
Fluid bed
Waterloo (Spain)
Alten (Italy)
Fluid bed or stirred bed
Rotary kiln
Kiener (West Germany)
Fixed bed
Bio-Alternative (Switzerland)
Horizontal moving bed
Pyrosol (USA)
Pyrotech (USA)
Cyclonic reactor (planned)
5.7
Pyrolysis Costs
Of major importance in implementation of pyrolysis technologies is the economics of
production. A preliminary economic analysis is given in Figure 7 to show the effect of scale of
operation and feedstock cost on product price [49].
Current typical fuel oil prices are around 125 ECU/t, which is equivalent to 80 ECU/t
of pyrolysis oil on an equivalent heating value basis of 25 MJ/kg although it is not yet
established what conventional fuel product can be equated to bio-oil. This is shown as the
lighter shaded part of Figure 7 which identifies the plant capacities and feed costs that can be
justified at this price level. The larger darker shaded area represents an oil price 50% higher,
showing the sensitivity of production costs to scale of operation and feed cost. Special credit
might be given to bio-oil because of the extremely low sulphur content and possibly low NOx
production. Thus pyrolysis oil could be competitive on a relatively small scale of production.
A more comprehensive assessment of bio-oil and bio-slurry fuel costs has recently been
completed [AVB 164/165].
6
6.1
LIQUEFACTION
What is Liquefaction?
Liquefaction is low temperature, high pressure thermochemical conversion in the liquid
phase, usually with a high hydrogen partial pressure and also a catalyst to enhance the rate of
reaction and/or to improve the selectivity of the process. This approach gives a more
physically and chemically stable liquid product requiring less upgrading to produce a
marketable hydrocarbom product. Catalysts are also employed to provide enhanced
hydrognation and de-oxygenation, as well as some selectivity in product formation.
The attractions of this technology include heat transfer to a liquid phase which is more
effective than to a gas phase, the liquid phase reduces the reactor and ancillary equipment
volume requirements, and the product is a higher quality liquid than from pyrolysis processes
in terms of higher heating value and lower oxygen content.
150
Pyrolysis Liquid Production Cost F eed Cost

400Product
cost, ECU/t
300'
2t/h
3t/h
5t/h
20 Vh
100t/h
200'
100'
40
50
60
Feed cost, ECU/t
Figure 7
Pyrolysis Oil Production Cost in relation to Fuel Oil Prices now &+50%
The high cost of high pressure processing, and unresolved problems of feeding
biomass slurries at high pressure, product separation from solvent if used, and use of high
pressure hydrogen have all caused significantly less activity in this area of thermochemical
conversion. Most work has been on a batch scale of operation (for example [75, 76] in
Europe, with only a few examples of continuous processing, including a 25 kg/h plant that was
built at Albany in the USA but has now been dismantled; a 1 kg/h plant in the USA [77] and
another in the UK [78].
More activity has concentrated on black liquor as a feedstock in recent years due to the
adverse economic situation for biomass derived fuels, and the economic and environmental
attractions of reducing the waste management problems surrounding black liquor [79].
The potential processing and reaction advantages of this conversion route should not be
ignored for longer term possibilities
6.2
Why is Liquefaction Interesting?

The particular interest of liquefaction is that a lower oxygen content product is produced
that is more stable and requires less upgrading to a hydrocarbon product. There are also
processing advantages with a liquid phase system that requires a lower volume reactor and
ancillary equipment, and also lower reaction temperatures that result in lower heat losses and
easier materials of construction problems.
A particular disadvantage is the high pressure requirement which is costly and
potentially more hazardous. This gives rise to feeding problems associated with slurries.
Hydrogen is often added to effect reducing reactions which increases problems and costs, and
In addition catalysts are often employed to improve yields of desired products which can lead
to more complex catalyst recovery systems or high costs from catalyst losses. A solvent is also
necessary as a solid carrier which requires separation and recovery and this also increases
process complexity and cost.
151
6.3
What products are produced?

The main product from biomass liquefaction processes is a low oxygen content oil
(around 10-15% wt oxygen on a dry basis), with a heating value of around 35-40 MJ/kg. The
byproduct gas may be used to generate hygrogen or used a low heating value fuel gas. Water
and a small proportion of char and ash residue are also usually formed. Similar products are
derived from black liquor. The oil product may be used directly as a liquid fuel to substitute
for fuel oil, or may be upgraded by hydrotreating to hydrocarbon fuels followed by refining for
assimilation into the transport fuel market.
6.4
Liquefaction Technologies and Status

Most work has concentrated on small scale batch type experimentation (L2), but some
work has also been carried on continuous flow systems (LI). Compared to gasification and
pyrolysis, there is comparatively little activity currently due to the high cost of establishing a
research facility and low conventional fuel costs. Examples of current activities are listed in
Table 14.
Table 14
Examples of Liquefaction Processes
Status
Bench
Reactor type
Autoclave
Autoclave
Autoclave
Flow reactor
Fluid bed
Pressure screw
Example, (country)
Inst Wood Chemistry (West Germany)
VTT (Finland)
University of Toronto (Canada)
T.U.Berlin (West Germany)
UMIST/MANOIL (UK)
University of Arizona (Canada)
Related to liquefaction is solvolysis in which biomass is dissolved in a solvent at high

pressure and elevated temperature, such as [80, 81] and supercritical extraction in which a
similar effect is carried out more selectively in a solvent under supercritical conditions, such as
[82]. Both technologies are at a relatively early stage of development.
8
8.1
CONCLUSIONS
Gasification
Low joule gasification of biomass for heating applications is a technically proven and
often viable technology, provided that the scale of operation is sufficiently large, and that
feedstock is available in sufficient quantities at an acceptable cost.
Low Joule gasification of wood for shaft power presently is commercially proven at
capacities up to a few MWe. Smaller units below 0.5 MWe have promising economic
potential in developing countries. The economics of retrofitting diesel fuel generator
sets with a biomass fueled gasifier can also be attractive in the industrialised world in
site specific situations.
Significant progress has been made in the field of medium joule gasification.
Demonstration projects now have reached the scale of 2-10 tons wood/day operating at
pressures up to 30 bar.
Short term opportunities for medium joule biomass gasification are probably in power
generation rather than in methanol production but this remains an interesting long term
opportunity.
The potential for catalysis both in enhancing gasification rates in double fluidised bed
processes and in improving synthesis gas quality has been recognised in the E C with
fundamental research at bench scale and larger scale applications. There is still much
progress to be made [83, 84].
The most likely short term markets for industrial use of fuel gas from biomass and
wastes are where gas quality specifications are undemanding such as in boiler
retrofitting and direct firing (in the production of lime, cement, bricks and unglazed
152
pottery). Current and short term economic applications lie in utilising wastes and
residues to produce power, and fuel gas where quality requirements are less
demanding. There is potential for the production of transport fuels and chemicals in the
longer term, particularly in less developed countries and those with few indigenous
conventional energy resources.
8.2
Pyrolysis
Pyrolysis offers the potential to convert solid biomass into a high energy density
product that is easy and inexpensive to transport and that may be readily utilised in existing
installations. The recent EC Energy from Biomass Programme actively examined many
aspects of the production, upgrading and utilisation of pyrolytic liquid fuels which will be
continued in the successor programme. There are still problems to be resolved, however, if the
potential of biomass pyrolysis is to be optimised, including product yield improvement,
product quality improvement, new upgrading methods, product testing and utilisation and
resolution of environmental problems [84, 85].
8.3
Liquefaction
Liquefaction produces a higher quality product in terms of heating value and physiscal
properties, but at the expense of the higher costs of pressurised processing and use of
hydrogen. Waste conversion, such as black liquor, is a potentially interesting option.
8.4
General C omments
The production of higher value products in combination with fuel production would
enhance the economic viability of the processes. An objective comparison of the various
technologies for different applications would be useful.
In general, there are still some technical gaps between biomass production and
conversion, and between conversion and application. These will need to be resolved as
attention continues to turn to renewable energies.
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Bio-Alternative S A, CH-2063 Engollon, Neuchatel, Switzerland
Cemagref, Parc de Tourvoie, 92160 Antony, France
Meier, D . in: G. Grassi, D Pirrwitz and H. Zibetta (Eds), Energy from Biomass 4,
Elsevier Applied Science, London (1989)
Meier zu Kocke, H, and Nelte, A in: G. Grassi, D Pirrwitz and H. Zibetta (Eds),
Energy from Biomass 4, Elsevier Applied Science, London (1989)
White, D , and Wolf, D , in: A V Bridgwater, and J L Kuester, (Eds) Research in
Manoil Ltd, c/o G Mortimer, Salford University Business Services Ltd, Business
House, University Road, Salford M5 4PP, UK
Solantausta, Y and McKeough, P, in: H Egneus and A Ellegard (Eds) BioEnergy 84
Vol , Elsevier Applied Science, 1985
155
80
81
82
83
84
Heitz, M, et al. in: A V Bridgwater, and J L Kuester, (Eds) Research in

Overend, R P, and Chornet, E, in: A V Bridgwater, and J L Kuester, (Eds) Research in
Labrecque, R et al,. I. and E. C. Prod. Res. and Dev. (1984) 23, ppl77
Bridgwater, A V, van Swaaij, W M and Beenackers, A A C M, "Thermochemical
biomass conversion: research development and demonstration requirements", in
Biomass for Energy and Industry, 4th EC Conference, edited by G Grassi, Delmon,
J-F Molle, and Zibetta, pp 441-456 (Elsevier Applied Science, 1987).
Beenackers, A A C M, Bridgwater A V and van Swaaij, W M, in: G. Grassi, D
Pirrwitz and H. Zibetta (Eds), Energy from Biomass 4, Elsevier Appi. Sci., London
(1989)
156
APPENDIX 1
RECENT EC SPONSORED RESEARCH IN EUROPE
References to all these projects may be found in Proceedings of EC Contractors Conferences,
including the Biennual ENERGY FROM BIOMASS Conference Proceedings published by
Elsevier Applied Science. Projects are identified in the text by the reference numbers below.
Gasification
G1 Air gasification of biomass for
fuel-gas production
G2 Catalytic steam gasification in fluidized
bed of some biomasses existing in
Spain to obtain a methane rich gas
G3 D evelopment of a new method for hydrogen
recovery from lean gas mixtures using metal
hydride slurries
G4 Further developments of the AVSA biomass
gasfication process
G5 Improvement of the dualfluidizedbed wood
fast pyrolysis gasification process; use of
catalyst and optimization of particulate solids
circulation techniques
G6 Modelling and application of biomass
gasification based power plants
G7 Modelling of biomass conversion processes
G8 Production of synthesis gas from biomass
gasification. Final data gathering.
G9 R&D of gasification module complete with
filters for rice husk & Biomass residue
energy conversion
G10 Study of biomass gasification kinetics
under pressure
G i l Syngas production from wood; the
pressurised gasification unit of Clamecy
Pyrolysis
1 Accoustic agglomeration to clean
pyrolysis gas
P2 D evelopment of a biomass utilization
system at the power plant in Avezzano
P3 Evaluation of potential penetration of
pyrolysis conversion technologies in
the mediterranean areas of Italy
P4 Improvement of pyrolysis emulsion/slurry,
P5 Improvement of pyrolysis conversion
technology utilizing agricultural and
forestry wastes,
P6 New process of suspension pyrolysis
and use of charcoal slurry,
P7
P8
P9
Production and utilization of synthetic

liquid fuels
Quality improvement of pyrolytic
oils from biomass
Study on the production of charcoal slurry
based on biomass pyrolysis products
J. M. Lemasle
FRAMATOME, France
J. Corella
University of Zaragoza
Spain
W.P.M van Svaaij
Twente University
Netherlands
H.A.Masson
INIEX, Belgium
A. Le Lan
T.N.E.E, France
J.Heaton
Energy Options Ltd., UK
B. Rhodes
A.Bernardini
CHAM Ltd., UK
ALTEN, Italy
G. Bonino
B.E.S., Italy
Universit de Compigne
France
A.S.C.A.B, France
M.Gelus
J Carr
G. Botti
Progettazioni Industriali, Italy
F.Cherubini
F. Uccelli
Consorzio Cooperative
della Marsica, Italy
Italy
L Antonelli and F Fonzi,

F Fonzi and L Antonelli
M Chassin
F Cailliez
C Esnouf
IA Vasalos
B Delmon
L. Leonardini
G. Salvi
Alten, Italy
Alten, Italy
GRADT, France
CIRAD, France;
Cemagref, France
CPERI, Greece
UCL, Belgium
CRITA, Italy
COGIS, Italy
157
PIO Study on biological degradation of the
acidic condensates coming from
pyrolysis of biomass
P i l Study of optimisation of the use of biomass
derived from forest for pyrolysis oil.
production
P12 Thermal conversion of biomass
in molten salt media
Liquefaction
LI Direct liquefaction of wood and
solid agricultural waste
L2 Production of synfuels and chemical
feedstocks by direct hydroliquefaction of
ligno-cellulosic biomass,
F.Fonzi
L.Antonelli
ALTEN, Italy
C. Erbaggi Societ Cooperativa Agricola

Forestale "Collelongo", Italy
JKMaund
H Meier zu Kcker Technical University

Berlin, West Germany
O Faix
Institute of Wood Chemistry
West Germany
158
A SURVEY OF BIOHASS LIQUEFACTION PROCESSES
R. CAPART, A. ELAMIN, S. AMMAR, M. GELUS
University of Technology - B.P. 649
F - 60206 - COMPIEGNE
Summary
From the 1970's, the liquefaction of wood or biomass has been
extensively studied in order to provide a liquid product easily
pumpable and stockable, very like to gasoline or fuel produced from
petroleum Industry. In this paper are exposed different methods to
obtain this liquid (oil) at a laboratory scale or from process
development units working in a continuous mode.
The oil from direct liquefaction or pyrolytic processes are often
ameliorated by a subsequent catalytical treatment which makes use of
either
hydrocraking catalyts (CoMo, NiMo, Pd, etc....) under
reductant atmosphere or zeolite - type catalysts (HZSM-5) without
reductant gas.
1. INTRODUCTION
Thermo-chemical conversion of biomass produces always gases, liquids
and solids. How the products share between these three states depends on
the process and temperature is the more important parameter.
Pyrolysis is the breakdown of biomass by heat in the absence of air
or oxygne. If pyrolysis is run at slow rates and temperatures less than
500C, then the process yields a maximum of solid residue, the charcoal.
In flash pyrolysis as in fast pyrolysis, heating rates are very high. The
solid residue is very small and the production of high quality gases is
very important, due to thermal craking of pyrolytic oils.
Liquefaction
processes
are
related to direct high pressure
hydrotreatment. The aim is to maximize the liquid yield, with a low
oxygen content. It is obvious that liquids, because of their energy
density, appears to give the only way to use biomass in transportation. A
high yield of liquids could be obtained not only by liquefaction, but
also by pyrolysis and upgrading of pyrolytic oils.
There
is no clear definition of the different processes of
thermochemical conversion. Neither the mass balance, nor the operating
conditions could bring a clear understanding of the lot of terms used in
the field of thermal biomass valorization. That could be a problem for
people in charge of reviewing the state of art of liquefaction.
In liquefaction processes, it is not obvious to evaluate the mass
balance and the results depends on the analytical methodology. Oil could
be the part which is extracted by a solvent as acetone or benzene or
159
methylene chloride and oil yields depend on the solvent, which is often
acetone. In this paper, conversion is evaluated as :
weight of wood - weight of solid residue
weight of wood
Water is always produced during thermochemical conversion of wood.
So, we can roughly consider that liquefaction leads to form fractions :
- gases
- oil
- water
- solid residue
and comparison of yield could be interesting from an economical point
of view.
2. DIRECT LIQUEFACTION OF WOOD - PROCESS DEVELOPMENT UNITS IN CONTINUOUS
Appell
(1) first studied the liquefaction of lignocellulosic
material at the Pittsburg Energy Research Center (PERC). He obtained a
heavy oil by reaction of wood at 350C in the presence of H 2 and/or Co in
aqueous Na 2 C0 3 . This preliminary work encouraged the PERC to. pursue
development of studies leading to the conversion of wood into liquid in a
single step.
A pilot demonstration unit (PDU) has been constructed in the 1970's
at Albany (Oregon) (2). This PDU being able to work following two
different processes which have been developped by the PERC and the LBL
(Lawrence Berkeley Laboratory).
The PERC process consisted of converting dried wood flour in an
anthracene oil, between 300 - 370C in the presence of N a 2 C 0 3 as catalyst
(2 - 8 wt * based on dry wood), under reductant gas, mixing C0/H 2 in the
proportion
60/40 and at 200 bar of pressure. Anthracene oil was
progressively replaced by recyling the oil produced. The original PDU was
submitted to many modifications to improve its working capacity and wood
treatment. In the best case it has been working during 572 hours with an
average flow rate of 8.75 kg/hour of produced oil. However, the wood
concentration in the slurry is dramatically low, no more than 8 * by
weight. In addition, serious technical problems due to undissolved solid
and increase of oil viscosity prevented the Albany PDU to work after
1981.
In order to increase the wood concentration in the slurry as well as
its pumpability, the LBL induced a pretreatment of the wood prior its
liquefaction. The pretreatment consisted to a mild hydrolysis in diluted
H 2 S 0 A at 180C. After milling, an aqueous suspension containing 30 * of
undissolved
lignocellulosic material is obtained. The liquefaction
reaction is performed from this suspension, the pH of which being
increased to 8 by adding N a a C0 3 . Contrarily to the PERC configuration
process, the LBL process did not require the recycling of produced oil.
The experimental difficulties encountered with the Albany pilot plant
conducted the LBL to study the liquefaction through a bench scale
laboratory unit (BLU) of much smaller capacity. From litterature data,
the LBL process operating either in PDU or in BLU mode provides no
advantage with regard to the PERC process. The working time and the oil
yield are inferior to those of the PERC process obtained in its best
configuration.
160
OPERATING CONDITIONS
TYPE OF REACTOR
REACTOR TEMPERATURE
PRESSURE (bar)
WOOD FEED RATE (Kg/h)
SLURRY FEED RATE (Kg/h)
Na 2 C0 3 /Wood
PERC (Run 12)
LBL (Run 7)
Univ. ARIZONA
PLUG FLOW
STIRRED
P.F. EXTRUDER
330
345
400
210
210
210
17,4
7,7
3,6
245
71
54
0,1
0,12
REACTANT GAS (Nm/h)
14,9
4,5
H 2 % IN REACTANT GAS
39,2
37,7
SLURRY VEHICLE
ANTHRACENE OIL
WATER
WATER
CHARACTERISTICS OF CRUDE OIL

GHV (Kcal/Kg)
OIL YIELD
(wt % on Wood Basis)
VISCOSITY (CPS)
8236,2
53,3
135
8025,3
25,1
142
8325
27
103
ANALYS] S (ON DRY BASIS)

C
79
79,2
80
8,5
7,8
8,4
12,5
14,4
10
Table 1
DIRECT LIQUEFACTION OF WOOD
CONTINUOUS PROCESS DEVELOPMENT UNITS
The major difficulties encountered with the Albany process plant was
the
pumpability
and
the
transfer of the slurry througout the
installation. To overcome these difficulties, some searchers such as
Eager (3) and White (4) used a screw-feeder or an extruder-feeder which
allow a certain defibration of the woody Material and a good circulation
of the slurry. The experimental device designed by Eager and al consisted
of an horizontal tubular reactor with an internal screw (Auger) which
vehicles water-wood slurry from a pressurized container through the
reaction zone. The liquefaction technique was not different from that of
LBL (catalyst Na 2 C0 3 , reductant gas : CO). The wood/water ratio being
about 0.4, Eager obtained good yields in produced oil (37 - 42 %)
nevertheless with a certain formation of wood char (1 - 15 * ) . Different
types of Auger have been tested. They were all subjected to serious
erosion or corrosion problems.
White and Wolf, at the University of Arizona have developped an
extrusion technique which permits a good feed and the pressurization of
the reactor as well as a mechanical pretreatment. The vertical reactor,
of plug flow type, was feeded with steam and CO so that H 2 was formed in
161
situ by water gas shift reaction catalysed by Na 2 C0 3 . Various tests up to
52 hours have been performed, covering a range of pressures from 50 to
210 bar and temperatures from 350 to 430C. Crude oil containing 6 to
10 % of residual oxygen were obtained and nothing was mention about char
formation, probably prevented by steam injection in the reactor.
3. DIRECT LIQUEFACTION OF WOOD WITH REDUCTANT GAS AT LABORATORY SCALE
A lot of research works has been devoted to the direct wood
liquefaction in order to prove the feasibility of a process and to define
the best experimental conditions, i.e temperature, pressure, choice of
carrier
solvent
or catalyst from numerous repetitive experiments
conducted in batch autoclaves generally of small capacity.
Early works due to Appell and the Bureau of Mines were exclusively
based on the use of very cheap catalysts such as Na a C0 3 . Boocock (5) (6)
has particularly studied the liquefaction of wood in aqueous suspension
and discussed the effect of various Ni basis catalysts as Ni Raney, Ni
salts or oxydes, at temperatures around 350C and initial pressures of
hydrogen in the range 17 - 100 bar. He obtained relatively low yields of
oil containing about 10 wt % of residual oxygen. No noticeable difference
was observed between the different Ni - basis catalysts upon the oil
yield.
Rogers (7) investigated the catalytic effect of different salts of
transition metals in the presence of steam and CO. The nature of chemical
bonds on the metal are determinant : the chloride, sulfate, acetate and
nitrate are not efficient. Only the oxyde and cyanid have a real
catalytic effect.
Soyer (8) liquefied wood sawdust in water suspension by using
various Fe basis catalysts under pressure of reductant gas H 2 or neutral
He at 340C and 40 - 60 bar. Among all the tested catalysts, finely
divided iron powder revealed the more efficient, but its activity is
decreasing during the reaction. With a sufficient initial quantity of
iron powder (14 wt * based on wood), Soyer obtained a total conversion of
wood and observed that the nature of gas (H 2 or He) has no significant
effect on the yield (about 40 %) and the quality of the oil produced.
From systematic experiments of wood liquefaction in organic solvents
(anthracene recycled-oil, pyrolysis oil) under hydrogen pressure, Meier
and Faix (9) have tested many current catalyts of hydrocraking. Because
of the high wood content in the carrier solvent, total wood conversions
were rarely reached and wood char was formed. Meier and Faix concluded
that only Pd on activated charcoal support and iron powder meet important
requirements of the liquefaction process such as complete recovery of the
carrier with simultaneously high yields on the net product oil. The use
of iron powder is preconized because of its very low cost. About the
influence of pressure, a minimum of 100 bar is necessary to recover the
whole carrier oil and to obtain low char formation. Gupta and Weiss (10)
made
an extensive study of the nickel promoted hydrognation of
celluloslc materials. Using both powdered newspaper and pure cellulose as
feedstock, they demonstrated the feasibility of converting celluloslc
materials into liquid hydrocarbons by reaction with hydrogen at 425C and
70 atm in a slurry phase with paraffinic oil and in the presence of
0.2 wt * Ni OH catalyst. Oil yield of 45 % was reported.
Delmon (11) and al. have used mainly tetralin as solvent and the
sulfided CoMo as catalyst. They have emphasized the role of CS a to
maintain the catalytic activity of CoMo during the reaction.
Araya (12) and al. compared the effect of gas, neutral or reductant
162
on the liquefaction in a typical hydrogen donor solvent : the tetralin.
The production of lighter organic liquid is favoured under an atmosphere
of hydrogen and with CoMo catalyst, particularly if the catalyst is
finely ground and dispersed in the reacting mass.
In the case of liquefaction of pure cellulose, Vasilakos and Austgen
(13) have obtained good oil yield for that type of catalyst in
conjunction with tetralin as solvent. When using 2-propanol, the best
catalyst is the Ni-Raney, giving very good yield in net product oil,
about 75 wt % (on the basis of cellulose), with an oxygen content
comparable to that of the cellulose derived oil in the tetralin/palladium
series (24 - 27 * ) .
4. LIQUEFACTION OR SOLVOLYSIS OF WOOD WITHOUT REDUCTANT GAS
In the early 1970 s' the Bureau of Mines (14) conducted some
interesting experiments using formic acid or sodium formate in place of
carbon monoxyde. This lowered the operating pressure at 250C to the
range 1000 - 1100 PSIG and still gave good oil yields as shown by the
table.
Water
ml
100
100
100
50
Catalyst: g.
Type
Amount
HCOaNa
HC0 2 H
1
5
2.5
2.5
5
1
2.5
2.5
Oil yield
60
55
55
41
Conversion
99.6
99
99.8
90
Table 2 : LIQUEFACTION OF WOOD WITHOUT REDUCTANT GAS
The products obtained at these mild conditions were pitches instead

of oils and revealed to be instable. The Bureau of Mines studied the
effect of recycling wood derived oil. A series of run at 250 to 275C
showed that the product become too viscous to use after only 4 cycles.
Without using catalyst and reactant gas, Yan (15) in 1980 liquefied
a variety of wood species and paper in aromatic solvents with high
boiling point (340 - 484C). Various experiments at temperature of
320 - 400C in batch or semi continuous reactor give yields of oil, gas
and water around 60 Ss, 17 % and 23 * based on the original wood. Yu (16)
selected organic solvent such as phenol and ethylene glycol and used them
with
an acid catalyst H 2 S 0 4 at temperatures lower than in most
liquefaction processes i.e 180C and 250C. Almost complete conversion of
wood into oil was obtained nevertheless with high oxygen content
(20 - 30 %).
Continuous liquefaction in mineral oil has been performed by Kaufman
and Weiss (17) using a finely divided paper slurry with 20 wt * solid
content.
Vanasse, Chornet et Overend (18) have tested two different solvents
in a continuous process (known as the UDES-S process) ethylene glycol and
creosote oil rich in by-phenol compounds. The reactor of plug flow type
was feeded by a wood-solvent slurry in the concentration range 14 - 18 S>.
The slurry was obtained after a pretreatment which associates an heating
163
up to 240C with a mechanical defibrating of the suspension through an
homogeneizing valve placed in a recirculation loop. The results are
clearly different from a solvent to another. With the creosote oil, the
yield in final oil is in the range 61 - 51 % and the wood conversion is
almost complete. With the ethylene glycol, the conversion is limited and
plateau 65 *. Nevertheless the yield in produced oil between 40 - 55 * is
satisfactory. The cellulosic fraction is relatively resistant to the
solubilization by ethylene glycol and can be isolated by this way. In
both cases, the oxygen content of the produced oil (ranging 21 - 29 %)
was much higher than that of the PERC process.
A recent study (19) has been reported about the dissolution of a
tropical prototype wood (eucalyptus) in various organic solvents. Simple
alcohol
(C 2 to C ) , ethylene glycol, water, phenol and phenolic
compounds : guaiacol and cresol. The experiments have been conducted in
batch autoclaves, heated up to 250C. Discussed in term of a kinetical
parameter, termed severity, the results show that an almost total
conversion of wood is obtainable with ethylene glycol and like phenol
products, only for a high degree of severity. Selective dissolution of
hemicellulose, lignin and cellulose are observed only with the polyol and
phenolic solvents.
Recently Boocock (20) has given up the use of Ni-Catalysts with
reductant gas and performed the liquefaction of wood samples of different
sizes by rapid steam injection at temperature between 335 and 355C. He
obtained good oil yields, around 50 wt % based on the original wood.
Some interests exist to process the biomass with solvents in their
supercritical state. As explained by Modell (21) in the case of water
(T 374C), the hydrogen bonds are weaken in critical conditions and
the solvent behaves very much like a polar organic solvent which leads to
prevent char formation by keeping intermediates highly solvated and well
dispersed. At the same time the presence of hydrogen, a product of
reforming can aid in stabilization of the intermediates. In supercritical
water, pure cellulose is completely degraded, after Modell. Supercritical
methanol has been employed by Grandmaison et al. (22) to perform
selective extractions on wood material.
5. THE CATALYTIC HYDROREFINING OF WOOD DERIVED OIL
Soltes (23) compared the activity of 20 different catalysts for the
upgrading of the oil produced from wood pine pyrolysis. The catalysts
were either metal transition oxydes or noble metals such as Pd, Pt, Rh.
The experiments were conducted with decaline or methylcyclohexane as
solvent at 400C and initial pressure of H 2 of 66 atm. The formation of
water
and hydrocarbons are enhanced by noble metal, however the
increasing in temperature leads to coke formation, a decreasing in light
products and an increasing in aromatic compounds.
Baker and Elliot (24) have successfully converted both high pressure
liquefaction oils and pyrolysis oils to a highly aromatic gasoline range
fuel. Their studies were conducted in a one liter continuous flow reactor
system. From Baker and Elliot, the production of high quality gasoline
boiling range liquid requires hydrodesoxygenation without saturing the
aromatic rings in the oil and the sulfided CoMo catalyst is the best
choice which satisfy this constraints. As shown by table (3) good quality
of oil have been obtained by BAKER particularly in the case of LBL
process oil leading to a final product with a 0-content near to zero.
164
PROCESSING
CONDITIONS
Source of oil
LIQUEFACTION PROCESS
OIL
PYROLYSIS PROCESS
OIL
LBL (N 7) PERC (n 12) GEORG TECH.
LAVAL
SERI
398
397
353
258-400
259-376
Total oil
1/1 feed oil
0.99
0.92
0.43
0.42
0.37.
Aqueous phase
1/1 feed oil
0.20
0.20
0.61
0.57
0.51.
H_ consumption
171 feed oil
616
548
457
711
689.
14.1
17
Temperature
YIELDS
Carbon conversion to gas wt %
35.5
25.
PRODUCTS
INSPECTION
Oxygen %
0.0 (14.4)
0.8 (12.5)
2.3 (52.6) 0.8(44.2) 1.3 (43.)
H/C ration
1.65(1.18)
1.5 (1.3)
1.67 (2.2) 1.7(1.77) 1.7 (1.7)
CS-225C Vol. *
> 87
37
72
87
73.
Table 3 - HYDROREFINING OF CRUDE OIL (BAKER and ELLIOT)

CATALYST CoMo/Al a 0 3 - PRESSURE 140 BAR
(
) Value related to feed oil
Various pyrolysis processes can produce oil at a lower cost than
high pressure liquefaction but the oils have a lower quality. The
pyrolysis oils have the tendency to form coke quite rapidly and to plug
the reactor bed. The Pacific Northwest Laboratory (24) has developped a
method to upgrade these oils and produce hydrocarbon fuels similar to
those obtained from high pressure liquefaction oils by increasing the
reaction temperature from a low value (about 280C).
GEVERT (29) upgraded PERC-process oil in a batch reactor in the
presence of sulfided CoMo finely ground and decahydronaphtalin as
solvent. All the distillation products of the upgraded oil i.e lights,
heavy gas oil and residue have an oxygen content less than 1 wt % as
indicated by table 4.
The pyrolysis oil obtained from wastes of olive industry can be
valorized by hydrotreatment. DELMON and CHURIN (30) preconized the same
methodology as BAKER and ELLIOT i.e. to avoid the coke formation, the
bio-oil must be pretreated at low temperature (< 300C) before to be
heated at the reaction temperature, around 380C. They reported also a
good
recovery of the solvent (tetralin) by distillation and the
possibility to replace tetralin by the distilled fractions from the
produced oil.
165
Fraction
Boiling
range
Lights
< 60
0.6
Heavy gas oil

Residue
250
50 - 350
> 350
H/C
14
85.4
2.0
0.7
14
85.2
2.0
0.8
9.5
89.7
1.3
Table 4 : ELEMENTAL COMPOSITIONS OF HYDROGENATED PRODUCTS Wt %

GIVEN BY GEVERT (29).
6. THE UPGRADING OF WOOD DERIVED OIL BY ZEOLITE CATALYSTS
Another approach to valorize the wood derived oils is to convert
these oils by using an appropriate catalyst in absence of reductant gas.
The appropriate catalysts can be classical cracking catalysts such as
silica/alumina bust the most used are zeolites known as SM-5 and
particularly HZSM-5 in pellet form with silica/alumina as binder. This
type of catalyst was already known to have a good efficiency for the
upgrading of alcohols, phenolic and many other oxygenated compounds. It
has a middle size pore structure and is constituted by cristallites of
various oxydes, principally Na a 0, Al a 0 3 , Si0 a , TiO a and eventually ZnO or
MnO.
The conversion reaction with zeolite is conducted at atmospheric
pressure, under neutral atmosphere, at temperature ranging from 400C to
550C. The feeding material can be either a condensed oil or the vapor
emitted from a pyrolysis process plant whithout condensation. In the
1980's
several
laboratories
have
studied
a
variety
of
pyrolysis/liquefaction oil over HZSM-5, the feedstock ranging from high
pressure oil (31) (32) to low pressure pyrolytic oils and vapor (33) (34)
(35) (36) (37). A review of upgrading possibilities for pyrolytic oils
from wood was prepared by Kaliaguine (38).
As for the simple model of oxygenated compounds, the upgrading
action of the ZSM catalyst consists of an almost complete removal of the
oxygen in the feed material under the form of H 2 0, CO and C0 3 . The
upgraded product is particularly rich in C, - C 1 0 gasoline fraction,
characterised by boiling points ranging from 70 C to 213C.
The components of the gasoline fraction are essentially aromatic and
are of a great economical interest due to the expected high octane
number, between 115 and 135, as reported by Diebold and Scahill. The main
compounds identified by mass spectrometry are :
Benzene
Toluene
m, , o Xylene
m, , Ethylbenzene
1, 2, 4 and 1, 2, 3, 4 Mthyl-Benzene
Indene/Indane
Cresol
Xylenol
Naphtalene
Milne and al. (39) have established a summary of hydrocarbon yields

reported from different works based on the use of HZSM-5. The yield in
hydrocarbon C + 2 (in wt * of original wood) is ranging from 12 % to 21 *
while the gasoline fraction C s - C 1 0 is ranging from 7.8 to 15 Ss,
depending on the method of pyrolysis which gives more or less char. The
166
ratio of aromatics (benzene, toluene, xylene) to olefin (ethylene,
propylene, butene) ranges from 3.8 to 8.3.
However, the zeolite catalysts are rapidly deactived by coke
formation which is more important for wood tar or derived oil than for
simple model compounds. Different solutions are suitable to reduce the
coke formation as the injection of steam in the bed of catalyst or the
coprocessing of the wood derived oil with methanol.
Till now, experiments have been performed in microreactor at a
laboratory scale. Scahill and Diebold (36) have proposed a technoeconomic
study about an industrial process-plant which would include :
- a continuous regeneration of the zeolite in a fluidised bed burner
- a separation step of the produced olefins.
7. CONCLUSION
Numbers of studies have been carried with different thermochemical
processes, i.e. pyrolysis, direct liquefaction and solvolysis show that,
liquid-oil can be obtained from a variety of wood materials. The yield of
this oil is in the range of 30 - 70 wt % based on the original solid
material. Whatever the type of the process, the oil produced is very
oxygenated compared with the petroleum products. The pyrolysis have an
oxygen content around 30 - 40 %; solvolysis oil in organic solvent
20 - 30 wt * and the oil obtained with direct liquefaction at high
pressure have a less oxygen content about 10 wt %.
Oxygen removal and molecular weight reduction are necessary to
produce usable hydrocarbon fuels. This can be actived either by catalytic
hydrotreatment on catalytic cracking. Catalytic hydrotreatment if often
carried in the presence of catalysts based on transition metals such as
CoMo, CoMos, MiMo, NiMos supported on alumine on in the presence of
Raney-nickel and noble metals like Pd, Rh under hydrogen pressure around
100 bar and at temperature range of 330 - 400C. Catalytic cracking could
be realized with zeolite supported on silice-alumine at high temperature
450 - 550C, zeolite such as HZSM-5 could eliminate the need of hydrogen
in the upgrading process and can effectively deoxygenate biomass oil to
produce hydrocarbons.
We can conclude that, for the feasibility of a liquefaction process
for producing hydrocarbon fuels, the research should be oriented to :
- regeneration of the solvent which gives maximum oil yield for
continuous liquefaction process ;
- catalysts development for cracking and hydrognation of the higher
molecular weight components.
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wood vapor and Model Compounds over HZSM-5 Catalyst pp. 287 - 296.
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Renaud J., and al. Conversion of vacuum pyrolytic oils froms populus
Deltoides over HZSM-5 , pp. 276 - 286. ACS preprints, Vol. 32, n 2,
DENVER, Colorado, April 1987.
DIEBOLD
J.P.,
SCAHILL J.W. Engineering Aspects of upgrading
pyrolysis oil using zeolites. Research in Thermochemical Biomass
Conversion. Phoenix, Arizona, April 1987. Eds Bridgewater and al.
Elsevier App. Sci. Pub, London.
CHEN .Y. and al. Fluidized Bed Upgrading of wood pyrolysis liquids
and related compounds, pp. 264 - 275. ACS Preprints. Vol. 32, n 2,
DENVER, Colorado. April 1987.
KALIAGUINE S. Upgrading pyrolytic oils from wood and other biomass
an annotated bibliographic review. Report for the Energy Project
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HZSM-5. Activity during wood pyrolysis product conversion, pp.
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Pub., London.
169
THE GEORGIA TECH ENTRAINED FLOW PYROLYSIS PROCESS
R. J. Kovac and D. J. O'Neil
Energy and Materials Sciences Laboratory
Georgia Tech Research Institute
Georgia Institute of Technology
Atlanta, GA 30332, USA
Summary
The Georgia Tech Research Institute has developed an atmospheric flash
pyrolysis process for the conversion of biomass to liquid fuels. The
successful demonstration of pyrolysis oil production of 60Z (moistureand ash-free) has been achieved in a large-scale Process Development
Unit (1.4 DRY TONNE/DAY).
Nearly fifty steady-state trials have
confirmed the technological reliability of the process. The liquid
biofuel product is a uniform mixture of oxygenated hydrocarbons and
modest levels of stably bound water. Char and non-condensable gases are
ancillary products. Gross product thermal efficiency of 94Z and a net
thermal process energy efficiency of 73Z are achieved. Oil and char
recovery exceeds 70Z (moisture- and ash-free). A conceptual manufacturing process and an economic analysis for oil production for a 200 TPD
plant is presented. The plant proves to be profitable even at current
fuel costs and investment costs (June, 1989 basis). Rate of return on
investment is 39.AZ. The payout period is 2.1 years. Total capital
investment is $2.28 million. Manufacturing cost per GJ is $2.70. The
process is being prepared for further scale-up from the PDU stage to a
commercial prototype.
1.
OVERVIEW
During the 1960's the Georgia Institute of Technology (Georgia Tech)
began the successful design and development of a patented Moving-Bed
(Vertical-Bed) Pyrolysis System for the conversion of biomass, municipal
wastes and sludge to high-energy density, transportable fuels (pyrolysis oil
and char) and a low-energy process gas which was used on-site for drying of
feedstocks (1). In the 1970's the Georgia Tech Moving-Bed Pyrolysis Process
was licensed to the Tech-Air Corporation (which became a subsidiary of
American Can Company) which, through a sub-license to American Carbons Co.,
has commercialized the technology. This technology was developed by Georgia
Tech and Tech-Air in four large-scale pilot plants and a commercial prototype
of fifty tonnes per day (TPD) which was operated continuously at a sawmill,
around the clock (24 hours per day) over a period of eighteen months before
the demonstration was terminated. That research, development and demonstration program, spanning 1968-1978, confirmed the reliability and high
efficiency of pyrolysis technology with biomass and municipal wastes, and the
economic viability of vertical-bed pyrolysis plants of 50-250 TPD.
That
170
Georgia Tech Moving Bed Pyrolysis Process, in commercial form, remains the
standard for commercial biomass pyrolysis technology.
The design for the Georgia Tech Entrained Flow Pyrolysis Process
originated in 1978 with an internally-sponsored project for the development
of an innovative process for the thermochemical conversion of biomass to
synthesis gas via a combined pyrolysis-gasification process. Following a
contract award from the U.S. Department of Energy in 1980, and after
completion of bench-scale studies and the construction of a preliminary
conceptual design and preliminary economic studies, which indicated very high
potential for an economically viable, stand-alone process for liquid biofuel
production, continuing research and development focused on the design and
development of a new pyrolysis process. With the revised objectives, the new
Georgia Tech Entrained Flow Pyrolysis Process was focused on the maximal
production of the liquid biofuel, pyrolytic oil.
A 1.5 TPD Process
Development Unit (PDU) was designed and installed in 1983. The purpose of the
experimental PDU was to investigate the entrained pyrolysis of wood under
steady-state conditions. The experimental parameters which have been studied
included feed material characteristics, particle size, pyrolysis temperature
and residence time. The data was analyzed in parallel and interactively, to
develop mathematical models of the kinetic and transport processes occurring
in the pyrolysis process.
By this methodology the process model was
progressively refined and improved process parameter predictions were
developed for maximal oil production.
In the later stages of program
development, after identification of key parametric parameters, oil yields
(dry basis) consistently in excess of 552 and achieving 602 were demonstrated
in steady-state operation of the PDU. Modeling indicates that 632 oil yields
are achievable in the PDU. The prospect of reaching 702 yields was indicated
with process design modification in future prototypes.
The program
consistently demonstrated mass and energy closures of 100 52 in which all
elements of the applicable equations were measured.
The validity of
engineering data is unlike that of most other pyrolysis projects. It is of
significance that the excellent closures have been achieved in a large-scale
process demonstration unit. The experimental results have demonstrated a
gross product thermal efficiency of 942 and an overall process efficiency of
732. Oil and char yields (dry mass) exceed 702. A detailed summary of the
development of the Georgia Tech Entrained Flow Pyrolysis Process has recently
been presented (2) . This paper will focus on the conceptual design for a
manufacturing process using the proprietary Georgia Tech Process for the
production of liquid biofuel and co-products.
The results of a detailed
economic analysis for a 200-dry TPD plant will be presented.
2.
PROCESS DESCRIPTION
A manufacturing flow diagram which highlights the key pieces of
equipment and systems for commercial scale operation of the Georgia Tech
Entrained Flow Pyrolysis Process is given in Figure 1.
There are three
principal sections to the manufacturing process: feed preparation, pyrolysis,
and product collection. A process flow block diagram is presented in Figure
2.
The incoming feed and outgoing product streams are identified in
relationship to the key process operations of a 200-dry TPD plant.
By
reference to both figures, the manufacturing process may be described.
Green wood chips at 502 moisture (wet basis) are brought from a
receiving and storage area and conveyed to a wood-burning dryer using a frontend loader. The dryer is a fan-circulatory design fitted with a metering bin
and a particle collector. The burner is a co-fuel design and uses wood and
product gas. (The exhaust gases from the wood dryer burner will be passed
through, and air-cooled in, a heat exchanger and used as a conveying carrier
171
ROTARY
SEPARATORS
AT
EXCHANGE*
ELOWBl A H)
AND
PYROLYBB
REACTOR
FEED PREPARATION
PYROLYSIS
PRODUCT
COLLECTION
FIGURE 1 MANUFACTURING FLOV DIAGRAM
gas for the reactor feedstock.) The wood chips are dried to less than 10Z
moisture (wet basis) and are transferred to a storage bin which supplies feed
to the pyrolysis unit on demand and provides surge capacity. The feed is next
comminuted in a hammer mill, fitted with a vibratory screening circuit, where
grinding reduces the average particle size of the wood and the moisture
content to 6 (wet basis).
The dried feedstock is screened to segregate
oversized pieces which are recycled to the hammer mill for regrinding. The
screened dry wood feedstock is transported to an enclosed feed bin mounted on
a lossinweight feeder. The particulate feed is dropped into a conveying
"inert" (nonreacting) gas carrier stream which consists of the combustion
products exhausted from the dryerburner.
This stream is fed into the
pyrolysis reactor mixing zone where the wood and conveying gas are mixed with
the entraining hot, inert (nonreacting) combustion gases of a woodfired
burner.
The wood is rapidly transported upwardly through the vertical
pyrolysis reactor and is completely pyrolyzed before exiting the reactor. For
a 200 TPD plant the entrained flow reactor will consist of a cluster of five
vertical tubes. The stream leaving the pyrolyzer consists of newlyformed
char, pyrolysis gases, water vapor (water of reaction, feedstockassociated
water, and combustion product water), and conveying/entraining combustion
gases. The char is removed by cyclone separation and is cooled before being
discharged into a sealed conveyor, whence it is fed via a rotary airlock to
a char conveyor. The char is conveyed to a storage bin from which it may be
retrieved by gravity flow for subsequent shipment. The char bin incorporates
a pressurerelief system.
The hot pyrolysis gas and vapor stream passes
through a multiple organic spray (pyrolysis oil) quencher system to condense
vapors.
The pyrolysis oil is collected in a series of patented high
efficiency, Georgia Tech proprietary rotary separators (3) as a relatively
narrow molecularweight fraction. This oil consists of a total liquid product
in total yield of 70.6Z with moisture content of 15Z (60Z dry oil yield).
172
Recycled go
Wood
ractmng
Recycled gas
id
Recycled gas
storage
pstr
Dried
ground
wood
Gas to
co-sited
users
Exhaust gai
^Juntar
st n a M
Dried
ground
wood
itary
Grinding
and
Pyrotyw
Char
Oil
Exhaust
9
Oried
ground
Char
storage
Dried
ground
wood
Oil
storage
Dried
ground
wood
PRODUCT MASS AND ENERGY YELDS FOR A MIXED HARDWOOD FEEDSTOCK

DRYOLYELO
Kg dry ol/
KgrraffMd
0.6
FIGURE 2
TOTAL CHAR
TOTAL OL (15%HO)
TOTAL GASEOUS
FUEL (DLUTED)
MASS
ENERGY
MASS
BBK3Y
MASS
ENERGY
Ko/hr
OVrr
Ko/rr
OVtir
Kp/lr
QJ/rr
1056
28.8
5837
111.4
15003
13.3
GT ENTRAINED FLOW PTROLYSIS SYSTEM; 200 dry TPD
N.B. The water is uniformly dispersed and bound in the pyrolysis oil fraction.
Maintenance of operating conditions above the dew point of water prevents
4
3.
DESIGN BASIS
Mass and energy balances were calculated for a 200-dry TPD in support
of the economic analyses. The product mass and energy yields for a 200-dry
TPD plant, based on a mixed hardwood feedstock, is included in Figure 2.
173
The product yields and other design conditions for
performance of the economic analyses are given in Table I.
TABLE I
DESIGN BASIS - GT ENTRAINED FLOW PYROLYSIS PLANT
Location
of
200-dry TPD
Southeast USA
FEEDSTOCK - (MIXED HARDWOODS)

Average Moisture Content, Wet Basis
Ash Content, Moisture Free
Higher Heating Value, Moisture Free
PRODUCT YIELDS
Pyrolytic Oil, Dry Wt/Wt Dry Wood
Char, Dry Wt/Wt Dry Wood
Pyrolysis Gas, Dry Wt/Wt Dry Wood
Water of Reaction, Wt/Wt Dry Wood
PRODUCT SPECIFICATIONS
Pyrolytic Oil
Specific Gravity
Product Oil Moisture Content, Wet Basis
Char
purposes
Pyrolysis Gas (Diluted)

Higher Heating Value, Dry Basis
COOLING AND COMBUSTION AIR
Temperature
Relative Humidity
Pressure
PYROLYSIS REACTOR CONDITIONS
Temperature
Pressure
Throughput, kg/hr-m2
50Z
0.77Z
19.5 MJ/kg
0.60
0.12
0.10
0.18
1.10
22.4 MJ/kg
15Z
29.0 MJ/kg
0.9 MJ/kg
25C
40Z
1 bar
550C
c.l bar
2200
4.
ECONOMIC ANALYSIS
For purposes of the economic analysis, the entrained flow pyrolysis
system was divided into six sections according to the operations performed:
wood delivery, wood drying, size reduction and storage, entrained pyrolysis
in the reactor, char removal, handling and storage, and oil removal, handling
and storage.
4.1
Capital Costs
Both purchased and installed capital equipment costs were specified
(Table II) . A number of sources of information were used to arrive at capital
equipment costs. For some of the equipment the requirements were discussed
with manufacturers and vendors and direct quotes were obtained.
The most
accurate information was used for critical items, that is, the ones which had
a major influence on the total cost. A rotary separator had been recently
specified and purchased, giving accuracy to that estimate. The installation
cost for each item was determined separately rather than by using a uniform
174
rate of the capital equipment cost to determine installation costs.
Installation costs were obtained by estimating material and labor requirements
directly for each capital item or by using estimated installation material and
labor for various classes and types of equipment. The major reference for the
economic analysis was the monograph of Peters and Timmerhaus (4).
TABLE II EQUIPMENT COSTS
200-dry TPD
Purchase
Cost ($)
Installed
Cost (S)
WOOD DELIVERY
Front-End Loader
Conveyor
100,000
10,000
100,000
11,700
DRYING
Metering Bin
Dryer (with Fan)
Dryer Particle Collector
Dry Wood Storage Bin
Dryer-Burner System
1,650
119,800
9,700
34,650
15,500
2,250
166,600
13,500
38,100
21,600
SIZE REDUCTION
Hammer Mill (with Screening)
Feed Storage Bin
141,650
105,900
198,300
116,500
PYROLYSIS
Pyrolysis Reactor System
Feeder system
Gas Blower
41,400
22,000
26,950
55,700
27,500
35,050
CHAR REMOVAL
Cyclone Separators
Storage Bin
43,600
71,100
60,600
78,200
OIL COLLECTION
Rotary Separators
Quench Spray System
Hold-Up Tank
Oil Storage Tank
30,500
12,000
19,000
73.600
42,450
16,650
22,850
91.250
$ 879.000
SI.098.800
TOTAL
The total capital investment for the 250-day TPD plant (60Z dry oil
yield) is given in Table III. No land cost is estimated since (a) the
pyrolysis process is based on a rural location where purchase cost is minimal,
(b) land may be leased at modest cost, (c) land is provided, and/or (d) the
plant only occupies A,460 sq.m. (48,000 sq.ft.) on a 1.0 ha (2.5 acre) site
which accommodates a thirty-day supply of wood feedstock.
The total direct plant cost amounts to $1.35 million and the total
capital investment (TIC) amounts to $2.3 million for the 200-dry TPD pyrolysis
plant. The total purchased cost of equipment was $0.88 million and the
installed equipment cost, as noted in Table II, amounted to $1.1 million.
175
TABLE III
TOTAL CAPITAL INVESTMENT
200-dry TPD
DIRECT COST
Installed Equipment Cost
Building and Services (5Z of Total
Purchased Equipment Cost)
Yard Improvements (4Z of Total
Service Facilities (14Z of Total
Land: 1.0 ha (2.5 acres)
TOTAL DIRECT PLANT COST
1,, 0 9 8 , ,800
44, ,000
35, ,200
1 2 3 , ,100
N.C.
1,, 3 0 1 , ,100
INDIRECT COST
Engineering and Supervision (15Z of
Total Purchased Equipment Cost)
Construction Expense (10Z of Total
Direct Plant Cost)
131,900
TOTAL INDIRECT PLANT COST
262,000
TOTAL DIRECT AND INDIRECT PLANT COST

CONTRACTOR'S FEE (5Z of Total Direct Plant Cost)
CONTINGENCY (8Z of Total Direct and Indirect Cost)
FIXED CAPITAL INVESTMENT (FCH
130,100
1.563.100
65,100
125.000
1.753.200
WORKING CAPITAL (3 months total labor expenses +

2 months, all other operating expenses +
1 month feedstock supply)
389,200
START-UP COSTS (8Z of FCI)
140.300
TOTAL CAPITAL INVESTMENT (TCI)
S2.282.700
4.2
Manufacturing (Product) Costs

The total manufacturing costs for a 200-dry TPD plant amounted to $3.25
million as described in Table IV. The operating labor cost is based on four
men per shift, three-shift operation, and a labor rate of $8.00/hr.
4.3
Sales Revenue
The total annual sales revenue for the products of 200-dry TPD (Table
V) wood pyrolysis plant includes sale of the pyrolytic oil, the char, and the
sale of product pyrolysis gas to a co-sited commercial or industrial user.
The oil-revenue was based on a selling price indexed on an energy-equivalence
basis to a barrel of crude oil at $21.00/barrel, i.e. $0.132 per liter
($0.50/U.S. gallon). This is clearly a conservative value for the pyrolysis
oil since petroleum heating fuel derivatives of crude oil, for which it will
substitute, will have a higher value than the crude oil itself. No. 2 fuel
oil was priced in the market at $0.93/U.S. gallon in 1981 (Wall St. Journal,
Oct. 12, 1981). Current inventories, based on earlier cheaper supplies of
crude oil, have a depressed current market price. At an expected mid-1990
176
TABLE IV
TOTAL MANUFACTURING (PRODUCT) COSTS
60Z OIL YIELD

200 MT/d
RAW MATERIAL ($24.25/DT)
2,1*5,400
OPERATING LABOR
268,800
OPERATING SUPERVISION (15Z of Operating Labor)

UTILITIES
40,300
252,300
MAINTENANCE AND REPAIRS (4Z of Fixed Capital

Investment
70,100
OPERATING SUPPLIES (15Z of Maintenance and

Repairs
10,500
LABORATORY CHARGES (10Z of Operating Labor)
26,900
DIRECT PRODUCTION COST
2.814.300.
FIXED CHARGES (Depreciation, Taxes, Insurance,

Rent; 10Z of Total Product Cost)
PLANT OVERHEAD COSTS (30Z of Operating Labor,
Supervision, Clerical and Maintenance + Repairs)
TOTAL MANUFACTURING (PRODUCT) COST
TABLE V
ANNUAL SALES REVENUE
OIL PRODUCTION (15Z Moisture)

liters per annum
gals (US) per annum
60Z OIL YIELD
325,300
113,800
S3.253.400
200-dry TPD
44.6 million
11.8 million
CHAR PRODUCTION
Tonnes per annum
Tons (short) per annum
9,325
10,260
GAS PRODUCTION
GJ per annum
MMBTU per annum
94,750
89,800
OIL REVENUE
$3,167,200
CHAR REVENUE
820,500
GAS REVENUE
449.000
TOTAL REVENUE
S4.436.700
177
1990 stabilization price of $25.00 per barrel of crude oil, No. 2 fuel oil could
range from $0.63 $0.75/U.S. gallon (i.e. $0,166 $0.20 per liter). The
char revenue was based on a market price of $80/ton for briquette charcoal
(the sales price of the TechA ir charcoal in 197678). The gas revenue is
based on a value of $5.00/MMBTU ($4.74/GJ) which is significantly less than
liquid propane which it would displace ($9.25/MMBTU; $8.77/GJ). The total
projected sales revenue is expected to be $4.44 million per annum at current
market prices.
4.4
Profitability A nalyses
Three methods were used for the evaluation of profitability: (a) the
(engineering) rate of return (ROR) on investment expressed on an annual
percentage basis, (b) payout (payback) period, and (c) discounted cash flow
(DCF) rate of return (ROR) on investment for the book life of the plant (taken
as ten years, based on depreciation).
TABLE VI
A NNUA L RATE OF RETURN ON INVESTMENT
200dry TPD
Years 15
Years 610
$4,436,700
$4,436,700
MANUFACTURING COST
3,253,400
3,253,400
GROSS PROFIT
1,183,300
1,183,300
DEPRECIATION
374,300
4,400
TAXABLE INCOME
809,000
1,178,900
INCOME TAX
Case I Tax at 35Z
Case II No tax
283,150
412,615
525,850
809,000
$ 766,285
$1,178,900
SALES REVENUE
NET ANNUAL PROFIT

Case I (A fter tax)
Case II (No tax)
$
$
Cash Flow* 100

Engineering Return on Investment = _ , . ,
_
,,.
, .
Total Capital Investment
v
(Years 15)
= 39.4 (A fter Tax)
= 51.8 (No Tax)
* Cash Flow Net Annual Profit + Depreciation
The engineering rate of return on investment analysis is presented in
Table VI. Both a "before income tax" and an "after income tax" case were
used.
178
The beforetax case could arise in subsidized situations. The after tax case
assumed a net income tax rate of 35Z. The plants were depreciated over ten
years with an accelerated rate applicable in years 15 per U.S. Internal
Revenue Service directives.
The law provides for depreciation of plant
equipment over a fiveyear period and, for buildings and services, over a ten
year period. The results for both cases demonstrate excellent rates of return
on investment: 39.42 (after tax), 51.8Z (without tax). The respective net
annual profits were $526,000 and $809,000.
The payout period analysis and the discounted cash flowrate of return
analysis (DCFROR) are summarized in Table VII. Both "before tax" and "after
tax" cases were used as cited above.
The results of payout period analysis indicate that the capital
investment can be "paid back" in 1.6 years in the case of no income taxes, and
in only 2.1 years for the "after tax" case. The payout period corresponds to
the minimum length of time necessary to recover the original capital
investment in the form of cash flow to the project based on total income, less
all costs excepting depreciation.
TABLE VII PAYOUT PERIOD AND DISCOUNTED CASH FLOWRATE OF RETURN ON

INVESTMENT 200dry TPD
PAYOUT PERIOD
DCFROR
Case I (Tax at 352)
2.1 years
30.32
Case II (No tax)
1.6 years
A
A .9Z
.. r>
j ,v,
,.
>
Depreciable FCI
Payout Period (No interest charge) =
*
r
: :
Avg. Profit A vg. Depreciation
per year
per year
DCFROR i, where i is calculated from

___ _ A nnual Cash Flow to 1
Project After Taxes [_1+
Working
^Capital
5.
1
d+i)2
Salvage"]
Value J
. . .
1 "I
d+i) 5 J
1 5
" i) J
[d+
SUMM
A RY
The Georgia Tech Entrained Pyrolysis Process is a technicallyproven and
costeffective method for the production of liquid biofuels and related
bioenergy products. Based on a detailed economic study for a 200dry TPD wood
pyrolysis manufacturing process the Georgia Tech process should be scaledup
to a commercial prototype scale and be actively commercialized. A summary of
the results of the economic analysis is given in Table VIII.
179
TABLE VIII SUMMARY OF ECONOMIC ANALYSIS
200-dry TPD Plant
60Z Oil Yield
TOTAL CAPITAL INVESTMENT
$2.2
million
MANUFACTURING (PRODUCT) COST (ANNUAL)
$3.25 million
SALES REVENUE (ANNUAL)
$4.44 million
AVERAGE ANNUAL RATE OF RETURN
39.4Z (51.8Z)*
PAYOUT PERIOD
2.1 (1.6)* years
DISCOUNTED CASH FLOW RATE OF RETURN
30.3Z (44.9Z)*
MANUFACTURING COST, PER GJ
$2.56
FIXED CAPITAL INVESTMENT, PER GJ
$1.38
* Before (or no) tax case.
ACKNOWLEDGEMENT
This work was supported by the U.S. Department of Energy through the
Biomass Thermochemical Conversion Program, managed by the Battelle-Pacific
Northwest Laboratories, under subcontract B-C5863-A-Q.
REFERENCES
(1)
(2)
(3)
(4)
BOWEN, M.D. et al. (1978). A Vertical-Bed Pyrolysis System. Chapter 6

in Solid Wastes and Residues: Conversion by Advance Thermal Processes
(ed. Jones, J.L. and Radding, S.B.), ACS Symposium 76, Americom Chemical
Society, Washington, D.C.
O'NEIL, D.J., KOVAC, R.J. and GORTON, C.W. (13-17 February 1989). Liquid
Biofuels Production by an Entrained Flow Pyrolysis Process.
Paper
presented at Energy from Biomass and Wastes XIII. New Orleans, Institute
of Gas Technology.
ELSTON, W.E., KOVAC, R.J. and O'NEIL, D.J. (7-9 October 1986).
Proceedings of the Fourth Southern Biomass Energy Research Conference.
University of Georgia, Athens, Georgia.
PETERS, M.S. and TIMMERHAUS, K.D. (1980). Plant Design and Economics
for Chemical Engineers. Third Edition. McGraw-Hill Book Co., New York.
180
PILOT PLANT DEMONSTRATION OF USED TIRES VACUUM PYROLYSIS
CHRISTIAN ROY
Universit Laval, Dept. of Chemical E n g i n e e r i n g , Ste-Foy, Qubec, GIK 7P4
and
JOHN UNSWORTH
P e t r o - T i r e Inc., Hamilton, Ontario, L8P 1X1
Summary
Tire r e c y c l i n g has become a n e c e s s i t y b e c a u s e of t h e h u g e piles of t i r e s
which r e p r e s e n t a t h r e a t to t h e environment. By and l a r g e , t h e r e is
a b o u t one worn t i r e p r o d u c e d p e r y e a r and p e r p e r s o n in t h e developed
c o u n t r i e s . However t h e used t i r e s r e p r e s e n t a s o u r c e of e n e r g y and
valuable chemical p r o d u c t e . By vacuum thermal decomposition of r u b b e r ,
it is possible to r e c o v e r t h e initial compounds which c o n s t i t u t e a t i r e .
We have used a s t e p - t o - s t e p a p p r o a c h , from bench scale batch s y s t e m s ,
to p r o c e s s development u n i t and finally pilot plant u n i t to experiment
and develop vacuum p y r o l y s i s of used t i r e s . Vacuum p y r o l y s i s of r u b b e r
yielded 55% oil, 25% c a r b o n black, 9% eteel, 5% fiber and 6% g a s . The
maximum r e c o v e r y of oil was performed at 415* C below 2 kPa (abe.
p r e s s u r e ) . The specific g r a v i t y of t h i s oil was 17.8"API and i t s g r o s s
heating value was 43 000 J / g with a total sulfur content of about 0.8%.
It was rich in benzol and o t h e r petrochemical components. The carbon
black favorably compared with the s t a n d a r d g r a d e s and will p r o b a b l y find
s e v e r a l applications as a semi-reinforcement or reinforcement c a r b o n in
r u b b e r p a r t s . I t s main limitation comes from t h e high level of impurities
(ash) it contains. The heat of p y r o l y s i s for the reactions is low and has
been estimated to be a r o u n d 706 k J / k g . The p r o c e s s has been t e s t e d in
a 200 k g / h pilot plant which positively demonstrated the possibility to
continuously feed u n d e r a vacuo l a r g e c h u n k s of r u b b e r . Work is p r o g r e s s i n g to optimize t h e r a t e of heat t r a n s f e r in t h e pilot plant r e a c t o r .
The p r o c e s s feasibility looks promising, with r e t u r n s on t h e investment
of a b o u t 50% after t h r e e y e a r s of operation.
1. INTRODUCTION
Tire recycling h a s become a n e c e s s i t y b e c a u s e of t h e h u g e piles of t i r e s
which r e p r e s e n t a significant environmental r i s k . Each y e a r 24 million t i r e s
(220 kt) a r e disposed of in Canada and a b o u t 250 millions (2.3 Mt) in the
U.S. Table I r e p r e s e n t s c o n s e r v a t i v e estimates of used t i r e s for t h e EEC
and o t h e r c o u n t r i e s . While some of t h e s e t i r e s a r e recapped or g r o u n d u p
for special u s e s , most a r e simply dumped in r u r a l farm land or in landfill
s i g h t s . When buried in landfills t h e y eventually float to the surface, and if
piled t h e non biodegradable r u b b e r will cause serious harm if ignited by
l i g h t n i n g or v a n d a l s .
However, t h e t i r e s r e p r e s e n t a source of e n e r g y and raw chemicals for
t h e production of r u b b e r p a r t s . By thermal decomposition of r u b b e r , it is
possible to r e c o v e r to a c e r t a i n extent the initial i n g r e d i e n t s which c o n s t i t u t e a t i r e . T h e r e have been numerous a t t e m p t s to i n t r o d u c e economically
viable t e c h n i q u e s of t i r e p y r o l y s i s . It is beyond the scope of this p a p e r to
d e s c r i b e the v a r i o u s tire p y r o l y s i s v e n t u r e s worldwide and the many
181
a d a p t a t i o n s of t h e technology. A detailed review was published in 1983 b y
Dodds e t al (3) for t h e US Department of E n e r g y . To o u r knowledge t h e r e
a r e only a few s c r a p tire commercial p y r o l y s i s p l a n t s in t h e world, which
mainly o p e r a t e in J a p a n a s indicated in Table II.
Table I .
T o t a l A r i s i n g s of Used T i r e s i n D i f f e r e n t C o u n t r i e s
Country
Tonnage/Year
Reference
EEC
1 500 000
USA
2 300 000
(1)
(2)
JAPAN
579 000
CANADA
220 000
(1)
(2)
Table II. Existing Commercial Scrap Tire Pyrolysis Plants

Process or Company
Capacity
Location
Start-up Date
Hyben Recycler
Batch
Britain, Japan
1977
Kobe Steel
1 t/h
Aioi, Japan
1978
Onaharaa Smelting
and Refining
4 t/h
Iwaki, Japan
1981
Kleenair
1 t/h
Centrali a, Wash.
1986 (discontinued?)
Of all t h e s e p l a n t s , t h r e e o p e r a t e on a c o n t i n u o u s feed mode and one is

batch. Typical yields from the Kobe plant a r e 31% oil, 29% c a r b o n black,
14.5% gas and 10% steel. The oil is sold to a cement kiln company. The
p r o d u c t s do not overall a p p e a r to have met earlier expectations. The e c o n o mics of the plant was r e p o r t e d to be only marginal (1).
The Kleenair p r o c e s s was developed by Conrad I n d u s t r i e s back in 1986
for the recycling of used r u b b e r in g a s , oil and c a r b o n black. The plant
capacity was 1000 k g / h , similar to t h e Kobe plant.
In both c a s e s , t h e
feedstock consisted of s h r e d d e d t i r e s . C u r r e n t l y the plant operation has
ceased.
The distinct feature of t h e Onahama plant is t h a t whole t i r e s a r e used
as feedstock to the r e a c t o r . The major saleable p r o d u c t s a r e a heating oil
(25-30%), c a r b o n black (35-40%) and steel (10%). The carbon black is used in
the adjacent copper smelting plant (4). The economics of t h e p r o c e s s is
good, although it has been r e p o r t e d to be less profitable t h a n b u r n i n g t h e
t i r e s at the plant site.
Here a r e some of t h e conclusions we have reached after visiting t h e s e
plants:
The most successful recycling p r o c e s s e s a r e those which use whole
t i r e s a s feedstock. S h r e d d i n g t i r e s is expensive. It also r e s u l t s in materials
which a r e difficult to handle inside the r e a c t o r , eventually giving rise to the
so-called "ballmilling" problem.
The quality of the carbon black p r o d u c t g r e a t l y determines its e n d - u s e
and as a consequence, i t s value on the market.
The plant operation should be s u p p o r t e d by a h i g h - q u a l i t y control lab
which should be o p e r a t e d by low-level technicians. In addition, t h e company
should maintain a s t r o n g R and D activity for p r o d u c t improvement and
discovery of new m a r k e t s . None of t h e p l a n t s t h a n we visited afforded such
182
technical s u p p o r t .
The p r o c e s s is cost sensitive to the s u p p l y of r u b b e r feedstock. The
p r o c e s s will be more profitable if t h e r e is a tipping fee or management cost
a t t a c h e d to the reception of a t i r e .
Attempts should be made to replicate t h e p l a n t s elsewhere n e a r l a r g e
piles t h r o u g h licensed or franchise a g r e e m e n t s , in o r d e r to s h a r e t h e risk
and optimize t h e i n v e s t m e n t .
Marketing of the p y r o l y s i s technology is
r e q u i r e d , s t r e s s i n g t h e a d v a n t a g e s of t h e p r o c e s s in terms of t h e e n v i r o n
mental r e g u l a t i o n s . The p y r o l y s i s r o u t e has been lowprofile compared to
the o t h e r thermochemical t e c h n i q u e s so far, and it is a b o u t time t h a t a more
a g r e s s i v e marketing a p p r o a c h be launched in o r d e r to b r i n g to light the
d i s t i n c t a d v a n t a g e s of t h e p r o c e s s from an environmental point of view.
Our p u r p o s e is to meet a s many of t h e s e goals u s i n g t h e vacuum p y r o
lysis concept. This p a p e r will explain how t h i s can be done.
2. VACUUM PYROLYSIS PROCESS
Vacuum p y r o l y s i s is an old concept. It e n a b l e s t h e production of l a r g e
q u a n t i t i e s of p y r o l y s i s oils from an o r g a n i c s u b s t a n c e . When a vacuum pump
is a t t a c h e d to t h e p y r o l y s i s r e a c t o r , t h e g a s and v a p o r molecules a r e
immediately removed from t h e reaction chamber. This minimizes t h e e x t e n t
of s e c o n d a r y r e a c t i o n s s u c h a s thermal c r a c k i n g , repolymerization and r e c o n
densation r e a c t i o n s , g a s p h a s e collision, catalytic c r a c k i n g and r e d u c t i o n and
oxidation r e a c t i o n s . If t h e v a p o r p h a s e p r o d u c t s a r e p r o p e r l y q u e n c h e d , the
yield of o r g a n i c liquids s u c h as p y r o l y s i s oils is dramatically i n c r e a s e d a t t h e
expense of solid r e s i d u e s and g a s e s . B esides, t h e physicochemical p r o p e r t i e s
of t h e end p r o d u c t s a r e specific. For i n s t a n c e , t h e c a r b o n black p r o d u c e d
u n d e r a vacuo is more easily d i s p e r s e d t h a n t h e atmospheric p r e s s u r e p y r o l y
sis black which is a n important c h a r a c t e r i s t i c in reinforcing r u b b e r p a r t e .
3. B ACKGROUND DATA
L a b o r a t o r y t e s t s were performed in a bench scale r e a c t o r to s t u d y t h e
influence of t e m p e r a t u r e a n d p a r t i c l e size d u r i n g p y r o l y s i s . For t h e s e t e s t s
approximately 1 k g of feedstock was p o u r e d into t h e r e a c t o r v e s s e l . P r e s
s u r e was maintained below 3 kPa d u r i n g t h e whole r u n . Experiment was
stopped when the final d e s i r e d r u b b e r bed t e m p e r a t u r e was r e a c h e d . A
detailed d e s c r i p t i o n of t h e a p p a r a t u s and p r o c e d u r e u s e d will be found
elsewhere (5). Regular t i r e s with no steel belt were u s e d for t h i s s e r i e s of
r u n s . The t i r e s had been p r e v i o u s l y s h r e d d e d to 1/4" 1/2" Tyler sieves
(6.3512.70 mm). The chemical composition of t h e r u b b e r feedstock is given
in Table III.
Table III. Chemical composition of the used tires
Elemental Composition
81.5% C
7.1% H
3.4% O
0.5%
Proximate Analysis
65.2% Volatile matter
Gross Calorific Value

36800 J/g
28.7% Fixed C
6.1% Ash
(Moisture 0.5%)
1.4% S
(6.1% ash)
The yield of oil, c a r b o n black, p y r o l y t i c water and g a s p r o d u c e d d u r i n g
p y r o l y s i s a t v a r y i n g final t e m p e r a t u r e s a r e summarized in Table IV of t h e
183
paper. The temperature shown is that of the bed of shredded tires. The
maximum oil yield was reached at a plateau temperature of about 415*C as
appearing in Table IV. At 415"C the yield of oils was 56.6%.
Table IV.
Effect of temperature on product y i e l d during vacuum p y r o l y s i s

of used t i r e s (wt. %, t i r e a s - r e c e i v e d b a s i s ) .
Temperature C C )
Oil (%)
Carbon black
and
fibers (X)
Gas (%)
Water (%)
7.2
91.1
Traces
1.7
310
17.7
79.4
0.3
2.6
335
27.2
68.8
1.7
2.3
250
363
48.3
45.6
2.9
3.2
415
56.6
36.6
2.2
4.6
500
56.2
35.5
4.3
4.0
The gas phase was mainly composed of Ha, CO, COj and a few HCs. At
415'C, the gas has a g r o s s calorific value of 36800 J g - 1 with an average
molecular weight of 28.3. No H2S could be detected in the gas phase. If
any, its concentration must be low since a partial mass balance on the sulfur
gave 70.4% for the solid residue while 27.4% of the initial S found its way in
the oil, leaving 2.2% for l o s s e s and gases.
Two runs were also conducted at identical temperature (420 5'C), one
with pieces of rubber sieved between 6.35 and 12.70 mm, and the other run
with larger chunks of old rubber of 150 to 400 mm. According to Table V
there was no significant difference between the two runs on the product
yields:
Table V.
Influence of size in product yields during vacuum pyrolysis of

used tires at 420'C (wt. %, rubber as-received basis)
Size (mm)
Oil (%)
Solid residue (%)
Gas (%)
Water (%)
6.4 - 12.7
56.6
36.6
2.2
4.6
150 - 400
58.4
34.8
2.1
4.7
Similarly vacuum pyrolysis at 450'C of a steel belt (17.6% fiber + steel)

tire sample gave 59.0% oil, 33.8% carbon black, 5.2% gas and 2.0% water on
an organic rubber basis which was in line with the results shown in Table V.
4. PROCESS DEVELOPMENT UNIT STUDY
These preliminary results were further investigated using a vacuum
pyrolysie Process Development Unit. The system operated on a semi-continuous feed mode using shredded (regular) used tire material sieved to 6.412.7 mm mesh size. The reactor was a six hearth furnace, 2 m in height
and 0.7 m in diameter. It was externally heated by electric elements s u r rounding the reactor chamber. The maximum throughput reached with this
unit during this study was 13 k g / h . A schematic of the P.D.U. is shown in
Figure 1 below and a detailed description of this unit will be found e l s e where (5).
At a maximum flowrate and reactor temperature of 513 *C, the oil yield
184
was 54%, 37.8% carbon black and fiber, 4.2% gas and 4.0% water. These
results were in straight correlation with the previous bench scale data.
An important engineering parameter to be considered when designing a
full scale pyrolysis plant is the quantity of energy required for the pyrolysis
reactions. This value has been empirically determined using the P.D.U.
described in this paper, and the detailed procedure has been published elsewhere (5).
Figure 1. Schematic of the Vacuum Pyrolysis Process Development
Scrubber 1 Scrubber 2
Chentank
Flore
leter
lv
Ice P1?
trap
Filters
The quantity of heat required to decompose rubber ( Hr) will depend on

the operating conditions used and the extent of reaction which has been
reached. Under normal carbonization conditions, the reactions are exothermic. Under vacuum, the reactions were found to be slightly endothermal,
reaching 706 kJ/kg.
We concluded that the secondary reactions (e.g.,
thermal and catalytic cracking, repolymerisation, recondensation, oxidation
and reduction reactions) which occurred under higher pressure conditions,
released heat and hence contributed to the overall exothermicity.
5. PILOT PLANT STUDY
The experimental system was a further scale up to the pilot plant stage.
The new system was designed to continuously decompose 200 kg/h of steel
belt tires below a pressure of 1.3 kPa. Large chunks of rubber were continuously fed across a column of water which connected a tank on the
ground and the top of a horizontal reactor which was elevated 14 m in the
air (see Photograph I). The reactor was externally fired with gas and a
small portion of the pyrolysis oil. The vapors were sucked at the outlets of
the reactor and immediately quenched by two scrubbers set in series. The
carbon black was recovered at the bottom of another water head which
connected the bottom of the reactor and the ground. A sharp separation of
the fiber, steel and carbon black was made in the water phase. The process
schematic is illustrated in Figure 2 of the paper.
The objective of the pilot plant phase study was to demonstrate the
feasibility of the vacuum pyrolysis process using semi-industrial scale equipment under continuous operation during several hours. The reactor configuration and the reliability of the downstream equipment including the
scrubbers, gas cleaning system and pumps were tested. The results obtained
so far with this unit are the followings:
Continous feeding of tires under a vacuo was practicable.
Separation of steel, fiber and carbon black at the reactor outlet is
feasible.
185
The equipment designed for the condensation and r e c o v e r y of the
p y r o l y s i s oils well performed.
The overall thermal efficiency of t h e p r o c e s s is high, exceeding 80%.
The optimum t e m p e r a t u r e and p r e s s u r e conditions to p r o d u c e large
yields of oils have been found.
The t h r e e major p r o d u c t s , oil, c a r b o n black and steel, a r e saleable and
marketable.
No major problem is expected with the quality of the g a s e o u s emis
sions.
Photograph I:
Figure 2.
Vacuum P y r o l y s i s Pilot Plant in SaintAmable, Quebec
Schematic of the SaintAmable Pilot Plant

12
~1
Heat for
D L ^^
reactor
"
a.
l.Feed conveyor
2.Vacuum r e a c t o r
3.Cooling screw
4.Discharge screw
5.Crusher
6.Vibratory s c r e e n
7.Magnetic s e p a r a t o r
8.Heavy oil q u e n c h e r
9.Light oil q u e n c h e r
10. Decan ter
11.Vacuum pump
12.Flare stack
13.Carbon black
handling system
14.Steel r e c o v e r y bin
15.Heavy oil s t o r a g e
16.Light oil s t o r a g e
The main limitation with this system was t h e low r a t e of heat t r a n s

f e r r e d to the r e a c t o r for each s q u a r e meter of surface a r e a . Actually the
r e a c t o r o p e r a t e d at less t h a n half of its t h r o u g h p u t capacity, due to ineffi
186
cient heat exchange in the reactor chamber. Another improvement on which
we are working at the present time is a better system for handling the
rubber-material inside the reactor, using large rubber chunks as feedstock.
The pilot plant unit was built and tested during fall 1987 in SaintAmable near Montreal. Unfortunately the project was momentarily stopped
during early 1988 because of the bankruptcy of the licensed company (Petrc
Sun Intern. Inc.) due to facts unrelated to this project. With the financial
support of both Universit Laval and Energy, Mines and Resources Canada
(Bioenergy Development Program), the project wae continued at the P.D.U.
level during 1988 up to now. The pilot plant phase will be continued during
the second half of 1989 under the auspices of the new licensed company,
Petro-Tire Inc., Hamilton, Ontario.
6. OIL AND CARBON BLACK ANALYSIS
The two main products obtained from the pyrolyeis of tires are carbon
black and oil. Samples of each of these products obtained in the pilot plant
unit were tested in our laboratory and by different customers. Some of the
analytical results are reported in this paper.
The oil has a g r o s s heating value of about 43000 J g"1.
It has a
specific gravity of 0.95 (17.8'API) with a pour point of - 6 ' C . Its initial
boiling point is 112'C with a 50% cut at 376"C (simulated distillation). The
residual metal content is < 0.1% for Va, 0.1% for Ni and 0.6% for Na. A
typical elemental analysis for thie oil gave 87.3% C, 10.5% H, 0.8% S, 1.2% 0
and 0.2% N. It yielded upon distillation 8% (by vol.) of heavy naphtha, 16%
kerosene, 24% light gas oil, 35% cat. feed and 17% bunker.
The PONA
analysis of the fraction boiling below 204'C which constituted 26.8% of the
crude oils gave 24.9% paraffins, 43.3% olefins, 6.6% naphthenes and 25.4%
aromatics.
This oil can be used as a heating oil and would be classified as a
number 4 ASTM bunker oil. It can alternatively be refined as a crude oil by
the petroleum industry and it has also several other potential applications
which are under development in our laboratories. As an example, Table VI
constitutes a partial list of the major compounds which have been detected
in vacuum pyrolysis oils. There is no doubt that some of these compounds
have a potential value as petrochemical feedstock.
Table VT. Examples of compounds found in vacuum pyrolysis oils
Compound
Yield
(wt. %, as-received rubber basis)
Limonene-ld
2.26
Toluene
1.05
Xylene (o-,m-,p-)
0.93
Styrene
0.82
Benzene
0.38
Dimethylcyclopentadiene
0.24
Methylpentene
0.23
Dimethylpentane
0.16
Cyclopentanone
0.15
Table VII summarizes some of the main characteristics of the carbon

black produced at 550 C and 1.3 kPa. Pyrolysis carbon black was compared
187
with two reinforcement commercial blacks, N234 and N330, which price on
the market varied between 960 and 1040 Can $. As indicated in Table VII,
carbon derived from vacuum pyrolysis of used tires has an iodine number
greater than the standard blacks. The main disadvantage of the recycled
carbon is its high inorganic content (ash). Work is progressing in our
laboratory to purify the material in order to increase its potential value on
the market. It has numerous usages including reinforcement or semirein
forcement for bicycle tires, shoes, auto flaps, footwear, conveyor belts, dock
fenders. The carbon black acts primarily to strengthen and increase the
impact on abrasion resistance of rubber. Other uses also include pigments
for ink and reduction for ore refining.
Table VII. Physicochemical properties of used tirederived carbon black
compared with standard blacks
Physicochemical
properties
Iodine index (rag/g)
pH
Obtained after pyrolysis

at 550 'C and 1.3 kPa
N234
N330
112.7
80.5
144.5
4.2
7.3
7.9
Volatile material {%)
4.2
3.3
4.4
Ash (%)
0.6
0.3
14.5
94.8
96.0
79.2
Composition (%)
C
H
0.84
0.66
0.76
0.77
0.60
0.71
2.98
1.98
2.10
0.68
0.74
2.80
7. PROCESS FEASIBILITY
Based on the background and engineering data reported in this work, a

preliminary feasibility study of the process was performed. The assumptions
used are summarized in Table VIII below.
Table VIII.
Assumptions used for the process f e a s i b i l i t y study
Product
Yield
Price
Oil
55%
Regular grade:
Improved grade:
18.0 $/bbl
19.4 $/bbl
Carbon black
25%
Regular grade:
Improved grade:
100 $/t
485 $/t
Steel
9%
90 $/t
Fiber/Kevlar
5%
2 $/t
Gas
6%
Prices are in Can. $.
Used for makeup heat
All metric u n i t s .
188
Other assumptions
Tipping fee/Lean-up fee
1 $/tire
Tires per ton
110
Rate of inflation
5%/year
No credit given for re-usables or re-caps
Table IX shows that the profitability of a 3 tons per hour or 20 000

tons/year plant with a capital investment of 7 M $ ie attractive if a tipping
fee can be collected for the recycling of tires.
Table EC. P r o f i t a b i l i t y of a 20 000 t / y plant for vacuum pyrolysis of used
tires
Sales/Revenues
Year 1
Year 2
Year 3
Oil, regular
improved
733 000
1 538 000
Carbon black, regular

improved
250 000
525 000
Steel
81 000
170 000
179 000
Fiber
1 000
2 000
2 000
Tipping fees/Clean-up
1 615 000
2 425 000
1 100 000
2 200 000
2 200 000
Re-usables
NIL
NIL
NIL
Re-caps
NIL
NIL
NIL
2 165 000
4 436 000
6 421 000
479 000
1 160 000
1 329 000
1 686 000
3 276 000
5 092 000
Total Sales/Revenues
Cost of sales
Gross margin
Adm. and Comm. Expenses
136 000
192 000
244 000
Depreciation
675 000
675 000
675 000
Financial Expenses
675 000
675 000
675 000
Taxes
Profits (loss) of the year
Undivided profits (deficit) at
the commencement
Undivided profits (deficit) at
the end
8. CONCLUSIONS
NIL
200 000
NIL
200 000
NIL
NIL
1 734 000
3 498 000
200 000
1 934 000
1 934 000
5 432 000
A process for the recycling of used tires has been developed from bench
scale, to process development and pilot plant units. The project which is
still under development at Universit Laval under contract with Petro-Tire
Inc. has great potential. There is a market for the oil, the carbon black
189
and steel which c o n s t i t u t e t h e t h r e e main p y r o l y s i s p r o d u c t s . The p r o c e s s
feasibility would justify t h e c o n s t r u c t i o n of a l a r g e demonstration p l a n t (10
000 t / y ) which we foresee in t h e n e a r f u t u r e . This p r o c e s s would simultaneously r e p r e s e n t an e l e g a n t solution for t h e disposal of the tire piles.
REFERENCES
(1) Dufton, P.W. The Value a n d Use of S c r a p T y r e s .
Ltd. England. Report dated 26 November 1987.
Rapra Technology
(2) The Rubber Association of Canada, Mississauga, Ont. 1989.

(3) Dodds, J., W.F. Domenico and D.R. Evans. S c r a p Tires: A Resource and
Technology Evaluation of Tire P y r o l y s i s a n d Other Selected Alternate
Technologies. N.T.I.S. Report # EGG-2241. P r e s e n t e d to t h e U.S. Dept.
of E n e r g y . November 1983.
(4) Kono, H.
Onahama Smelting and Refining
Fukushima. P r i v a t e communication. (1987).
Co.,
Ltd.
Iwaki
City,
(5) Labrecque, B. Etude du t r a n s f e r t de chaleur p a r radiation thermique

d a n s u n r a c t e u r de p y r o l y s e sous vide des v i e u s p n e u m a t i q u e s . M.Sc.A.
Thesis. Universit de S h e r b r o o k e , S h e r b r o o k e , Qu. 1987. (In F r e n c h ) .
ACKNOWLEDGMENT
This work has been s u p p o r t e d by the National Research Council of

Canada, the Natural Science and E n g i n e e r i n g Research Council of Canada,
E n e r g y , Mines and Resources Canada, Energie et Ressources Qubec, U n i v e r sit Laval and P e t r o - T i r e Inc.
190
FLUIDIZED BED PYROLYSIS OF SEWAGE SLUDGE
U. BELLMANN, A.B. KUMMER, Y. YING, and W. KAMINSKY
Institute for Technical and Macromolecular Chemistry
Summary
Digested, thermally conditioned and dried sewage sludge
has been pyrolyzed in an indirectly heated fluidized bed
reactor at temperatures ranging from 620C to 750C. A
quantity of up to 40 kg of sewage sludge per hour has
been converted into pyrolysis gas, oil, product water and
carbonaceous residues in a continuously working pilot
plant. The pyrolysis gas has a calorific value of approximately 23 MJ/m3. The main constituents of the pyrolysis
gas are hydrogen, methane, ethane, ethene and propene as
well as carbon monoxide and carbon dioxide. The oil fraction yielded contains up to 30% aromatic compounds. The
heavy metals from the sewage sludge become to a large extent enriched into the solid residue on account of the
reducing conditions of the pyrolysis process.
1. INTRODUCTION
More elaborate and refined purification methods in the
treatment of communal and industrial crude waste water are
leading to a continuous increase of the amount of sewage sludge
to be produced. The expected annual amount of sludge is estimated to rise up to 320-430 mio m 3 in the EC in 1990 (1). At
present, the whereabouts of sewage sludge is distributed as
follows (2):
- agriculture + decompostion
- sanitary landfill
- incineration
32%
59%
9%.
The utilization of sewage sludge as fertilizer seems to be restricted because of the harmful components in the sewage
sludge, such a heavy metals, polyaromatic hydrocarbons (PAH)
and the polychlorinated biphenyls (PCB).
There are certain requirements to be met prior to the deposition of sewage sludge in landfills with the intention of
avoiding any kind of emission. In addition, neither the biological potential nor the chemical energy content are sufficiently exploited. In future, deposition of sewage sludge will be
made more difficult resulting from a decreasing deposition ca-
191
pacity on the one hand and increasing cost of deposition on the
other hand.
Thermal conversion processes such as combustion or pyrolysis, offer alternative waste disposal concepts. The combustion process yields a considerable amount of sulphur and nitrogen compounds. Expensive precautions as regards flue gas
purification have to be taken for the purpose of running combustion plants on an environmentally tolerable scale. In addition to that, problems arising from the increased elution capability of heavy metals out of the ashes from the oxidizing
treatment have to be solved.
The pyrolysis of sewage sludge according to the HAMBURG
PROCESS (3) seems to be advantageous as to the minimization of
emission due to a closed gas cycle in connection with an indirectly heated fluidized bed and the reduced volume of the depyrolyzed sewage sludge.
2. PYROLYSIS RESULTS
Figure 1 shows the flow scheme of the fluidized bed pilot
plant by means of which the pyrolysis of sewage sludge has been
investigated.
Core of the plant is an indirectly heated fluidized bed,
450 mm in diameter. Right at the start of the pyrolysis, the
fluidization material consists of quartz sand with particle
sizes between 0.3 and 0.7 mm. In the course of the run the sand
is gradually replaced by depyrolized sewage sludge. In order to
ensure a constant height of the fluidized bed of approximately
650 mm during continuous input of sewage sludge an overflow
vessel has been attached to the reactor.
Next to the reactor, a cyclone separates carbon and solid
particles from the product gases. The cyclone is followed by
three quench coolers where the pyrolysis oils are subsequently
quenched. At the end of the third cooler the temperature goes
down to 0-5C. During the last condensation stage the product
gas is freed from aerosols and entrained droplets in an
electrostatic precipitator.
The gas is then conveyed into five membrane compressors,
connected in parallel, and stored in three gas tanks. One portion of the gas is used to fluidize the sand bed, whereas the
rest of the gas may be used as fuel for the radiation heating
tubes, thus allowing an autothermal operating mode of the
plant.
As feed stock for the pyrolysis experiments all kinds of
digested or thermal conditioned and dried sewage sludge from
different communitities or industries could be used (4). The
water content of the sludge has to be 5-10 weight percent.
The pyrolysis experiments were carried out at temperatures
of 620C, 690C and 750C. The sewage sludge was acontinuously
and directly fed into the reactor from a silo via two crew conveyors. The conveying capacity was 25-40 kg/h and the whole
charge of converted sludge amounted to more than 360 kg.
The product fractions obtained consisted of gas, pyrolysis
oil, product water, soot and pyrolysis residue. This solid residue contained the formed pyrolysis coke together with the anorganic fraction of the sludge.
Fig. 1. Flow Scheme of the Fluidized Bed Pilot Plant for Sewage Sludge
d e s t i l l i n g columns
cryostat
~=H,0
cyclone
silo
uench c
l<=r
quench
cooler
quench cooler
3,
=1
:H,O
lock
electrostatic
precipitator
steam _,,_. steam

o i l .,, j .
r-
l^'
Kigh
bollinj
fraction
Toluene Benzene
fraction fraction
tafit
overflow vessel
compressed a i r
Xylene
fractlor
propane
pjrolysis gas/l
gasooeter
compressor
heat exchanger
n
flare
&
193
Table 1 shows the composition of the organic pyrolysis
products obtained at three different reaction temperatures.
Table I
Product Fractions of the Pyrolysis of Digested Sewage

sludge (% by Mass of Organic Dry Matter
Temperature ("CI
Sludge mass kq)
Organic dry matter (kg)
Product fraction (m%)
Pyrolysis gas
Oil
Product water
Soot
Pyrolysis coke
Loss
620
361.2
185.5
690
126.6.
62.9
750
118.7
60.0
22.7
40.1
12.6
3.7
20.0
0.9
30.7
34.3
10.8
3.1
19.2
1.9
40.8
21.1
8.0
4.9
22.3
2.9
100
100
100
The main contents of the pyrolysis gas are carbon monoxide, carbon dioxide, hydrogen as well as C1-C4 hydrocarbons.
Small amounts of carbonoxysulfide and hydrogensulfide are
likely to be found. The calorific value of the pyrolysis gas
amounts to 23 MJ/m*, that means up to about 70% of the calorific value of natural gas.
The gaseous portion of the pyrolysis products increases
with rising temperature from 620C to 750C from 22.7% to
40.8%.
The pyrolysis oil contains hydrocarbons and, in addition
to that, some amounts of nitriles, phenols and heterocyclic
compounds. With rising reaction temperature the oil yield decreases from 40.1% at 620C to 21.1% at 750C. The major portion of the pyrolysis oils is still tar after all, especially
at low temperature down to 620C amounting to 75.5%. This tar
consists of substances which cannot be separated by destillation. The increase of pyrolysis temperature leads to a rising
percentage of aromatic components due to progressing defunctionalization.
Investigations of the pyrolysis residues, composed of the
anorganic residue and the pyrolysis coke, show that the heavy
metals originated from the sewage sludge are enriched in this
fraction. This enrichment holds quantitatively true in the case
of all relevant heavy metals except the volatile elements mercury and cadmium which are condenced at the carbon black in the
eyeIon.
Elution experiments with water resulted in the finding
that heavy metals are evidently stronger incorporated in the
matrix of pyrolysis residue than in the incineration ash, produced at 1200C, or in the sewage sludge itself. Table II shows
that chromium, for instance, is more than 250-fold less liable
to be eluted from pyrolysis residue than from incineration ash.
Moreover, chromium is dissolved from ash essentially in the
oxidation state VI as compared to chromium II from pyrolysis
residues.
194
Table II
Elutions According to DIN 38.414 T4
Sample
Element ^ g / k g ) :
Cadmium
Chromium
Copper
Nickel
Lead
Sewage Sludge
8
100
8150
3860
350
Incineration
Ash (1200Ci
14
7750
100
125
55
Pyrolysis Residue (750C)

< 3
30
50
25
50
The investigations have shown that sewage sludge can be

pyrolyzed according to the HAMBURG-PROCESS. The gas/oil-ratio
is adjustable in a large extent by means of varying the reaction temperature. The use of the aromatic oils for petrochemical application seems to be promising
The reduction of volume and the strong incorporation of
the heavy metals in the matrix of the pyrolysis residue cases
the problem of sludge decomposition. This shows that the pyrolysis of sewage sludge can be looked upon as environmentally
tolerable alternative to the conventional sewage sludge utilization.
This research is sponsored by the BMFT, Federal Republic
of Germany.
3. REFERENCES
(1)
(2)
(3)
(4)
L'HERMITE, P., OTT, H. (1982). Recycling International,

Freitag Verlag Berlin, 342
BLICKWEDEL, P.T., SCHENKEL, W. (1986). Korrespondenz Abwasser 33, 680
KAMINSKY, W. (1985).J.Anal. & Appi. Pyrolysis 8, 439
KAMINSKY, W., KUMMER, A.B., BELLMANN, U. (1986). Phosphatentfernung und Klrschlammnutzung. Hoechst Symposium,
Frankfurt
195
RAPPORTEURS REPORT ON SESSION III
PYROLYSIS GASIFICATION AND LIQUEFACTION TECHNOLOGIES
A V Bridgwater
Energy Research Group
Chemical Engineering and Applied Chemistry Department
Aston University
Aston Triangle
Birmingham B4 7ET
UK
INTRODUCTION
This overview provides what were seen to be the significant points and conclusions
from the papers presented in this session, some recommendations and report on
the questions and discussion. It is hoped that the views of the authors are fairly
represented, and further details are contained in the individual contributions.
BIOMASS GASIFICATION IN DEVELOPING COUNTRIES
Dr M S Mendis
A summary of the World Bank monitoring programme has shown that biomass
gasification for heat applications has generally been successful, but for power
applications where gas quality is of prime importance, much less success has been
realised. Most projects have failed due to unacceptable fuels, untested equipment,
mismatch of system to application, poor training, lack of incentives and poor
economics. Proven fuels are charcoal, wood, rice husks and coconut shells.
Gasifiers cannot economically compete at present with diesel due to high capital
costs. Gasifier capital costs for charcoal are $500/kW, and for wood, $750/kW.
Total system costs for power generation for charcoal fuel are $1250/kW, and for
wood $1600/kW. A major breakthrough has recently been achieved at AIT in
Bangkok, Thailand with a ferrocement gasifier which costs about $50/kW compared
to $500 for a fabricated metal gasifier.
The economic attractiveness of biomass gasification systems for fuel and power is
very sensitive to fuel prices. The most interesting market is in the 10-300kW size
range, operating at more than 60% utilisation. Major inhibitions to development
are a lack of trained personnel, poor equipment maintenance, poor incentives for
implementation and environmental factors.
Recommendations
1
Continue support for monitoring to obtain better field data.
2
Learn from experiences to date and provide more technical and social
support for any new initiatives.
196
BIOMASS GASIFICATION & PYROLYSIS IN EUROPE
A A C M Beenackers and A V Bridgwater
Gasification
Low heating value gas production Systems are commercially available, but
generally not economic. Applications include process heat, for example drying,
and power from engines where considerable experience has been obtained. An
interesting system size for Europe is around 1MWe. Turbines offer considerable
potential but ideally require pressurised gasification and a particularly clean gas
both of which currently present problems.
Medium heating value gas production Considerable experience was gained in the
EC sponsored Methanol from Wood pilot programme. The Framatome pressurised
fluid bed oxygen gasifier at Clamecy is planned to be restarted which will provide
more data. Genedrally the technology is fairly well developed but uneconomic.
Catalytic gasification Good progress has been made in Spain and France on
catalytic gasification and in Sweden on secondary processing for gas quality
improvement.
Recommendations
1
Obtain more field experience and data from operational gasifiers,
2
Initiate work on gasifier driven turbine power generation,
3
Continue R&D on product gas quality improvement.
Pvrolvsis
Pyrolysis has been carried out in diverse processes to produce a wide range of
products including liquids, slurries, gases and solids. The technologies are less
developed, but there is more potential for production of liquid fuels as either fuel oil
substitutes, or by upgrading as synthetic hydrocarbons. More experience is
needed at pilot plant scale in Europe for pyrolysis processes and upgrading
technologies. Utilisation of the variety of liquid fuels that can be derived from
pyrolysis requires assessment and testing.
Recommendations
1
Improve the performance of pyrolysis processes,
2
Build pilot plant scale pyrolysis processes for liquids production at high
efficiency,
3
Continue liquids upgrading, particularly through zeolite synthesis of
hydrocarbons,
4
Provide wider experienceof utilisation of all pyrolysis products.
BIOMASS LIQUEFACTION PROCESSES
Prof M Gelus and Dr R Capart
Liquefaction and the related processes of solvolysis, hydrolysis and supercritical
extraction are the least developed of the thermochemical conversion technologies.
The processes are generally low temperature, high pressure processes which can
produce chemicals as well as higher quality oil liquids with a lower oxygen content
than pyrolysis oils.
197
Recommendations
As this is the least well developed conversion process, research should be
continued into as many variations as possible to more fully evaluate the technical
and economic opportunities for both chemicals and fuels production.
THE GEORGIA TECH FLASH PYROLYSIS PROCESS
Dr D O'Neill
The entrained flow flash pyrolysis process has been subjected to continued
development and 60% weight yield of liquids (dry basis) has now been achieved.
A robust computer model has been derived and developed which predicts that
yields of more than 70% oil by weight could be achieved in the optimum
circumstances.
A 200 t/d commercial plant has been designed and assessed which gives an oil
yield of 60% wt at an energy efficiency of 73%. No waste water would be produced
by maintaining the vapour temperature above the dew point of water. The 200 t/d
plant has a total capital cost of $2.28 million and, with the product oil valued the
same as crude oil on a heating value basis, gives attractive profitabilities even in
the current economic environment with a payback time of around 2 years and a
discounted cash flow rate of return of around 30%.
Development will continue on the piolt plant and opportunities for demonstration
will be sought.
VACUUM PYROLYSIS OF SCRAP TYRES
Prof C Roy
A novel tyre vacuum pyrolysis proces has been developed based on the
application of a biomass conversion technology to alternative feed, and a 250 kg/h
pilot plant has been built and operated This provides a more commercially
attractive opportunity than a biomass based process in the short term and enables
R&D activities to be maintained and provides valuable operating experience. The
products are oil, charcoal and carbon black, gas and steel. A 60 t/d (20 000 t/y)
plant has an estimated capital cost of CAN$ 7 million, and has been shown to be
profitable under current conditions. Development will continue and further
opportunities for this technology will be sought.
FLUID BED PYROLYSIS OF SEWAGE SLUDGE
Dr W Kaminsky
Fluidised bed pyrolysis of waste materials has been researched since 1970,
including earlier work on rubber and plastics which resulted in a demonstration
plant of 1 t/h operating in Southern Germany. This has been recently shut down
due to poor economics. Recent work on sewage sludge has given oil yields up to
40% by weight at lower temperatures of around 650C, which reduce as the
temperature of pyrolysis increases, while the gas yield increases. Considerable
data has been collated but commercial feasibility has not yet been assessed.
198
QUESTIONS and
DISCUSSION
QUESTION
ANSWER or COMMENT
How does gasification compare with

Gasification gives complete conversion
pyrolysis in terms of costs and benefits? to a single product - gas - which is difficult
to transport and can only be readily used
locally. Pyrolysis gives multiple products,
some which are liquid and can be
transported and used remotely. Capital
and operating costs are similar, and the
only difference, therefore, lies in the
product worths.
What hazards are involved
with pyrolysis oil?
Pyrolysis oils are no worse than coal tar

or crude oil.
How is water managed in the GTRI

process?
Water would be maintained in the vapour

phase in a commercial plant. This has
been achieved in a fixed bed operation
and is planned for the entrained flow
process.
What chemicals can be produced

from carbonisation plants?
Lambiotte operating but with little interest.

Extensive recoveryis practised in Brazil.
How does atmospheric tire pyrolysis.

compare with vacuum pyrolysis?
Vacuum increases the oil yield, and

improves the carbon black activity.
What are the power costs in

tire shredding?
As whole tires or 1/4 tires are processed,

power costs are very low.
What happens to the sulphur in the

products from tire pyrolysis?
Sulphur is fixed by CaO & ZnO present in

the tires
How are products from sludge

processing denitrified?
This is not a problem.
What is the cost of the sludge

conversion process?
A 20 000 t/y dry solids process would

cost $2million+ buildings + special costs
What is the conversion efficiency and

The process is not economic without a
economics of sewage sludge pyrolysis? disposal credit for the sewage sludge.
SESSION IV
FYROLYSIS CASE STUDIES
201
SUGARS FROM CELLULOSICS BY THE WATERLOO FAST PYROLYSIS PROCESS

D.S. Scott, J. Piskorz, D. Radlein and S. Czernik
Department of Chemical Engineering, University of Waterloo
Sunarna T-y
It has been found that fast pyrolysis in a fluidized bed of sand at

atmospheric pressure can convert cellulose into anhydrosugars and
other sugars if certain characteristics are present in the feed.
Normally some pretreatment will be required to condition the feed so
that high yields of sugars can be obtained.
For example, for wood,
treatment with 5% sulphuric acid at 100C will give a product which
on pyrolysis will result in a sugar yield corresponding to about an
80% conversion of the cellulose to glucose. Wood pretreated in this
way and then pyrolyzed also yields a pentose solution, and an aromatic fraction derived from lignin which has numerous possible uses.
The sugar produced by fast pyrolysis would be in the form of a syrup
with a concentration of 150 to 200 grams/liter.
Results are also
given for pyrolysis of wood pretreated by steam explosion, and for
some agricultural wastes such as wheat chaff.
1. INTRODUCTION
Over the last several years, the Waterloo Fast Pyrolysis Process
(WFPP) has been developed to maximize yields of liquids by the rapid thermal decomposition of lignocellulosic biomass.
The process operates at
atmospheric pressure and the reaction is carried out in a fluidized bed of
sand as a heat transfer medium. Optimal conditions for woody biomass are
450 C to 550 C and about 0.5 seconds gas residence time. The nature of
the fluidizing gas has little influence on yields.
Liquid yields from wood at optimal conditions are 70% to 80% of the
dry feed, with the organic liquid yields being 60% to 65% of the dry wood
fed. A description of the process and the yields obtained with various
types of biomass has been published previously by the authors (1)(2). Extensive identification and quantification of many of the individual compounds present in these pyrolytic oils has also been reported (3)(4)(5).
It has been known for many years, as described in the extensive literature on the subject, that slow heating of cellulose under vacuum can
lead to significant yields of anhydrosugars, principally levoglucosan.
However, pyrolysis of wood, whether slow or rapid, normally gives very low
yields of levoglucosan.
Instead, lower molecular weight oxygenated compounds are the major products, and, as pointed out by the authors in a
previous publication [6], if fast pyrolysis is employed, then hydroxyacetaldehyde will be one of the principal products.
In that publication, a
mechanism was also proposed to account for the formation of hydroxyacetaldehyde, in which it was assumed that levoglucosan was a precursor, and
202
that lower molecular weight products were formed in successive sequential
decomposition steps. However, more recent work has led us to believe that
levoglucosan and hydroxyacetaldehyde are produced in parallel reactions, a
mechanism which has also been proposed recently by Richards (7).
Shafizadeh and Stevenson (8) suggested that the yield of levoglucosan
from wood could be increased by pretreatment of the wood to remove hemi
celluloses prior to vacuum pyrolysis. Radlein et al. (9) in 1987 reported
the results of preliminary experiments which showed that a mild acid
hydrolysis of wood followed by fast pyrolysis at atmospheric pressure
completely changed the product spectrum, and, in particular, greatly in
creased the yields of levoglucosan and other sugars. A dditional experi
mental results are given here of investigations of the effects of various
pretreatments of wood on the yields of anhydrosugars obtained in the WFPP.
2. EXPERIMENTA L
Samples tested included poplar woods, both untreated as well as sub
jected to a variety of pretreatments, and a pretreated pine.
The St. Lawrence poplar was prehydrolysed with 0.5% HCl at 165C for
6 minutes in a plugflow reactor a procedure which led to substantial
hemicellulose removal.
Wayman poplar was whole wood pretreated with 2%
SO2 at 200C for 45 seconds in a Wenger extruder. Biohol pine was auto
claved with 3% S 0 2 at 110C for 2 hours.
Hemicelluloses were partially
removed by this treatment.
Stake poplar was steamexploded wood after
digestion at 322 psi for 2 minutes.
The acidhydrolysed samples were prepared by boiling the ground wood
meal in 5% H2SO4 for 2 or 6 hours as indicated in the tables, except in
the case of the Stake wood which was treated with cold (21C) 5% HOSOA for
21 hours. Following the acid treatment the samples were washed with de
ionized water till acidfree. "Deionized" wood was prepared by percolat
ing 10 cm g
of cold 0.1% H J S O A through a column of clean wood meal at a
rate of about 2 cm hr
(g wood) , followed by washing with distilled
deionized water at a similar rate until the wash was acidfree.
Analysis of acid hydrolysate and of the water extract of the pyroly
sis oils was done by HPLC (A minex 87 column at 65C, eluent 0.07N
H 3 P0 4 , eluent flow rate 0.32 2.25 ml/min).
Except where otherwise noted, pyrolysis of raw or treated wood or
cellulose was carried out at standardized conditions near optimal for the
Waterloo Fast Pyrolysis Process for all runs, that is at 500C, 0.46 to
0.50 seconds apparent gas residence time, nitrogen atmosphere, employing
the bench scale fluidized bed unit which has been described in detail
elsewhere (1).
Ash analysis was carried out by slow controlled combustion of biomass
in a muffle furnace at 650C to prevent loss of volatile inorganic salts.
It was estimated that this method gave ash values accurate to 0.01 weight
percent.
Cellulose content was determined by gravimetry of the residue remain
ing after hemicelluloses and lignin were dissolved in a mixture of acetic
and nitric acids according to the procedure of Updegraff (10).
A sample of wheat chaff, both untreated and acid pretreated in the
same manner as the wood samples, was also pyrolyzed. Pyrolysis conditions
and analytical methods were the same as for other samples.
3. RESULTS WOOD
The "commercial" feedstocks were pyrolysed without further pretreat
ment with the results shown in Table 1. Results for untreated clean IEA
poplar are included for comparison.
Pyrolytic lignin is the water
203
insoluble portion of the tar (5). Only the (anhydro) sugars and hydroxyacetaldehyde from among the water-soluble components are listed.
Total
liquid yields (water + organics) for the pretreated materials range from
-61% (Biohol) to 81% (St. Lawrence) compared to 78% for the un-treated
wood.
Sugar yields were in all cases relatively low. In the best case
(Wayman) 35.5% of the cellulose was converted to sugars.
Some of these materials were then subjected to hydrolysis with HoSO^
as described in the experimental section. This procedure causes extensive
hemicellulose removal resulting in an enhanced cellulose content.
Ash
levels are also reduced. The results of pyrolysis of the hydrolysed substrates are listed in Table 2. In all cases there is a sharp increase to
>66% conversion of cellulose to sugars. It should be pointed out that the
"char" in these cases is not solely primary but includes a fused material
accumulated at the reactor outlet and having the appearance of a carbonized sugar.
An attempt was made to identify the important variables controlling
sugar yields. Clean IEA poplar was hydrolysed with f^SO^ in the manner
already described and pyrolysed at different temperatures and feed rates,
with varying water content and, in one case, with an additive (NHo). The
results are summarized in Table 3 which includes a detailed breakdown of
the compositions of the gas and the water-soluble organics. In some cases
a distinction is made between the primary char and fused materials
("coke").
In all cases primary char yields are nearly zero.
Liquid
yields are uniformly high and gas yields correspondingly low as would be
expected from the pyrolysis of similarly treated substrates (cf. Table 2 ) .
In the case of Run S#l, following hydrolysis the lignocellulose was
steeped in dilute NHj for one hour, washed till ammonia free and dried.
Only in this case is the sugar yield significantly suppressed. Otherwise
no clear trends emerge of the effects of hydrolysis time, moisture content, pyrolysis temperature, particle size or feed rate.
We have also made a preliminary investigation of the feasibility of
obtaining high sugar yields from wood without preliminary hydrolysis of
hemicelluloses. For this purpose "de-ionized" IEA poplar was prepared in
the manner already described. In some cases 0.1 wt% of (NH^^SO^ or H2SO4
was added to the de-ionized wood by dissolving in a sufficient amount of
water to saturate the wood then drying at 105 C for one hour. The results
of these tests are shown in Table 4. Sugar yields are good with a presumably catalytic enhancement by small amounts of (NH^^SO^ or H2SO4. Though
less than those from lignocellulose (i.e. acid hydrolysed wood) they are a
great deal better than those from untreated wood. To our knowledge they
are the highest ever reported from whole wood.
Fermentation tests were carried out by an independent consultant on
the liquid products produced by pyrolysis of acid treated poplar in a
pilot plant scale reactor (3 kg/hr feed).
The anhydrosugars as produced
can be fermented only slowly, if at all, by the common ethanol producing
yeast strains. After hydrolysis of these anhydrosugars to glucose, however, fermentation proceeded to completion at a normal rate with common
bakers yeast, that is, in about 24 hours.
If the hydrolyzed sirup of
hexoses was treated with activated carbon before fermentation, quantitative conversion to ethanol occurred in 1.5 hours.
4. RESULTS - WHEAT CHAFF
Wheat chaff was investigated as a typical agricultural waste available in large quantities which might be a source of fermentable sugars.
It is a very different type of biomass from wood, having a lower cellulose
content (22.5%) and very substantial amounts of minerals, mainly silica,
204
which are not removed by acid pretreatment.
lhe chaff was given two
different acid pretreatments, 5% H^SO^ for 20 hours at 20C, and 5% f^SO^
at 100C for 2 hours. A summary of these pretreatment results is given in
Table 5.
Results of the pyrolysis tests at 500C for the untreated and the two
pretreated wheat chaff samples are given in Table 6.
Unlike wood, very
substantial amounts of a solid product were collected, which was in a
great part probably due to the high ash content of wheat chaff. However,
even if calculated on an ash free basis the amount of char product
obtained from acid prehydrolyzed wheat chaff was almost twice as high as
that from pretreated wood.
The composition of the liquid product obtained from pyrolysis of the
untreated wheat chaff was similar to that from wood.
Similarly, the influence of acid pretreatment on the change of concentrations of main components of the pyrolytic tar was much the same, that is, a very significant increase was observed in the yield of sugars, mainly levoglucosan,
and a drastic drop in the yield of monomer fragmentation products such as
hydroxyacetaldehyde and acetol.
The pretreatment of wheat chaff with
sulphuric acid at room temperature was more efficient in the enhancement
of the yield of pyrolytic sugars than was the hot acid pretreatment, in
contrast to the behaviour observed for raw poplar wood, but similar to
that of steam exploded wood.
The conversion of cellulose into anhydrosugars reached a value of about 71% (glucose equivalent), which is a
little less than that for prehydrolyzed wood.
In view of these preliminary and non-optimized results, the processes
for the pretreatment and pyrolysis of wheat chaff appear to merit further
investigation.
5. DISCUSSION
The factors which determine the yield of levoglucosan from cellulose
pyrolysis have been extensively studied. Apart from the hydrodynamic and
temperature regime, various intrinsic factors like cellulose morphology
and degree of polymerisation have been cited.
Definitive evidence has
been hard to come by but one of the most clearly established effects is
the role of certain types of cations, especially alkaline and alkaline
earth, in even trace amounts, in catalysing fragmentation and charring
reactions and suppressing levoglucosan yields.
Most of the published
studies of cellulose pyrolysis relate to slow, low temperature vacuum
conditions. The results from de-ionized wood indicate that the deleterious effects of cations persist in the case of fast high temperature pyrolysis of whole wood (cf. Runs A-2 and S#3 in Tables 1 and 4 respectively).
This cation effect appears to be one of the principal reasons why the
commercial pretreated wood samples gave only poor to modest yields of
sugars.
It will be noticed from Table 2 that acid hydrolysis of these
samples caused substantial reductions in ash content.
(Most of the remaining ash is likely to be inert material like silica.) In fact the data
suggest that a mild cold de-ionization of these samples
is likely to
cause substantial enhancement of sugar yield. The best results in Table 1
are for the SOn treated materials (Wayman poplar and Biohol pine). It is
possible that this treatment causes other changes which are conducive to
sugar formation. On the other hand the Stake wood gave excellent results
after a cold acid wash.
Acid hydrolysis under the conditions used also causes hemicellulose
removal. Our data (Table 4) confirm an earlier observation by Shafizadeh
and Stevenson [8] that, provided soluble ionic substances are removed, the
presence of hemicellulose in wood is not, per se, detrimental to
205
levoglucosan production. (Cations in fact would be expected to associate
with carboxylic groups in hemicellulose.)
The best results with deionized wood are not quite s good as those with lignocellulose but no
definite conclusion can be drawn as the degree of de-ionization has not
been optimized.
The other principal question addressed by our data concerns the precise role of acids. Apart from cation and/or hemicellulose removal, the
data in Table 4 clearly show what appears to be a positive catalytic
effect. Such an effect has been previously postulated by Shafizadeh [8].
(NH 4 ) 2 S0 4 decomposes at 235C to free H 2 S 0 4 (b.p. 338C and volatile NH3
gas which probably readily escapes. By this strategy the timing of the
release of acid is controlled and the problems of drying samples containing HOSOA are avoided.
(When the substrate of Run S#7 was dried some
surface charring was clearly visible - - a fact which might be contributory
to the lower sugar yields.) There remains a great deal of scope for optimizing the chemical nature, the quantity and the manner of incorporating
acid into wood or lignocellulose.
One final point concerns the completeness of the characterisation of
the water-soluble portion of the organic liquid. We are able to identify
by HPLC an average of only 73% for the wood samples in Table 4 compared
with 85% to 95% for the lignocelluloses in Table 2. GCMS showed the presence of significant quantities of two unidentified components in the wood
tars which were absent from the lignocellulose, suggesting a hemicellulose
origin. Preliminary work indicates they are anhydro-xylan substances but
positive identification has not yet been established.
The preliminary tests carried out on wheat chaff indicate that the
cellulose content of a wide range of biomass materials could be converted
to fermentable sugars in good yield by pyrolysis after an appropriate
pretreatment. The wheat chaff results, together with other work done in
our laboratory (unpublished) show that of the cations naturally present
only the alkali and alkaline earth cations appear to have a specific catalytic effect in promoting ring fragmentation rather than depolymerization
of the cellulose.
We summarize our principal conclusions as follows
(a) It is possible to obtain good yields of anhydro-sugars from wood and
agricultural lignocelluloses by fast high temperature pyrolysis.
(b) The highest yields were obtained when the feedstock was pretreated in
a suitable way.
Acid hydrolysis or acid washing proved to be very
effective leading to over 70% conversion of cellulose to sugars in the
most favourable cases.
(c) The acid appears to play at least two critical roles; to remove harmful cations and to catalyse anhydrosugar release.
(d) However, much more fundamental work remains to be done to gain a full
understanding of the effects of both pretreatraent and pyrolysis
variables on sugar yields.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the financial support for a
portion of this work by the Renewable Energy Division of Energy, Mines and
Resources Canada, and by the Natural Sciences and Engineering Research
Council of Canada.
The valuable assistance of Peter Majerski as operator of our pyrolysis pilot plant is also acknowledged with pleasure.
206
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
Scott, D.S. and Piskorz, J., "The Flash Pyrolysis of Poplar Wood",
Can. J. Chem. Eng., 60, 666674 (1982).
Scott, D.S., Piskorz, J. and Radlein, D. , "Liquid Products from the
Fast Pyrolysis of Wood and Cellulose", Ind. Eng. Chem. Proc. Des
Devei., 24, 581588 (1985).
Piskorz, J. and Scott, D.S., Symp. on Production, A nalysis and Up
grading of Pyrolysis Oils from Biomass, ACS Meeting, Denver, April 5
10 (1987).
Radlein, D. , Grinshpun, ., Piskorz, J. and Scott, D.S., "On the
presence of anhydrooligosaccharides in the sirups from the fast
pyrolysis of cellulose", J. Anal. Appi. Pyrolysis, 12, 3949 (1987).
Radlein, D. Piskorz, J. and Scott, D.S., "Lignin derived oils from
the fast pyrolysis of biomass", J. Anal. Appi. Pyrolysis, 12, 5159
(1987).
Piskorz, J., Radlein, D. and Scott, D.S., "On the mechanism of the
rapid pyrolysis of cellulose", J. A nal. A ppi. Pyrol., 9, 121 126
(1986).
Richards, G.N., "Glycolaldehyde from pyrolysis of cellulose", J.
Anal. Appi. Pyrol., 10, 251256 (1987).
Shafizadeh, F. and Stevenson, T.T., J. Appi. Polymer S c , 27 4577
4585 (1982).
Radlein, D., Piskorz, J., Grinshpun, A. and Scott, D.S., "Fast pyrol
ysis of pretreated wood and cellulose", ACS Preprints, Div. of Fuel
Chemistry, 32, No. 2, 2936 (1987).
Updegraff, D.M., A nal. Biochem. 32, 420424, 1969
Table 1
Pyrolysis of Raw and PreTreated Wood
Run No.
A2
Cellulose Content, X mf
Ash, X mf
Temperature, C
18
20
38
Poplar
St.Lawrence
Poplar
Wayman
Poplar
Biohol
Pine
Stake
Poplar
49.1
0.46
65.4
0.85
43.1
54.9
488
1.0
500
47.0
0.67
497
1.8
500
IEA
Feedstock
1SL
500
Yields, wt X mf
Gas
Char
Water
Organics
Total Recovery
Levoglucosan
Other Sugars
Hydroxyac etaldehyde
Pyrolytic Lignin
X Cellulose
Converted to Sugars
14.0
11.9
13.0
12.4
10.8
7.6
7.7
10.1
12.2
65.8
2.9
8.5
78.4
63.2
23.0
10.6
51.0
96.5
99.0
97.6
92.1
87.3
3.0
6.1
6.7
8.6
7.4
10.3
10.0
16.2
4.5
5.1
9.1
18.8
19.3
Trace
21.9
2.9
1.1
7.5
18.0
18.5
14.7
35.5
29.1
8.5
7.5
4.7
3.2
58.9
207
Table 2
Pyrolysis of Some AcidHydrolysed Woods
10
Run No.
IEA
Poplar
Feedstock
46
14
St.Lawrence
Poplar
Stake
Poplar
Celluiose Content, X ffl

Ash. X mf
Hydrolysis Time, hours
Temperature, C
65.5
0.02
6
480
70.6
0.30
2
480
66.5
0.16
2
490
Yields, wt X mi
Gas
Char
Water
Organics
6.9
S.2
2.2
80.9
6.4
10.5
5.2
75.0
6.6
6.7
3.2
82.1
Total Recovery
98.2
97.1
98.6
Levoglucosan
Other Sugars
Hydroxyacetaldehyde
Pyrolytic Lignin
30.0
13.2
0.9
21.0
30.1
18.8
0.9
17.9
25.3
20.2
4.3
18.8
66.0
69.3
68.4
X Cellulose Converted
co Sugars
Table 3
Pyrolysis of IEA LignoCellulose Under Varying Conditions
Run Ho.
A1
Temperature, 'C
Feed Rare, g/hr
Hydrolysis Tiae, hr
Moisture, wt
Particle Size, aa
501
46.9
6
16.5
0.25
Yields, wt % mf
Gas
Char
Coke
Organics
Water
6.4
0.0
6.7
79.6
0.9
Total Recovery
co2
cnu
c2+
Oligosaccharides
Cellobiosan
Glucose
Fructose (?)
Glyoxal
1,6Anhydroglucofuranose
Levoglucosan
Hydroxyacecaldehyde
Formic Acid
Formaldehyde
Acetic Acid
Acecol
ST11
480
71.5
6
6.5
0.5
475
116
2
6.0
0.5
501
86.9
6
3.5
0.5
485
41.6
2
13.7
0.5
6.9
6.4
6.3
4.4
0.0
6.2
77.0
10.0
4.3
0.0
4.2
78.1
9.6
92.6
97.6
96.2
8.2 11 6.3
80.9
2.2
93.6
CO
Pyrolytic Lignin
]1
|
ST10
98.2
173.6
S#ll
S*
2.79
3.07
0.38
0.10
2.13
2.29
0.6
2.5
1.9
0.4
2.00
1.96
0.33
0.10
1.96
1.93
0.33
0.11
1.19
5.68
1.89
3.89
0.11
4.50
30.42
0.37
1.42
0.8
0.17
0.06
0.69
4.74
1.34
2.21
0.28
3.90
30.0
0.9
0.89
4.77
1.96
2.12
0.28
3.89
28.7
0.9
0.50
3.71
2.56
6.05
Tr
2.01
2.32
2.40
18.80
3.96
4.96
2.36
2.32
0.07
1.06
1.03
0.12
19.0
21.0
*NH 3 treated.
21.8
See text.
Tr
0.50
0.65
1.96
25.56
1.62
) . ,,
1 "
...
23.7
...
...
0.70
23.9
208
Table 4
Pyrolysis of De-ionized IEA Poplar
S#3
S#5
S06
S#7
S#4
530
-530
493
495
-530
8.0
18.3
23.6
27.1
22.3
0
(0.1) (0.1) (0.1) (0.1)
0
28.9
11.4
7.0
3.0
-0.5
-0.5
-0.5
-0.5
-0.5
Run No.
Temperature, "C
Feed Rate, g/hr
Additive (wt X ) *
Moisture, wt
Particle Size, mm
Yields, wt X mf
Gas
Char
Coke
Organics
Water
Total Recovery
CO
CO 2
CH,,
C 2+
Oligosaccharides
Cellobiosan
Glucose
Fructose (?)
Glyoxal
1,6-Anhydroglucofuranose
Levoglucosan
Hydroxyacetaldehyde
Acetic Acid
Pyrolytic Lignin
X Cellulose
Conversion to Sugars
14.13
2.5
60.50
18.25
95.38
4.86
8.75
0.38
0.13
4.92
0.94
1.81
2.86
1.12
9.33
3.35
0.67
17.8
37.1
7.35
1.66
2.77
66.07
16.20
94.05
3.86
2.90
0.60
18.73
3.36
1.41
-21
53.9
6.63
3.93
75.24
5.70
91.50
2.94
3.09
0.47
0.13
1.35
0.81
1.22
2.34
2.24
16.53
2.57
1.15
18.9
45.1
2.61
0.67
4.68
75.93
13.96
97.85
trace
2.37
0.24
3.22
0.72
5.41
66.10
-17
92.45
0.61
2.27
0.29
0.05
1.92
1.12
1.92
2.65
2.87
17.11
1.95
1.34
22.4
50.8
1.68
1.00
1.84
2.26
2.72
15.52
1.65
1.17
23.1
46.4
* (NH 4 ) 2 S0 4 ,
Table 5
Properties of Raw and Pretreated Wheat Chaff, mf basis
Pretreatment
Feed removed A sh content Cellulose content
X
X
X
None
0
22.5
22.5
5X H 2 S0 4 ,
15.6
28.8
26.0*
room temp., 20 h
5X H 2 S0 4 ,
31.6
34.2
33.5*
b.p. temp., 2 h
Average of four tests
Table 6
Pyrolysis of Prehydrolyzed Wheat Chaff
66
56
57
Run #
500
502
495
Temperature, "C
Wheat Chaff
Wheat Chaff
Feed
Wheat Chaff
acid washed
acid washed
untreated
at 100'C
at room temp.
,
0.5
0.5
App. res. time, s
0.5
49.1
Feed rate, g/h
86.8
83.7
41.8
36.8
Amount fed, g
36.2
3.9
Moisture, w/w X
5.7
6.1
-0.25
-0.25
-0.25
Particle size, mm
mf
maf
mf
maf
mf
maf
Yields, w/w X
8.7 12.2
11.0 14.1
8.4 12.7
Gas
43.9 27.6
44.0 14.9
40.5 16.4
Char
6.0
8.4
8.6 11.1
7.7 11.7
Water
38.4 58.4
42.4 59.6
37.2 47.9
Organics
98.5 97.7
97.6 96.6
100.7 100.7
Total
0.9
1.2
10.5 14.7
13.7 20.8
Levoglucosan
5.5
8.4
6.3
8.8
0.6
0.8
Other sugars
2.5
3.2
tr
tr
tr
Hydroxyacetaldehyde tr
7.3
X Cellulose converted 70.8
63.1
into sugars (glucose
equivalent)
209
PRODUCTION OF BENZOLES AND ACTIVE CARBON FROM
WASTE RUBBER AND PLASTIC MATERIALS
BY MEANS OF PYROLYSIS WITH SIMULTANEOUS POST-CRACKING
PROFESSOR R. CYPRES and DR B. BETTENS
Universite Libre de Bruxelles (ULB), Centre de Transposition
Semi-Industrielle de la Recherche Applique (Centre for the
Semi-Industrial Transposition of Applied Research) TSIRA,
Charleroi, and the Association pour l'Incinration,
la Collecte et la Destruction des Immondices de la Region de
Charleroi (Association for the Incineration, Collection and
Destruction of Waste for the Charleroi Region) ICDI
Summary
The pyrolysis of' rubber has long been the subject of study. The
initial aim was to regenerate isoprene, the monomer of natural rubber.
Then,
after 1967,
research was carried out into cracking at
temperatures of between 300 and 1 000C. Temperature was seen to have
a marked influence on the kind of products obtained by cracking. At
low temperatures, aliphatic hydrocarbons predominate in the liquid
phase.
At high temperatures,
aromatic hydrocarbons,
BTX and
naphthalenes are formed to the exclusion of all other products.
Pilot installations have been constructed in various countries by Goodyear and Interco Inc. (37.5 tonnes per day) in the USA, Kobe
Steel (20 t/d) and Energy Recovery Research (20 t/d) in Japan, Foster
Wheeler in Great Britain,
Deutsche Reinfen- und Kunstoffpyrolyse
(15 t/d) and Mannesmann Veba Umwelttechnik (48 t/d) in the Federal
Republic of Germany, to name but a few.
The process developed by the ULB and the TSIRA Centre is based
on two-stage pyrolysis.
During
the first stage,
rubber
is
depolymerized at a relatively low temperature (around 500C). During
the second
stage,
the volatile substances thus obtained are
post-cracked at temperatures of between 750 and 800C. This process
exploits the fact that aromatization can take place only above 700C,
whereas deploymerization and the formation of mainly C4 olefins
produces maximum yields at low temperatures.
The aromatization
mechanism was studied in great depth by subjecting butane, butene and
butadiene to thermal cracking.
These are aromatized mainly into
benzene, toluene and xylene as a result of Diels Alder cyclization
reactions, with two molecules being converted into C4, followed by the
dehydrogenation of cyclohexenes into benzene and its derivatives.
Pyrolysis with simultaneous post-cracking maximizes the yield of
benzoles. It is also possible, by varying the period of time for which
volatiles are retained in the post-cracking zone, to obtain high
yields of naphthalenes. This makes for flexibility of operation, as
the process can be made to function according to the market prices of
benzoles and naphthalenes.
Research was carried out into a full working plant consisting of
a pyrolysis furnace with a conveyor belt, a depolymerization zone and
a post-cracking zone. The furnace is charged with whole car tyres
(lorry tyres are first sheared) and the solid residue is eliminated in
the lower section of the furnace.
210
Economic studies showed that it was not profitable to treat more
waste tyres than are available within a limited radius of a
conurbation. Collection costs become prohibitive if tyres must be
collected outside the area covered by municipal collection services.
This is why we explored the possibility of setting up units capable of
processing approximately 500 t of waste tyres per annum within
existing refuse treatment centres. Similar units could be set up in
all conurbations. In the case of large or very large cities, where
much more waste could be collected,
larger installations could
obviously be constructed using the same model.
The process is technically feasible and would be highly
profitable. The capacity of the installation must correlate with the
quantity of tyres available within a radius not exceeding that of an
urban centre together with its adjacent centres of population.
Treatment of such waste must be combined with that of household waste
within existing centres,
and suitable arrangements made for its
collection.
From an environmental point of view, the dumping of tyres in
quarries or elsewhere is not only detrimental to the sites in
question,
but also encourages the proliferation of rats.
The
incineration of tyres leads to atmospheric pollution unless expensive
devices are installed to clean the fumes. Pyrolysis is the only method
which produces aromatic hydrocarbons in the form of benzoles and
naphthalenes, together with solid carbon (from the carbon used to
reinforce tyres), which can either be converted into active carbon or
used for other industrial purposes. The scrap tyre is a unique source
of energy in that the only real cost involved is that of collection.
The price of benzole and naphthalene fluctuates according to the price
of oil.
1. INTRODUCTION AND LITERATURE SURVEY

Like any other organic compound, rubber decomposes when it is heated.
Natural rubber is a polymer of 1,3 methyl butadiene. Generally speaking,
pyrolysis is governed by the following parameters: temperature, retention
time at the reaction temperature, pressure, and type of gaseous atmosphere.
There are two stages to pyrolysis: primary cracking and post-cracking.
Post-cracking occurs at higher temperatures and enables primary products to
be converted into compounds which may have a higher market value.
Work on the pyrolysis of rubber first began in the 1920s. Initial
research was carried out with a view to regenerating the monomer of natural
rubber, isoprene. Williams (1) used atmospheric distillation to obtain a
distillate containing approximately 5% isoprene. The effect of pressure was
subsequently explored by Standinger and Fritschi (2) . These two authors
showed that distillation at temperatures of between 275 and 350C and at a
reduced pressure of 0.1 mm Hg yields 63.5% of liquid phase, approximately
half of which consists of isoprene and its dimer, dipentene. Standinger (3)
went on successfully to distil rubber in an inert atmosphere at atmospheric
pressure. Using this method, he managed to increase the weight of the liquid
phase, which consisted mainly of isoprene dimers such as limonene and other
monocyclic terpenes.
The author also reports the presence of cyclohexadiene and methylcyclohexadiene in the liquid phase. The rapid decomposition (4) of a crepe
211
of natural rubber at 700C produced olefins, dienes, cyclohexadiene, as well
as aliphatic and aromatic hydrocarbons.
Japanese authors (5) pyrolysed a solution of rubber in heavy oils at
temperatures of between 310 and 390C and at pressures of between 50 and 200
atmospheres. Reaction products consisted mainly of cracked oil, bitumen,
carbon and gas.
Since then, research has started up in a number of new areas, in an
attempt to discover ways of converting rubber waste into liquid combustibles
and fuel. One method is the aromatization of products generated by primary
pyrolysis. This has prompted a considerable number of researchers to carry
out investigations into the pyrolysis of isoprene and its dimers. Oro, Han
and Zlatkis (6), for instance, pyrolysed isoprene at temperatures of between
300 and 1 000C. The influence of temperature on the composition of the
reaction products is very marked. Whilst aliphatic components predominate in
the liquid phase at low temperatures, at high temperatures decomposition
products are entirely aromatic; they consist principally of naphthalene,
methylnaphthalenes, xylenes and trimethylbenzenes, together with toluene.
Pyrolysis produces optimum yields of aromatic components at temperatures of
between 700 and 800C.
It was not until 1974 that interest in the solid phase really
developed. Most studies concentrated on the recovery of the solid phase with
a view to using it in the treatment of waste water once it had been
activated. Mention should be made of the work of Tanaka and Gomyo (7), Jo
and Yoda (8), Sanga (9), Ishibashi and Noda (10) and Kudo (11).
A number of pyrolysis methods have been, or are being, developed at
pilot or industrial scale.
In 1977, Goodyear carried out tests using a rotary drum in which
ceramic beads were heated to 650C and used to pyrolyse shredded tyres.
Results showed that the profitability threshold for this type of reactor,
which had been developed previously for processing bituminous shale, was of
the order of 150 tonnes per day, which was too high.
Two plants came into operation in 1979, one in Japan and the other in
the USA. The Japanese plant has a capacity of 20 t per day and is run by
Kobe Steel Ltd. It consists of a rotary kiln with scraper blades to remove
carbon from the walls. The American plant has a capacity of 37.5 t per day,
is situated in Houston, and is run by Intenco Inc.
A third plant with a capacity of 20 t per day was set up in Osaka by
the American company Energy Recovery Research Group.
In Great Britain, Foster Wheeler Power Products Ltd uses a process
developed jointly by the Warren Spring Laboratory and the National Research
Council.
Pieces of waste tyre are held in place between two parallel
vertical grills and heated by a horizontal stream of hot flue gas from an
auxiliary furnace.
Some of the gases thus generated are burned in the
furnace to produce the hot flue gas.
In the Federal Republic of Germany, Deutsche Reifen- und Kunststoffpyrolyse GmbH set up a fluidized bed plant with a capacity of 15 t per day
in Hamburg in 1982. In this process, which was developed by the University
of Hamburg, whole tyres are used as a feedstock for the reactor. These
gradually sink into a fluidized bed of sand and carbon black as pyrolysis
progresses. The steel casings are collected on a grill and removed.
Mannesmann Veba Umwelttechnik GmbH (Federal Republic of Germany) is
currently planning to construct a rotary kiln with a capacity of 48 t per
day for pyrolysing rubber, plastics and resins.
Dunlop Holding Ltd has financed a research project at the University
of Aston (Great Britain) with a view to using molten carbonate salts as a
source of heat for pyrolysis.
212
With the help of subsidies from the US Department of Energy, Rockwell
International Corp. has carried out pilot-scale tests into pyrolysis at
Canoga Park, California, using molten sodium carbonate salts. Pieces of tyre
react with the sodium carbonate at temperatures of between 900 and 1 000C
and produce a combustible gas rich in hydrogen and carbon monoxide when
exposed to a reducing atmosphere fuelled by a fixed amount of air.
USBM Firestone pyrolyses scrap tyes in an electric furnace at
temperatures of between 500 and 900C and at a pressure of 150 bars. In
spite of the high pressure, products are not qualitatively different from
those generated by other processes, nor is the yield.
The Herbold process treats pieces of waste tyres and plastics
measuring between 30 and 40 mm at temperatures of between 430 and 450C. A
24 t/d installation would cost approximately $1 000 000 (1978 prices).
In the Reprox process (Japan), pieces of waste tyre which have been
reduced to a size of between 50 and 100 mm are pyrolysed in a fluidized bed.
Retention time is less than one minute. Gases from the furnace are burned
off after desulphurization, whilst the oils are used as commercial fuel.
Research is currently being carried out into the residual carbon which is
produced.
In the H. Rubber process, rubber undergoes catalytic hydrognation
after it has been pulverized to a grain size of approximately 0.1 mm and
suspended in oil. A desulphurization and hydrognation catalyst such as
cobalt molybdate is used on an aluminium support. Hydrognation takes place
at 450C and at a pressure of between 35 and 200 bars. Investment for a
plant with a capacity of 270 000 t per annum would be of the order of
$30 000 000 (1977 prices), and production costs (including hydrogen, labour,
energy and maintenance) around $76 per tonne.
In the DSR Firestone process, rubber is heated in aromatic oil to
induce depolymerization. The aim is to produce carbon black suspended in the
oil, the mixture then being used to make new rubber compounds. Particle size
is 35 mesh at a temperature of between 250 and 275C and after a reaction
time of between 12 and 24 hours, unfortunately, the suspension produced by
this method is not of a sufficiently high quality to permit its use in the
rubber industry.
The H Oil process is also designed to recover high-quality carbon
black and fuel oil. Waste is pulverized and then dissolved in oil before
being depolymerized. This is done at a temperature of 200C and a pressure
of 3 bars.
Mention should also be made of the low-temperature process (around
300C) developed at the university of Compiegne.
The Tyrolysis method used in Wolverhampton (GB), is based on thermal
decomposition at temperatures which are carefully selected to give the
maximum yield of fuel oil. The Wolverhampton plant began operating in 1984.
It is designed to treat 50 000 t of waste tyres per year, producing 20 000 t
of fuel,
17 500 t of carbon and 7 000 tonnes of steel.
It is a
self-sustaining process, burning preheated pyrolysis gases. Tyres must be
shredded twice in succession before the reactor can be fed with ground
feedstock.
Although this list of waste tyre pyrolysis plants is far from
exhaustive,
it does show that the pyrolysis of waste tyres is widely
developed throughout the world. Methods vary according to the technology
used.
At low temperatures (below 500C), fuel oil is produced but not much
gas. At high temperatures, light aromatics and lavjer quantities of gas are
produced.
213
In our process, advanced depolymerization of rubber takes place at low
temperatures. The C3 and C4 olefins thus produced are continuously aromatized into BTX at high temperature.
2. EXPERIMENTAL RESULTS
The results of our laboratory research were published in 1981 (12) and
were the subject of a feasibility and development study (13) which was
financed by the Walloon region and carried out jointly by the following
bodies working together on a temporary basis: the TSIRA Centre, the ICDI,
the Centre de Transposition Semi-Industrielle de la Recherche Applique
(Charleroi),
and the Intercommunale de Collecte et de Destruction des
Immondices de la Rgion de Charleroi.
We studied a two-stage process comprising an initial low-temperature
pyrolysis phase followed by continuous post-cracking of resultant volatile
materials at a higher temperature. This concept is based on a fact revealed
by previous studies into the aromatization of short-chain olefins (14, 15,
16), namely that aromatization begins to take place at 750C as a result of
the cyclization of olefins into C2, C3 and C4. Post-cracking at a carefully
chosen temperature effectively allowed an additional fraction of the gases
corresponding to these ethylene compounds to be aromatized.
2.1
Pyrolysis with Post-cracking
The material to be pyrolysed is heated to a temperature of between 400

and 450C. The gaseous phase thus produced is entrained by a vector gas
stream into a second post-cracking furnace (600 to 800C).
The large
isothermal zone in this furnace ensures that the gas remains in the reaction
zone for a sufficient length of time to enable aromatization to take place.
The composition of mass balances for the different phases is given in
Figure 1. The composition of the gaseous phase is given in Figure 2 and that
of the liquid phase in Figure 3.
It will be seen that the ethylene compounds disappear at higher
temperatures. They are aromatized, producing H and CH in accordance with
the following general reactions :
and
C
4H8
4H8
+ C
+ C
2H4 - C6H6
3H6 - C6H6
+ CH
3H
2
2H
In the liquid phase, isoprene quickly disappears above 600C. At high

temperatures, naphthalene and plenanthrene seem to be most common, whereas
the concentration of BTX does not vary significantly above the 600C
threshold.
The heating of elastomers induces depolymerization reactions. These
depolymerization mechanisms are very complex and are described differently
by various authors; they can lead to the formation of dipentene (17), or of
numerous dienes of lighter molecular weight.
In the case of rubber,
butadiene and its methylated derivative probably account for an important
fraction of such dienes.
As has been seen, the pyrolysis of rubber leads to the production of
ethylene, propene and 1,3 butadiene. These induce aromatization as a result
of Diels Alder reactions, which have been amply described in the relevant
literature (18, 19, 20). These reactions can be represented as follows:
Moles
%
Liquid
Weight
60
%
70
BTX
^--^^Styrene
50
30
20
to
li
Phenanthrene
20
\ o
20
^Naphthalei
10
^
6O0
700
800
P o s t - c r a c k i n g temperature
Fig. 1. Mass balance for tyre

pyrolysis with 450C hot charge
600
700
800
P o s t - c r a c k i n g temperature
Fig. 2. Molar percentages of

constituents of the gaseous phase
obtained by tyre pyrolysis with
45cPC hot charge
600
7O0
Isoprene
800
Post-cracking temperature
Fig. 3. Weight percentage of

constituents of the liquid phase
obtained by tyre pyrolysis with
450C hot charge
215
2 C 2 H 4 + 1 C 4 H 8 - 1,3 C 4 H 6 +
.110
C- r O
1.3 butadiene ethylene
cyclohexene
4-methyl-l-cyclohexene
4-vinyl-l-cyclohexene
Dehydrogenation causes cyclic compounds with six carbons to produce

aromatic derivatives corresponding to one cycle. As a result of subsequent
associative reactions,
these may lead to the formation of polycyclic
compounds such as naphthalene and phenanthrene.
2.2
Influence of Contact Time
Pyrolysis was carried out three times, with the contact time being
varied by changing the rate of flow of vector gas (N ) . Three values were
used: 20, 40 and 60 ml per minute.
Michelin X tyres were used in all the tests. The results are given in
Tables I, II and III.
TABLE I. Mass balance produced by tyre pyrolysis,
as a function of contact time (% weight)
Rate of flow of nitrogen in ml/min
20
40
60
Gaseous phase
13.96
15.12
13.42
Liquid phase
34.44
36.54
41.58
Solid phase
51.60
48.34
45.00
216
TABLE II. Molar % of constituents of the gaseous phase as
a function of the rate of flow of carrier ga:
Rate of flow of nitrogen (ml/min)
20
40
60
23.28
23.30
30.65
56.15
53.85
47.36
2H4
14.95
16.78
13.56
2H6
3.21
3.56
4.51
3 R
0.15
0.32
3H6
2.26
2.52
3.60
CH
C
TABLE ill. Percentage weight of the constituents of the

liquid phase as a function of the rate of
flow of carrier gas
Rate of flow of nitrogen in ml/min
Octene + lights
Benzene
Toluene
m + p-xylenes
p-xylene
Styrene
Indane
Indene
Naphthalene
2-methylnaphthalene
1-methylnaphthalene
Acenaphthene + ...
Plenanthrene
Heavy fraction
20
40
60
3,.55
33..85
14..55
4,.16
1..24
4..17
1..27
2..60
11..21
3..41
1..87
7..47
4.,58
6..08
1.04
36.41
16.78
4.83
1.35
4.58
1.68
2.47
9.15
2.42
4.06
4.35
3.19
7.68
2.89
30.57
15.66
5.22
1.48
5.83
2.18
3.26
7.97
2.71
5.43
6.13
2.98
7.69
An increase in the flow rate N2 appears to improve the yield of liquid

phase but somewhat diminish the benzene content. This is because depolymerization products are entrained more rapidly at lower temperatures, whereas
at high temperatures aromatization is less marked owing to the reduced gas
retention time in the hot zone.
2.3
Pyrolysis of Various Tyres and Brands of Tyres
Different brands of tyres were pyrolysed at temperatures of between

450 and 800C. The results appear in Tables IV to VII.
There do not appear to be any significant differences, although it
should be pointed out that the yield of liquid is greater when V 10 tyres
are used.
217
TABLE IV. Mass balances produced by pyrolysing various types of tyre
Michelin
Rad. X
Michelin
Rad. XAS-P
Uniroyal
Rallye
Uniroyal
Rallye
Wet Weather
Kleber
V 10
Kleber
V 10GT
Gaseous phase
16.77
17.55
16.05
19.47
16.98
16.16
Liquid phase
38.46
37.15
39.72
37.02
41.34
42.17
Solid phase
44.77
45.30
44.23
43.51
41.68
41.67
TABLE V. Molar percentage of constituents of the gaseous phase

Michelin
X
H
CH
Michelin
XAs
Uniroyal
Uniroyal
Wet Weather
Kleber
V 10
Kleber
V OGT
31.69
26.50
29.01
15.75
32.91
39.49
54.88
53.25
54.61
63.84
56.60
46.98
14.90
7.18 . 10.99
2H4
10.06
12.72
11.89
2H6
2.54
4.38
3.51
3.96
2.75
2.12
0.06
0.84
3.18
0.97
1.49
0.57
0.42
0.18
3H8
3H6
4 8
TABLE VI. Weight percentages of the constituents of the liquid pha se

after pyrolysis at 450C- 800C
Michelin
X
Micheln
XAS-P
Uniroyal
Rallye
0.04
0.16
42.07
15.32
2.84
0.62
0.10
0.07
0.27
34.43
15.06
3.95
0.82
0.11
0.06
0.25
41.51
17.14
3.52
0.69
0.11
0.05
0.09
30.42
14.25
3.28
0.66
0.10
0.15
41.89
15.55
2.88
0.65
0.07
33.93
13.04
2.61
0.46
0.09
2.35
12.67
2.42
11.69
2.98
10.72
2.69
12.96
1.87
11.19
2.10
14.17
12.97
14.59
9.79
15.85
10.10
12.29
5.59
1.41
5.38
8.47
3.92
5.74
5.62
9.52
5.04
7.32
5.89
12.41
Uniroyal
Wet Weather
Kleber
V 10
Kleber
V OGT
Non-aromatic
c6c7 +
isoprene
Octene
Benzene
Toluene
Ethylbenzene
m + p-xylenes
o-xylene
Styrene
(intermediate
fraction,
propylbenzene,
indane, indene,t
etc)
Naphthalene
Methylnaphthalenes
(diphenyl,
fluorene, etc)
Phenanthrene +
anthracene
Heavy fraction
218
TABLE VII. Comparison of various mass balances
Gaseous phase
Liquid phase
Solid phase
Average over
6 pyrolyses
450-800C
Average over
6 pyrolyses
500-750cC
17.16
39.31
43.53
lb.87
39.02
45.11
Pyrolysis of a
mixture of all 6
tyres 500-750C
13.82
39.23
46.95
Mixtures of tyres give approximately the same results

obtained for one type of tyre, as can be seen from Table VIII.
as
TABLE VIII. Comparison of the different phases obtained by pyrolysing

a mixture of 6_ tyres with that obtained from an average
of 6 pyrolyses of the same tyres
Analysis of the liquid phase as % of weight
C
3H6' C4H8'
5H10
5 H 8 ' C 5 H 6 ' C 6 H 12
C 7 H 1 4 , Isoprene
Cyclohexadiene
Octene
Benzene
Toluene
Ethylbenzene
m-xylene + p-xylene
o-xylene
n-propylbenzene
Styrene
Ol -methylstyrene (unidentified)
Indane
Indene (unid.)
Methylindene (unid.)
Naphthalene
unid.
2-methylnaphthalene
1-methylnaphthalene
Diphenyl (unid.)
Acenaphthene (unid.)
Dibenzyl (unid.)
Fluorene (unid.)
Phenanthrene
m-phen., pyr., benzanth., H.F.
4.10
1.88
26.15
17.27
6.42
1.86
0.61
0.11
5.97
2.34
2.42
2.47
1.35
5.08
0.21
2.66
2.18
2.67
2.62
2.25
2.91
2.37
4.81
3.59
2.06
27.80
17.81
8.27
1.94
6.51
3.23
4.00
5.52
2.72
5.81
4.71
2.25
3.69
Analysis of the gaseous phase as a % of volume

21.05
22.37
51.66
53.63
2H4
13.92
12.10
2H6
7.48
6.66
3H8
0.82
0.59
3H6
5.06
4.64
CH
C
those
219
3. EXPLOITATION OF RESIDUAL CARBON
Carbon residue accounts for between 35% and 40% of the weight of a
pyrolysed tyre. Its minimum value is that of a good smokeless fuel, since
all the organic matter has been decomposed thermally and the combustion
fumes no longer contain tar.
We studied the adsorption properties of various types of residual
carbon obtained from tyre pyrolysis after they had been activated by steam
and so converted into active carbon. This is an excellent adsorbent and is
well known on the market as a purification medium. Its high price does,
however, make it unsuitable for large-scale use as a water purifier.
There is clearly an interesting potential in being able to convert 40%
of a particular type of waste, in this case the scrap tyre, into active
carbon.
Overall results are given in Figure 4, which shows isotherms of phenol
adsorption by carbon, where q represents the amount (in mgs) of phenol
adsorbed by a quantity g of carbon.
Activation is by steam heating at approximately 900C. Activation time
is about 30 minutes. Under these conditions, the weight loss of carbon is of
the order of 30-40%.
The test solution had a phenol concentration of
100 mg/1.
Some types of active carbon obtained from tyre pyrolysis (550, 600,
700C) have adsorbent qualities which are very similar to those of
commercially-produced active carbon. Other types, obtained at pyrolysis
temperatures of between 450 and 500C could also be used provided the higher
residual concentration of phenol is acceptable. Carbon produced by pyrolysis
could even be used "raw" for the pretreatment of heavily polluted water.
It will be seen from the isotherms that carbon obtained by pyrolysis
at 550C is the best.
As far as abatement rates are concerned (Figure 5) , it will be seen
that in the case of high weight concentrations of active carbon (approximately 5 g ) , carbon obtained at 600C adsorbs all molecules of phenol (rate
= 100%). For other types of carbon, the abatement rate is approximately 95%.
At lower concentrations
(approximately 1 g) , carbon obtained at 500C
adsorbs the most molecules (90%), followed by carbon obtained at 600C and
700C. Rates for carbon obtained at the latter two temperatures are of the
order of 75% to 85%.
In order to improve classification of the various types of active
carbon obtained,
we also studied their adsorption properties vis-a-vis
methylene blue and iodine.
The solid phases used in these tests were obtained by steam or carbon
dioxide activation. Figures 6 and 7 show the adsorption capacity of these
types of carbon vis--vis methylene blue (curve a) and iodine (curve b ) , as
a function of activation time.
The specific surfaces of the various types of carbon derived from tyre
pyrolysis were measured both before and after activation.
The specific
surface before activation, of the order of 60 m 2 /g, is the same whatever the
speed of pyrolysis. Steam activation creates specific surfaces of around
390 m 2 /g for slow pyrolysis and 290 m 2 /g for rapid pyrolysis.
To sum up, it can be said that this method, in which waste tyres are
used as a feedstock, produces oils with a high BTX content and carbon with
good adsorbent properties as a result of pyrolysis at a low temperature
(450C) and simultaneous post-cracking at a high temperature (700 to 800C).
Figure 8 shows the mass balance produced by treating one tonne of used
tyres.
220
A
C
D
E
F
G
Commercial
550
70O
600
500
450
Non-active
Abatement rate
Residual concentration
Fig. 4. Isotherm of phenol

adsorption by carbon
Amount of carbon (in g)
Fig. 5. Rate of phenol adsorption

by active carbon
Iodine
Methyle
blue
100.
80
.3
60 -
.. .2
20
10
15
20 min
Fig. 6. Steam activation
Fig. 7. CO? activation
221
1 t TYRES
Pyrolysis
450500C
Postcracking
75O80OC
"2
CH4
C 2 H
C H
2 6
c
3
Mise.
3.8
O. 35
32
18.6
20.1
3.15
148
_^ LIGHT
BTX 2 6 0 kg
Sty.
Misc.
.HEAVY
1 3 2 kg
SOLID
4 6 0 kg
Naphth.
Phen.
carbon
steel
ash
105.8
68.6
37.4
24.4
29.8
21.2
18.0
359
70
31
Fig. 8. Mass balance produced from the pyrolysis of 1 t of used tyres
4. STRATEGY FOR THE COLLECTION OF WASTE TYRES

4.1
A vailability of Used Tyres
ICDI and TSIRA, working together on a temporary basis, carried out a

detailed study into the amounts of used tyres available in Belgium, and the
cost involved in collecting these. They considered the Charleroi region for
the purposes of the study.
This study, which cannot be described in detail here, concluded that
between 45 000 and 50 000 tonnes of scrap tyres are available each year in
Belgium. They are the main source of rubber waste. Table IX gives a very
approximate breakdown of the different ways in which this waste is used.
222
TABLE IX. Use of waste tyres
Retreading
Ground feedstock
Export
Pyrolysis
Artificial reefs
Incineration
Tipping
Regeneration
Marginal users
20%
0.5%
10%
0%
0%
25 to 30%
+ 35% (difference)
3%
5%
At least 65% of all waste tyres are incinerated or dumped.

Incineration
Incineration exploits the energy content of tyres.
They have a
calorific value of between 6 000 and 9 000 Kcal/kg, and are thus ideal for
this purpose.
Free-air incineration is banned, but has in any case several obvious
drawbacks :
it produces large quantities of black, acrid and highly noxious smoke;
it produces high concentrations of SO;
the considerable calorific value of tyres is wasted.
The main pollutants produced by the combustion of tyres are sulphur
oxides, nitrogen, carbon, zinc, very fine "carbon black" dust (carbon black
is used to reinforce tyres), and condensed polyaromatic hydrocarbons, which
are carcinogenic.
Tyres are incinerated in furnaces specifically designed for the
purpose (types include LUCAS, UHDE, CEC-CEA, etc.). Conventional furnaces
can also be used if incineration plants are modified by means of scrubbers,
electrostatic dedusters, desulphurizers, etc. but appliances such as these
are expensive.
Tipping
In many countries, tipping is the most common form of waste tyre
disposal.
In Belgium, as in many other European countries, waste disposal sites
are becoming increasingly rare. Tyres cannot continue to be disposed of in
this way if the environment is to be protected.
Because they are not
biodegradable, they simply accumulate. Tyre dumps constitute a fire hazard
and make the ground spongy and soft, thus creating problems if the site is
ever redeveloped. Rats proliferate in dumps which are either poorly covered
or left completely uncovered, and this clearly presents a health threat to
the general public.
As has been pointed out, tyres have a high calorific value. Tipping
does not exploit this potential energy, nor does it exploit the hydrocarbon
and carbon content of used tyres.
The cost of tipping varies according to the method used: a simple
tipping costs between Bfrs 300 and 400 per tonne, controlled tipping with
tyres shredded at the site costs Bfrs 2 500, and controlled tipping with the
tyres shredded before they are transported costs Bfrs 4 000.
223
4. 2
Cost of Collection
An evaluation was made both of the cost of collecting tyres in the

Charleroi area, and of the scrap tyre potential of the region.
Most used car tyres are located in the main distribution outlets for
new tyres. These are, in descending order of importance:
tyre specialists: 57%
garages, service stations and dealers: 30%
hypermarkets: 13%
Used lorry tyres are mainly found at the following places :
tyre specialists : 60%
end users (army, haulage firms, etc.): 35%
major distributors: 5-10%
ICDI carried out a detailed investigation into the cost of collecting
1 000 tonnes of used tyres per year in the Charleroi region. Collection is
carried out using Berliet Saviem refuse lorries with GDA skips with a
capacity of 20.4 m 3 . Normal manning costs are assumed. When all expenses are
taken into consideration, the total cost of collecting one tonne of used
tyres is approximately Bfrs 1 550 (1984 prices). This figure assumes that
used tyres can be taken away free of charge,
and that there are no
collection fees.
The remaining tonnage treated at the plant comprises tyres which are
delivered to the treatment centre, and for which payment is made. This is
the system used for incineration. In 1984, the CBR cement works at Lixhe
paid Bfrs 600 for each tonne of tyres delivered to the plant. This figure is
much lower than that quoted above for specific collection (Bfrs 1 550 per
tonne) . In the case of incineration, it is not possible to increase this
price without making it economically unviable to use old tyres as fuel.
Higher prices can, however, be paid for pyrolysis, although these must still
remain well below the cost of collection if there is to be a real advantage.
It has been estimated that, on the basis of the Lixhe experience, 45% of
used tyres in the Charleroi region could be obtained for Bfrs 600 per tonne
delivered to the plant.
The ICDI study showed that collection price increases rapidly in
proportion to distance from the treatment plant, particularly since there
are much fewer tyres to be collected near the outer limits of the region
concerned.
The conclusions drawn by the ICDI led us to develop a new strategy for
the pyrolysis of used tyres. We do not think it reasonable to construct one
large plant in Belgium with an annual capacity of between 20 000 and 25 000
tonnes. (This figure corresponds more or less to the quantity of scrap tyres
which are not used for other purposes. ) Tyres would have to be collected
over long distances and the cost would soon become prohibitive. Moreover,
the need to guarantee the supply of tyres to the pyrolysis plant would leave
the plant in a weak position vis--vis collectors. The price of used tyres
would inevitably rise.
If, however, existing centres for the incineration of household refuse
were made to include small-scale,
"sub-regional" units (i.e.
units
corresponding to the amounts of used tyre waste produced by any one urban
area), this would constitute an extension of existing activities carried out
by such bodies. The collection of tyres would be carried out by the same
bodies responsible for collecting household waste.
224
5. 2 OOP TONNES PER YEAR PLANT
5.1
Description of the Plant
The tonnage of tyres available in the Charleroi region was used as a

basis for designing a 2 000 tonne per annum industrial plant to carry out
pyrolysis with simultaneous post-cracking. The plant design is illustrated
in Figure 9. The main element is the furnace, the design and dimensions of
which were drawn up by EUROFOUR. This consists of a conveyor belt within the
horizontal part of the oven, which is heated to between 450-500C.
The tyres, which are left whole, are fed into a charging chamber,
which is kept free of air by circulating nitrogen. It is thus not necessary
to cut up the tyres. The estimated saving is between Bf rs 1 000 and 1 500
per tonne.
Depolymerization and primary cracking take place progressively.
Volatile material is entrained by the stream of nitrogen into the vertical
post-cracking furnace at 700-800C, where olefins are converted into light
aromatics. The post-cracking furnace is heated by radiant tube burners
(automatic heat recuperators), which are fitted with fins. These can easily
be removed or replaced.
Gases are separated from oils in the condenser. Light oils are drawn
towards the top of the fractional condensation column, whilst heavy oils are
drawn to the bottom.
To sum up, this installation has the following features:
1.
2.
3.
5.2
Whole-tyre feedstock, which cuts down on shredding or cutting costs.

Depolymerization and primary shredding by heating the tyres to between
450 and 500C.
The aromatization of volatile products produced at low temperatures by
continuous and simultaneous post-cracking.
Investment and Running Costs
Investment will be of the order of Bfrs 31 million

divided up as follows :
1.
(1984 estimate),
Specific equipment for the plant, comprising the following:

Pyrolysis and post-cracking furnace;
Containers for solids;
Oil condensers ;
Compressors, vibrating separators and other
accessories.
2.
3.
4.
22 370 000
800 000
600 000
Installation
Electricity
Miscellaneous (safety, civil engineering,
maintenance , engineering etc.)
TOTAL Bfrs
6 980 000
30 750 000
Running costs including personnel, supply of tyres, electricity and

nitrogen, have been estimated at approximately Bfrs 6 000 000 per annum
(1984 prices), or Bfrs 3 000 per tonne of tyres for a plant with a capacity
of 2 000 tonnes per annum.
The profitability study for this project was carried out by ACKERMANS
and VAN HAAREN - N.V.
(Antwerp) . This concluded that small units for
treating used tyres by means of pyrolysis with simultaneous post-cracking
Tyre
Gas
Nitrogen
Water
Extractor
pump
circuit
circuit _
circuit
c i r c u i t *.
j Light aromatics
(200 1 barrel)
Production
Heavy o i l s
(200 1 barrel)
to
iWater reject)
jWater
Water entry c i r c u i t
point
)
Fig. 9. Operating diagram

Industrial unit for the pyrolysis of used tyres with
simultaneous postcracking. Capacity: 2000 t / a
Carbon
con
tainer
Metal
con
tainer
Production
780 t/a
Production
140 t / a
Ln
226
(2 000 tonnes per annum capacity) would not only prove to be a profitable
investment, but would also solve a serious environmental problem.
If the hypotheses on which the operation of an industrial unit are
based can be shown to be realistic by the pilot plant, it could reasonably
be assumed that a considerable number of plants of this type might be
marketed both in Belgium and abroad.
6. GENERAL CONCLUSIONS
The following conclusions can be drawn from
pyrolysis of tyres with simultaneous post-cracking:
1.
this
study
into
the
Originality of both the process and the prototype
The process is original because it enables the depolymerization of

rubber by thermal cracking and the aromatization of olefins thus produced to
take place in one stage and within the same plant. This produces high yields
of benzene, toluene and xylene (BTX), which have a higher market value than
heating fuel. The prototype as designed is also original, and the plant
could be built by companies from the Wallonia region:
this is amply
demonstrated by the fact that EUROFOORS (Lige),
after carrying out a
detailed technical study, drew up a cost estimate for a demonstration unit
with a capacity of 2 000 tonnes per annum.
2.
Tyre pyrolysis: location strategy
The study into the cost of collecting used tyres shows that
expenditure increases rapidly in proportion to distance, and that a large
number of lorries and containers is needed if they are to be used solely for
this purpose.
This is why the authors of the study believe that the
processing of used tyres must be carried out within existing structures for
the collection and treatment of urban waste.
The current collection capacity for the Charleroi region has been
estimated at 2 000 tonnes per annum. The tonnage of tyre waste that can be
treated by any one pyrolysis plant will depend on the size of the urban
centre which supplies it. Treatment capacity has been estimated at between 4
and 5 000 tonnes per year per million inhabitants.
We recommend that the idea of a single, large-capacity plant serving
an entire country or region, as has been proposed in the past, be abandoned.
A pyrolysis plant with a capacity of 40 to 50 000 tonnes per annum
creates a number of problems. Quite apart from the fact that the distances
to be covered within such a large region would drastically increase
collection and transport costs, there is also the danger that suppliers
might begin to speculate by stockpiling available tyres.
A large plant must be guaranteed regular supplies and would thus be
highly vulnerable to any manipulations in this supply. Furthermore, a large
plant requires a much greater level of investment and thus constitutes a
much higher financial risk for developers.
A large plant also needs the appropriate infrastructure, and since
this would have to be created from scratch, investment and running costs
would again be pushed up. We thus propose that the treatment of tyres be
integrated into existing regional and local centres (this solution could
also be adopted for other types of waste). This will effectively constitute
an extension of existing activities, and will mean that advantage can be
taken of the infrastructure and experience already to hand. It should be
emphasized that, under this scheme, the collection of tyres would be carried
out by bodies which are already highly experienced in the field of household
227
refuse collection.
This does not,
however,
mean that this type of
installation would always have to be limited to small units. Indeed, these
could be of a considerable size where large centres of population are
concerned. It is clear that large urban centres such as Paris, London,
Tokyo, etc., represent a potential of tens of thousands of tonnes per annum.
3.
Profitability
The difference between the price of crude and refined products is

between 80 and 100% in the case of benzols. For carbon, the difference
between the fuel price and the price of either carbon black or active carbon
varies by a factor of 1 to 10. Pyrolysis thus has enormous development
potential and will have a great impact on job creation within the treatment
plants themselves and within industrial undertakings wishing to develop
their activities or specialize. Initially, however, it would seem advisable
to stick to the collection of raw products separated into fractions which
are sufficiently differentiated to enable exploitation to take place. The
demand for, and price of, these raw products will help determine which
strategy should be adopted in order to optimize the exploitation of these
by-products.
A profitability study carried out by Ackermans and Van Haaren S.A.
(Antwerp) came to the following conclusions :
"Results of the profitability analysis show that small units for
treating used tyres by means of pyrolysis with simultaneous postcracking and having a capacity of 2 000 tonnes per annum would
represent a profitable investment and would also solve a serious
environmental problem."
"If the hypotheses on which the operation of an industrial unit are
based can be shown to be realistic by the pilot plant,
it could
reasonably be assumed that a considerable number of plants of this
type might be marketed both in Belgium and abroad."
The report does, however, draw attention to the sensitivity of benzol
and oil prices to fluctuations in the price of oil.
4.
Market
Two aspects must be considered here: firstly, the market for pyrolysis
products, and secondly, the market for the sale of pyrolysis plants. As far
as pyrolysis products are concerned, i.e. BTX and residual carbon, the
market is favourable. It has been estimated that the demand for benzene both
in Belgium and worldwide will continue to increase steadily. The price of
BTX varies according to the price of oil, because light aromatics are
obtained by the steam cracking of oil fractions. Marketable quantities of
BTX produced by tyre pyrolysis are small in comparison with those produced
by the petrochemical industry, and would therefore have little or no effect
on prices.
Carbon can fetch prices of up to 10 times its minimum value (based on
calorific value) when it is used as a reinforcing medium in the production
of tyres, or as active carbon used in water purification (high-quality
utilization). However, since there are currently insufficient quantities of
this type of carbon to enable industrial tests and demonstrations to be
carried out, it is not yet possible to say that it will sell on the market
without additional and specific processing being carried out for each
individual application.
228
As far as the sale of pyrolysis plants is concerned,
it should be
possible to build four or five units in Wallonia and an equal number in the
north of the country and in Brussels. The export potential is considerable,
and the technology could be sold if it were shown that the chosen formula
(plants constructed on a decentralized basis and integrated into existing
waste treatment centres) were economically viable.
5.
Economic and social benefits
One obvious
advantage is that this process converts waste into
valuable raw materials.
In doing so, it produces fuel and combustibles and
so results in an overall energy saving. This in turn means that less money
m u s t be spent on importing energy from abroad.
Integration of this process into existing waste treatment centres will
create new jobs within these centres and within those branches of industry
involved in exploiting the by-products obtained.
6.
Ecological
implications
One of the roles of waste treatment centres is to protect the

environment by eliminating waste.
If used tyres can be disposed of in a
profitable way, numerous ecological benefits can be reaped at no extra cost.
The treatment of used tyres is receiving priority attention from the
Commission of the European Communities in the context of environmental
protection.
This project is thus entirely appropriate in the light of the
Commission's current concerns.
7.
usefulness of a semi-industrial pilot plant
The process as a whole must be tested at pilot level in order to

ensure that all component parts work at optimum efficiency.
A pilot plant
will also serve to establish yields and will ensure that products are
generated in sufficient quantity to be of use to industrial operators.
The pilot plant could provide a number of useful services once the
development phase comes to an end:
it could be used for training personnel
from other treatment centres wishing to acquire a similar unit,
or for
carrying out research into the pyrolysis of wastes other than tyres (plastic
material,
wood,
etc.).
The existence of a training unit for personnel
employed in businesses who wanted to purchase such a plant would be
extremely useful for promoting the method on a commercial basis .
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
WILLIAMS, Philos. Trans. Roy. Soc. London. Ser. A 1 5 0 , 241 (1860).

STANDINGER and FRITSCHI, Helv. Chim. Acta, 5, 758 (1922).
STANDINGER and GEIGER, Helv. Chim. Acta, 9, 549 (1946).
MIDGLEY and HENNE, J. Amer. Chem. S o c , 26, 1215 (1929).
KATO and SOMESHIMA, J. Soc. Chem. Ind. Japan, 3 8 , 596 (1935).
O R O , HAN and ZLATKIS, Anal. Chemist., 39, 27 (1967).
TANATA and GOMYO, Japan, Kokai 7438, 895 (CI. 14 E 331, 13(9) F2) 11
Apr. 1 9 7 4 , Appli. 7281, 419, 16 Aug. 1972.
JO and YODA (Nippon Zeon C o , L t d ) . Japan Kokai 7 4 , 102, 595 (Cl. 14 E
331, I,
12(9)F2, 91 C 9 1 ) , 17 Sep. 1974, Appli. 73 1 4 , 588, 05 Feb.
1973.
SONGA, G e r . Offen., 2, 3 2 8 , 400 (Cl. c 01b) 20 Jan. 1974.
ISHIBASHI, NODA and TERADA, Japan Kokai 7545, 799 (Cl. C O I B , B O I D ) , 24
Apr. 1975, Appli. 7396, 413, 27 Aug. 1973.
229
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
KUDO, Japan Kokai 7575, 593 (CI. COIB, BOID), 20 Jan. 1975, Appli. 73
126, 013, 09 Nov. 1973.
R. CYPRES and B. BETTENS,
"Traitement pyrolytique des dchets de
caoutchouc". Ann. des Mines de Belgique, 10, 873-890, 1981.
Convention Region Wallonne-Association Momentane ICDI-TSIRA, "Faisabilit de petites units de pyrolyse de pneus usags avec postcraquage
simultan", 171 pp, 1984.
R. CYPRES and C. BRAEKMAN-DANHEUX, "Processus d'aromatisation dans la
formation des goudrons de haute temprature".
Ann.
des Mines de
Belgique, 11, 1109-1115, 1974.
R. CYPRES, C. BRAEKMAN-DANHEUX, R. DERIE and M. BERKOL, "Aromatisation
of a C 4 alkane/alkene/hydrogen mixture obtained by catalytic dehydrogenation of isobutane". J. Anal. Appi. Pyrol., 1, 339-246, 1980.
R. CYPRES, "Aromatic hydrocarbons formation during coal pyrolysis",
Fuel Process. Technol., 15, 1-15, 1987.
MADORSKY, "Thermal Degradation of Organic Polymers", p. 219, Interscience (1969) .
WEIZMANN, BERGMANN, HIGGETT, STEINER and SALZBACHER, Ind. Eng. Chem.
43, 2312-18 (1951).
BREDAEL P., Ann. Mines Belgique, 12, 1045, 1975.
BENSON and HAUGEN, J. of Phys. Chem., 71, 6, 1967.
ACKNOWLEDGEMENTS
We should like to thank Miss GILLET and Mr PILATI, engineers at the
ICDI and TSIRA respectively,
for their contribution in drawing up the
feasibility study.
We should also like to thank the Wallonia region and Minister BUSQUIN
for the financial support which was granted to TSIRA and ICDI for the
purpose of carrying out this feasibility study.
230
CHEMICALS FROM ALMOND SHELLS BY PYROLYSIS IN FLUIDIZED BED
R. Font, A. Marcilla, E. Verd and J. Devesa

Divisin de Ingeniera Qumica. Universidad de Alicante. Spain
Summary
Flash pyrolysis of almond shells at moderate and high temperatures
in a fluidized bed reactor and an Analytical Flash Pyrolysis A pparatus
(Pyroprobe 100) have been studied, with almond shells nonimpregnated
and impregnated with inorganic chemicals. The A nalytical Flash Pyro
lysis A pparatus was used for screening of catalysts and selecting
operation conditions. A t moderate temperatures, the yields of the
following fractions and chemicals have been obtained: solid, liquids
(water, methanol, formaldehyde, acetone, 2propanol, acetic acid,
hydroxyacetone, propionic acid, 3methyllbutanol, 2furaldehyde,
dry residue at 120 sc, gases ( CO , CO, CH , H ). At high temperatures
the gases analyzed have been the following: H , CO, CO , CH ,
C H , C H , C H , C H , C hydrocarbons.
The greatest yields (,.%
basis) obtained in the different operating conditions in the fluidized
bed reactor have been the following: A ) A t temperature range 440
610 C, pyrolyzing almond shells (without impregnation): 1056 acetic
acid; 1.8% hydroxyacetone; 1.0% lhydroxy2butanone; 0.7% 2furalde
hyde; 1.0% methanol+formadehyde. B) A t temperature range
470610
-C,
pyrolyzing almond shells impregnated with CoCl
(14.1% g
CoCl /total g ) : 7.0% acetic acid, 7.0% 2furaldehyde, 0.6% methanol +
formaldehyde. C) At high temperature (820900 2 C) pyrolysis of almond
shells
(without impregnation): 30% CO, 16% CO,

5.7 % CH,
2.8%
0.8% H , 1.0% C , 0.7% C H . Recovery ofXoCl from the char
2H4'
as also Been studied. Kinetic expressions for the pyroly
coal formed
sis of almond shells nonimpregnated and impregnated with CoCl, have
also been deduced.
C
1. INTRODUCTION
Pyrolysis is one of the alternatives to be considered for conversion
of biomass to activated carbon, fuels and chemicals. Pyrolysis processes
of biomass at moderate temperatures (380600 a C) yield a pyrolytic oil
which is a mixture of organic chemicals with water, a low BTU gas and char
coal. Flash pyrolysis of lignocellulosic materials leads to an increase
in the amount of liquids produced.
High temperature (>700 9 C) flash pyrolysis of biomass yields a mixture
of gases: carbon oxides, hydrogen and light hydrocarbons. Flash pyrolysis
can be achieved discharging the biomass on a hot sand fluidized bed
reactor.
The process of biomass decomposition occurs via both primary and se
condary reactions. By selecting the operating conditions (temperature,
heat transfer and residence time of volatiles), it is possible either to
accelerate or to slow down the different reactions involved in the process,
according to their apparent activation energy. Using catalysts is another
way to change the most favourable reaction paths.
Catalysts may be classified as primary or secondary. Primary catalysts
231
act on the primary reactions (directly from biomass). Secondary catalysts
have their effect on the products of the primary reactions (carbon, vola
tiles).
A research of the pyrolysis of almond shells (an abundant and readily
available agricultural byproduct in the area) is being carried out at the
Chemical Engineering Division of the A licante University. The scope of
this investigation is to study the chemical products which can be produced
at moderate and high temperatures from the almond shells,nonimpregnated
and impregnated with chemical compounds.
2. EXPERIMENTAL SECTION
Almond shells were washed, dried, crushed and sieved to obtain a uni
form material. The almond shells composition (wt%) is the following: 29%
cellulose, 19% hemicellulose, 51% lignin, 0.2% ash (d : 0.2970.500 mm).
Calcinated sand, at 900 2 C was used as an inert bed in the fluidized
bed reactor (see references 1, 2, 3 ) . Pyrolysis in the experimental system
was run as follows: First, a dried almond shells sample of the selected
particle size was placed in the feed hopper. The inert gas flow (from an
industrial
source) was set and the oven switched on. Once the reactor
reached the selected temperature, the feeding valve was opened and the
sample fell into the sand bed fluidized reactor.
In order to carry out the experiments at moderate temperature with
almond shells impregnated with CoCl , the samples were prepared as follows:
Five batches of 60 g of almond shells mixed with catalysts solutions of
known concentrations were prepared in a "rotavapor" Buchi, providing agita
tion and a 60 mmHg vacumm for 2 hours. Afterwards, the samples were dried
at 110 9 C for 20 hours. Once the five samples were prepared, they were
mixed well.
In addition, an A nalytical Flash Pyrolysis A pparatus (Pyroprobe 100)
was used for catalyst screening (nominal heating rate 20 s C/ms).
Analytical methods and more details of the equipment and procedure
used can be found elsewhere (1, 2, 3 ) .
3. EXPERIMENTAL RESULTS AND CONCLUSIONS
A. MODERATE TEMPERATURE. NONIMPREGNATED A LMOND SHELLS
Table I shows the overall yields obtained in the experiments carried
out between 365 and 710 a C. The residence time of the vapours inside the
fluidized bed is considered lower than 0.5 s, and the residence time of
the vapours inside the reactor on the sand bed is around 3 s. The heating
rate, according to Scott and Piskorz (4) is about 500 s C/s.
Liquid fractions present a maximum within the 420610 S C temperature
range, decreasing from 610 S C due to their cracking and reforming. The
high yields in liquids obtained (about 65% dry basis) are similar to those
obtained by other researchers (5, 6 ,7).
The acetic acid yield is around 10% (dry basis) within the 440610
a
C temperature range. This yield is significantly higher than those report
ed by other authors working with other biomasses, typically around 7% from
hardwood and 7.84% from beechwood (5 ,8).
A kinetic study has also been carried out (3). Two schemes of reac
tions have been considered:
Scheme I
(biomass, )
a(gases, G)+b(liquids, L)+c(solids, S)

1
Scheme II
w gases, G
(biomass, )^2^liquids, L
^"^ solids, S
(g)
232
Assuming first-order reactions, it has been tested that similar expressions can be obtained from both schemes.
On considering the expresions deduced, the correlation of the yields
of the total of the gases, the total of the liquids and the solid residue
to the schemes suggested is good. The expressions obtained for the kinetic
constants in the 400-460 *C temperature range are the following:
k = 7.11.107exp(-32.0/RT) s _ 1
k = 1.49.108exp(-35.1/RT) s" 1
k = 14.73exp(-10.8/RT)
s-1
(R in Kcal/molsK)
B. MODERATE TEMPERATURE. ALMOND SHELLS IMPREGNATED WITH CoCl

Samples of almond shells impregnated with different catalysts have
been pyrolyzed in an Analytical Flash Pyrolysis Apparatus (AFPA) at 440
a
C. From previous results (1), it was concluded that AFPA was a suitable
device for experiments to select catalysts and operating conditions. Different catalysts have been tested: KCl, NaCl, BaCl , CaCl , CdCl , MnCl ,
CoCl , CuCl , NiCl , CrCl and NaOH, NiSO , CoSO . An increase in 2-furalcfe
hyde yield can be observed when increasing the acidity of the cation. A re^
markable increase was obtained for the cations of intermediate acidity Cd ,
Mn
and Co . An increase of hydroxyacetone yield with respect to non-catalytic pyrolysis of almond shells was observed with NaOH (basic catalyst).
From the screening carried out, three catalysts (NaOH, MnCl
and
CoCl ) were selected for study the influence of the catalyst to almond
shells ratio, using the AFPA. An increase of some yields has been observed
when increasing the amount of catalyst impregnated at 440 2 C. With NaOH
(3.7 g of NaOH/100 total g of almond shells+NaOH), the yield of hydroxyacetone is 1.3%. With MnCl
(14 g MnCl /100 total g) and with CoCl
(13.5
g/100 total g ) , the yields of acetic acid and 2-furaldehyde are about 78%.
CoCl was selected for the study of the pyrolysis in the fluidized bed
reactor, Because this catalyst allowed a better control of the homogeneity
of the impregnation step due to the blue color acquired by the dried almond
shells impregnated previously with CoCl .
Table II shows the results obtainea in a series of experiments carried
out at 500 2 C in a fluidized bed reactor and with different catalyst to
almond shells ratios, including the results corresponding to almond shells
without catalyst.
A similar variation of the composition of the liquids obtained, compared to that obtained in the test of catalyst selection can be noted. Acetic
acid yield was around 7% when using CoCl , as compared with 9.8% when pyrolyzing without catalyst. On the other hand, 2-furaldehyde yields increased
up to 7.5% (at 14.1% of CoCl ) when increasing the catalyst to almond
shells ratio, as compared to 0.57% when no CoCl was used. Due to this,
the amount of organic liquids analyzed increased up to 16.9% when almond
shells were impregnated with 14.1% of CoCl .
A slight increase in the water yield due to the presence of CoCl
can also be noticed, although this yield remains almost constant when increasing the catalyst/almond shells ratio. With respect to the rest of
the components analyzed, the absence of compounds such as acetaldehyde,
hydroxyacetone, isoamyl alcohol and l-hydroxy-2-butanone, and an increase
in the yields of methanol+formaldehyde, acetone, 2-propanol and propionic
acid, are notable when pyrolyzing with 14.1% of CoCl .
This liquid distribution is typical of the acidic catalysts, since
the latter favour the dehydration reaction versus the fission reactions
233
(10). Furthermore, we observed a decrease in tar yields (dry residue at
120 ? C ) , which is also typical of this type of catalysts (11, 12).
With regard to the gases, no significant variation in the composition
of the gas obatined was observed. Nevertheless, a decrease in the yield
of gases as well as an increase in the solid residue yield can be noted.
In order to study the influence of the temperature a series of experi
ments at 410, 425, 445, 470, 500 and 610 = c was carried out with almond
shells impregnated with 14.1% of CoCl . Table III shows the operating con
ditions and the results obtained in this series of experiments. The follow
ing can be observed:
A
decrease in solid residue occurs when the temperature is
increased, but the drop is not as marked as that observed when pyrolyzing
without catalyst (1). This fact may be due to two opposing effects. On
one hand, the solid decomposition occurs to a greater extent when the tem
perature is increased but the presence of CoCl
favours the reactions of
condensation leading to the formation of carbon flO).
The liquid fraction remains almost constant within the 425610 S C
temperature range, probably due to the fact that the primary reactions
are almost completed, and to the small residence time which produces almost
no decomposition of the condensable volatiles.
With respect to the liquids analyzed, it can be observed that the
yield of acetic acid decreases by 30% at 500 sc when using CoCl , whereas
the yield of 2furaldehyde increases up to 1000% within the 425610 S C
temperature range, when using CoCl . Thus, when pyrolyzing almond shells
impregnated with CoCl at 500 *C it is possible to obtain a yield of acetic
acid around 7.2%. This is similar to values obtained by other researchers
working with other biomass without catalyst. Goldstein (8) reported around
7% from hard wood while Beaumont and Schwob (5) obtained around 7.84% from
beech hardwood. In addition, a yield of 7.5% of 2furaldehyde, which is
very high for a pyrolytic process and similar to that obtained by the con
ventional methods used for obtaining this compound by acid hydrolysis of
lignocellulosic materials can be obtained by using CoCl as catalyst.
Total recovery of the CoCl , from the charcoal formed at 445 sc, is
achieved by extraction with a solution of HCl under the following condi
tions: concentration of HCl lmol/L, extraction time 17 h, ratio g extrac
tant solution/g charcoal 33 and temperature 46 sc.
From the kinetic study carried out in the 410500 ? C temperature ran
ge, with almond shells impregnated with CoCl
(14.1%), the following ex
pressions for the firstorder reactions of tne scheme II previously pre
sented have been obtained:
k =8.93exp(13.29/RT) s _ 1
k2=0.097exp(4.28/RT) s 1
k3=0.0055
s1
(R in kcal/molSK)
C. HIGH TEMPERATURE. ALMOND SHELLS NO IMPREGNA TED

By high temperature pyrolysis around 820900 =C the following yields
(% weight) have been obtained (2): 0.7 1.6%H , 2546% CO , 1528% CO ,
58.6% C H , 0.70.8% C H , 2.34.2%C , 0.060.09% C H , 0.91.2% CH^,
6
0.30.5% C ^ 2 , 0.440.60% ^hydrocarbons* 47. 588.0% Tolal gas.
Most of the gas produced is formed by secondary reactions correspond
ing to the cracking of tars in the hot zone of the reactor on the fluidized
sand bed (residence time of volatiles around 12 s ) .
On the other hand, by pyrolysis of the dry residue at 890 sc (obtained
from the tar produced in the pyrolysis of almond shells at 610 sc, by dis
tillation up to 120 sc), the following yields in gaseous products are ob
Table I.
Constant temperature pyrolysis results
Temperature
Solids
Liquids
acetic acid
2-furaldehyde
water
methanol+formaldehyde
acetone
2-propanol
hydroxyacetone
l-hydroxy-2-butanone
3-methyl-l-butanol
propionic acid
acetaldehyde
dry residue at 120 2C
Gases
CO
CO
CH
H
4
2
Total
*acetone+2-propanol
365
400
420
425
440
440
460
495
495
495
610
710
69.2
21.1
54.2
36.3
47.0
41.4
46.8
41.6
29.4
57.0
30.6
52.0
27.5
56.0
26.4
58.5
26.3
57.2
26.4
59.3
11.3
65.1
6.7
43.2
0.42
0.77
10.6
3.2
0.045
16.6
3.5
0.46
16.4
4.0
0.5b
16.7
10.3
0.91
18.7
9.0
0.64
16.4
9.0
0.67
17.7
10.0
0.75
16.7
9.6
0.57
17.7
9.9
0.40
16.7
10.4
0.85
16.5
7.7
0.67
14.2
0.33
0.04
0.01
0.79
0.59
0.67
1.4
0.06*
1.0
0.14*
1.5
0.16*
0.92
0.12
0.06
2.1
1.1
0.44
0.49
0.06
24.1
13.1
9.0
3.8
0.37
1.3
0.26
0.18
1.4
1.1
0.77
0.28
0.56
0.08
0.05
1.9
1.4
0.41
0.10
0.10
27.0
14.4
10.2
3.6
0.61
1.1
0.07
0.06
1.9
1.3
0.90
0.17
0.21
23.0
15.7
10.3
4.7
0.70
1.2
0.06
0.04
1.7
1.2
0.78
0.15
0.24
26.1
14.3
10.0
3.8
0.50
0.70
0.25
20.6
13.3
9.0
3.7
0.47
0.09
1.1
0.25
0.33
1.5
1.2
0.81
0.33
0.01
22.3
14.2
9.9
3.6
0.61
0.10
1.8
1.3
0.46
0.18
0.10
34.5
22.9
10.6
10.7
1.6
0.58
0.17
0.04
1.4
0.66
0.22
0.26
0.16
18.1
53.2
13.3
34.5
5.4
0.23
99.6
95.9
97.7
99.2
99.2
100
99.2
7.9
5.3
4.4
0.90
0.04
0.88
0.40
0.26
0.10
0.92
0.52
0.33
0.13
0.85
0.50
0.41
0.15
13.0
8.1
6.0
1.9
0.13
0.09
18.0
8.3
4.8
2.9
0.36
0.15
16.4
8.6
4.9
3.1
0.44
0.15
95.6
97.3
96.7
95.1
103
Tables IIII
Influence of the CoCl to almond shells ratio. Yields (wt%) on moisture free almond shell
Catalyst
temperature
Solids
Liquids
Major compounds
acetic acid
2-furaldenyde
water
Minor compounds
methanol+formaldehyde
acetone
2-propanol
hydroxyacetone
3-methyl-1-butanol
propionic acid
acetaldehyde
dry residue at 120C
2-furaldehyde yield/added cation mol
Gases
COCO2
CH4
Total
CoCl (3.0%)
CoCl 2 (6.4%)
CoCl, (14.1%)
C
500
500
500
26.4
58.3
28.1
54.6
37.9
45.9
41.3
46.1
9.8
7.2
7.5
495
0.57
17.0
7.4
3.3
23.6
6.5
5.2
0.95
0.07
0.05
0.50
0.36
0.78
0.70
0.15
0.37
0.19
0.17
1.8
1.3
21.1
23.2
1.4
0.69
0.14
0.18
25.4
0.04
0.13
0.13
0.42
15.4
11.7
14.8
10.2
13.9
0.60
0.80
0.54
0.60
99.5
96.6
96.5
99.8
4.0
143
9.1
4.0
5.7
106
12.7
69.2
12.4
8.1
4.1
9.3
2.4
to
Table III
Influence of the temperature on the pyrolysis of almond shells impregnated with 14.1% of CoCl . Yields
(wt%) on moisture free almond shells. Fluidized bed reactor.
Temperature (aC)
Solids
Liquids
Major compounds
acetic acid
2-furaldenyde
water
Minor compounds
methanol+formaidenyde
acetone
2-propanol
hydroxyacetone
3-methyl-l-butanol
propionic acid
acetaldehyde
dry residue at 120SC
Gases
CO
CO
H
Total
*acetone+2-propanol
410
57.0
34.6
425
46.3
42.8
445
45.2
42.3
470
44.7
42.1
500
41.3
46.1
610
24.8
42.8
3.7
6.1
19.4
5.8
7.7
22.7
5.5
6.9
23.2
5.5
6.9
24.2
7.2
7.5
23.2
6.4
7.2
21.5
0.61
1.3
0.13
0.07
1.0
0.14*
0.69
0.18
0.08
1.4
0.19
0.17
0.34
0.24
0.35
0.09
0.07
0.42
0.44
4.8
4.4
4.1
0.23
0.05
0.03
5.1
6.7
5.3
1.1
0.33
0.02
4.2
7.5
5.0
2.0
0.41
0.09
4.5
7.7
4.8
2.3
0.45
0.14
5.7
12.4
9.3
2.4
0.60
0.16
6.3
26.7
17.5
7.8
0.86
0.55
96.0
95.8
95.0
04.5
99.8
94.3
to
\
237
tained: 0.88% , 20.9% CO, 22.8% CO , 6.1% CH , 0.37% C H , 3.0% C H ,
0.02% C H , 0.37% C H , 0.18% C and 0.1% C hydrocarbons. These yields
are expressed in wt% on a dry residue basis.
In order to study the influence of different catalysts on the hydro
carbon yields from high temperature pyrolysis, a set of experiments with
almond shells impregnated with different organic chemicals (NaOH, NaCl,
KCl, CaCl , BaCl , MnCl , ZnCl , CuCl , NiCl , CoCl , CrCl , NiS0 4 ) were
carried out using the A TPA '(Pyroprobe 100) at 850 ?C (2). A general de
crease can be observed in hydrocarbon yields with respect to the pyrolysis
of almond shells without catalysts. On the other hand, no significant chan
ge has been observed in the composition of the hydrocarbons.
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
Font, R., Marcilla, ., Verd, E. and Devesa, J. (1986) Fluidized

Bed Flash Pyrolysis of Almond Shells. Temperature Influence and Cata
lyst Screening. Ind. Eng. Chem. Prod. Res. Dev., 25, 491.
Font, R., Marcilla, ., Devesa, J and Verd, E. (1988) Gaseous Hydro
carbons from Flash Pyrolysis of A lmond Shells. Ind. Eng. Chem. Res.
27, 1143.
Verd, E. (1988) Thesis Dissertation. Pirlisis de Cascara de Almendra.
Universidad de Alicante.
Scott, D.S. and Piskorz, J. (1984)The Continuous Flash Pyrolysis of Bio
mass. Can. J. Chem. Eng., 62, 404.
Beaumont, 0. and Schwob, Y. (1984) Influence of Physical and Chemical Pa
rameters on Wood Pyrolysis. Ind. Eng. Chem. Process Des. Dev. 23, 6377
Finney, C S . and Garret D.E. (1974) Flash Pyrolysis of Solid Wastes. E
nergy Sources, 1, 295.
Sass, A. (1974) Garret's Coal Pyrolysis Process. Chem. Eng. Prog., 70,
72.
Goldstein, I.S. (1981) Organic Chemicals from Biomass. CRC. Boca Raton
Fl., Chapter 5.
Thurner, F. and Mann, U. (1981) Kinetics Investigation of Wood Pyroly
sis, Ind. Eng. Chem. Process Des. Dev., 20, 482.
Shafizadeh, F. (1975) Industrial Pyrolysis of Cellulosic Materials, Ap
plied Polymer Symposium, John Wiley & Sons, 28, 153.
Smicek, S. and Cerny, C.T. (1970) Active Carbon, Elsevier Pubi. Co.,
Amsterdam.
Gray, M.R., Corcoran W.H. and Gavalas, G.R. (1985) Pyrolysis of a Wood
Derived Material. Effects of Moisture and Ash Content, Ind. Eng. Chem.
Process Des. Dev., 24, 646.
238
BIOMASS PYROLYSIS IN MOLTEN SALTS FOR FUEL
PRODUCTION
J.K.Maund and D.M.Earp
Department of Chemical Engineering & Applied Chemistry,
Aston University, Birmingham, B4 7ET, United Kingdom.
SUMMARY
Molten alkali metal salts are recognised as having considerable potential as
high temperature liquid phase media lor the pyrolysis, gasification,
combustion and catalytic conversion of organic chemicals. A two litre
capacity molten salt system for the pyrolysis of biomass is described. The
heating rate of wood, in both air and molten salt, has been studied and
compared, and has been found to be between four and ten times faster in
molten salt. The pyrolysis of wood in both molten Li/Na/K carbonate and
Na/K hydroxide eutectics has been studied and the results of these studies
are presented. The hydroxide melt system is favoured as it produces good
purity hydrogen. However, the melt system becomes contaminated with
carbonate and organic residues and the hydroxide, being consumed,
requires regeneration; preliminary studies indicate this to be feasible.
1.
INTRODUCTION
Molten salt processes are already well established, particularly in the
metallurgical industry, where they are used for thermochemical and heat
treatment and for cleaning (1). More recently, molten alkali metal salts, in
particular, have been recognised as having considerable potential as high
temperature, liquid phase media for the pyrolysis, gasification, combustion, or
catalytic conversion of organic materials such as biomass, coal and a variety of
waste products. A number of examples, from laboratory scale to demonstration
plants, have been developed throughout the world for coal gasification (2)(3)(4);
biomass and waste gasification (5) and combustion (6); and plastics pyrolysis (7).
Fused metal salts as reaction media for the thermal conversion of biomass
have a number of advantages over conventional gas phase processes:
(i) Chemical stability in the liquid phase at temperatures up to 1000C;
(ii) Appropriate physical properties of high thermal conductivity, low
viscosity, low volatility, and appropriate melting point temperature;
(iii)The ability to dissolve biomass into the liquid phase, so that heat and
mass transfer become homogeneous and, therefore, very rapid;
(iv)The possibility of homogeneous catalysis or chemical reaction to control
the chemical composition of the products.
The Department of Chemical Engineering and Applied Chemistry at Aston
University has been carrying out a 2-year contract with the European Community
continuing its research into thermal processing of biomass in molten salts (8)(9).
This paper summarises the experimental work performed to date within the
contract . Molten salt processing has been studied for some ten years in the
Department, and biomass conversion for almost as long, with the thermochemical
processing of biomass in molten salts first being studied in 1980 (10).
239
2.
EXPERIMENTAL EQUIPMENT
The experimental equipment has been described in detail before (11)(12). It
consists of a two litre capacity stirred tank reactor into which the biomass is fed by
a sealed laboratory scale screw feeder. Vapour leaving the reactor is cooled by
water-cooled heat exchangers which condense the liquid products, which are
then collected for analysis. The product gas is burned in a flare. The reactor is
heated by a purpose built 3 kW electric resistance furnace, with a three-term
electronic temperature controller.
The product gas composition is continuously monitored for H2, CO, CO2 and
CH4 using dedicated gas analysers and recorded, at about 10 second intervals,
by a micro-computer based data-logger, developed within the Department for
use with an open-core downdraft gasifier (13). Reactor pressure is measured
using a water manometer, product gas flowrate by rotameter and total volume of
gas produced by gas meter; these variables, along with the temperature of the
salt bath, are recorded manually.
To prevent the ingress of air into the system and to provide a 'carrier' for the
gas analysis system, the rig is operated with a nitrogen purge. This purge is
introduced at three points, the stirrer, the feeder and the reactor, the flow of each
being metered separately.
3.
EXPERIMENTAL WORK
The experimental work so far performed has covered three main areas,
particle heating rate tests, pyrolysis in the molten lithium/potassium/sodium
carbonate eutectic and pyrolysis in the potassium/sodium hydroxide eutectic.
3.1 Heating Rate
Before the experimental rig was finally piped up and closed, a number of
experiments were carried out, firstly to commission the furnace and its
temperature controller, and secondly to investigate the heating rate of wooden
dowels of different sizes in molten salts at different temperatures and to compare
these with rates in air at the same temperatures. These experiments were to
enable the relative heat transfer characteristics of the two media to be evaluated.
In order to obtain a reasonable range of temperatures for this work, the
sodium/potassium hydroxide eutectic (51 mole % KOH/49 mole % NaOH, melting
point 193C) was used, allowing a temperature range of 250 to 500C. However,
because of the risk of combustion the runs in air were only performed at 250C.
Dowels of 6, 9,12,15 and 22 mm diameter were used, each cut to a length equal
to its diameter. The temperature at the centre of the dowel was monitored by
drilling a small hole into the centre and fitting it with a chromel/alumel type
thermocouple. The temperature history was recorded using the data logging
system at frequencies of up to two readings per second. When the dowel
temperature had reached the furnace control temperature, it was removed from
the furnace.
3.2 Pyrolysis In Molten Alkali Carbonate Eutectic
For the initial pyrolysis runs, it was decided to employ the Li/Na/K carbonate
eutectic (43.5 mole % IJ2CO3/31.5 mole % Na2CO3/25.0 mole % K2CO3, melting
point 397C) as this was both non-corrosive and had been used successfully in
tyre and plastics pyrolysis at Aston (14)(15). A salt temperature of 500 C was
chosen,as this was the midpoint for the proposed experimental programme range
(12). To prevent "overloading" of the melt, a low feed rate was selected. This was
initially about 8.4 g/min continuous feeding, although due to operational
240
difficulties (see Section 4), was later reduced to a rate of 4.9 g/min in one minute
cycles (1 minute on/1 minute off). The feed material used consisted of in-house
manufactured pine 'chips' (without bark) sieved to the size range 0 to 4.75 mm.
3.3 Pyrolysis In Hydroxide Eutectic
As a result of difficulties encountered with the carbonate eutectic (see
Section 4), it was decided to employ an alternative salt system. Previous
experience at Aston (15) and simple solubility tests indicated that the K/NaOH
eutectic, as used in the heating rate experiments (see Section 3.1 above), was a
solvent for wood, so it was decided to employ this salt. The bath temperature was
set at 300C. This temperature was chosen as it was about the midpoint of the
solubility range for wood, this range of temperatures having been identified in a
series of simple solubility tests. A low feed rate of 4.9 g/min was selected in
order to prevent "overloading" of the salt, with the feeder being operated both
continuously and semi-continuously, as in the carbonate runs. The same feed
material as for the carbonate runs was employed.
4.
RESULTS AND
DISCUSSION
4.1 Heating Rate

A summary of the results of the heating rate work is presented in Figure 1.
These show that the particle heating rate in the molten salt was, as anticipated,
more rapid than in a gaseous environment. The heating rates measured in
molten salt were between four and ten times faster than those measured in air.
This is in close agreement with the results of Tada and Yasunishi (16)(17) of
Tottori University. It was also observed that in the alkaline melt the cellulose core
of the wood was dissolved leaving a honeycomb-like structure of lignin.
4.2 Pyrolysis in Molten Alkali Carbonate Eutectic
Each run performed with this system had to be terminated after
approximately 20 minutes due to a 'back-up' of feed in the feed inlet pipe up to
the feeder. On each occasion when the rig was stripped down after a run, it was
found that the surface of the melt was covered in a layer of char. On top of this
char layer there were layers of progressively less pyrolysed feed, until in the
feeder tube itself, fresh unreacted feed was found. Initially, it was felt that either
the feed rate was too high for the salt system and was therefore 'overloading' the
melt or there was insufficient agitation to provide adequate mixing of the salt and
feed. However, when these problems persisted at high agitation rates and low
feed rates, it was concluded that the molten salt was merely acting as a heat sink
causing the biomass to undergo conventional pyrolysis without any solution. This
theory was supported by simple solubility tests. Calculations based on previous
pyrolysis work at Aston (19) indicated that both the rate of pyrolysis and particle
heating rate were rapid at the conditions prevailing in the reactor.
It was decided that the carbonate salt system was unsuitable for the present
reactor arrangement when operating in the pyrolysis mode. However, it was
concluded that it could be operated as a gasifier, but such a study does not lie
within the scope of this project.
241
10
15 mm Air
15 mm Salt
12 mm Salt
10 u
20
40
60
80
100
% Ultimate Temperature
Figure 1 Dowel Heating Times in Air and Molten Salt

The products formed in the runs using the carbonate melt system were
typical of conventional pyrolysis and, as well as the char consisted of:
a thick smoke of fine tar particles. This was difficult to condense and to
disentrain from the gas stream. However, some was disengaged from the
gas, both in the condensers and the gas rotameter, and proved to be
reasonably fluid and readily soluble in acetone.
gas, at very low yields, this consisting primarily of CO and C0 2 (up to 95 %),
the balance being CH 4 and H2.
As some of the feed material added to the reactor was only partially
pyrolysed the mass balances and product yields could not be calculated.
4.4 Pyrolysis in Hydroxide Eutectic
A number of successful runs, of up to one hour in duration, have so far been
performed using a hydroxide melt system. In this case the wood fed to the reactor
dissolves in the melt to yield gaseous, liquid and solid products.
The gaseous product formed, consists of approximately 98% hydrogen, the
balance being mainly methane. The gas evolution was vigorous and resulted in
the melt foaming, with a volume increase of approximately 25%. This foaming
caused a blockage in the gas outlet line, due to frozen melt, which required minor
redesign (11) to prevent its recurrence.
The liquid product formed, consists of 97-99% water, the balance being an
organic product, which, due to its low yield and concentration, has not yet been
identified. This liquid is also alkaline, probably due to droplets of hydroxide
entrained in the product gas which dissolve in the condensate. The gas and
liquid products formed are very similar to those found in previous work at Aston
on small scale batch pyrolysis and solution of wood in molten hydroxides (10).
242
The work of I rdale and Hatt (10) also showed that the composition of the product
gas and the yield of gas were strongly dependent on the melt temperature. This
is currently under investigation to determine the optimum operating temperature.
The majority of the carbon in the feed is not liberated as part of the gaseous
or liquid products, but is retained in the melt either as an organic residue, which
may consist of formate or ethanoate ions (10), or by reaction with the hydroxide to
form carbonate. Melt with these 'impurities' is known as 'fouled'. Figure 2
illustrates the effect of the amount of wood pyrolysed on the hydroxide and
carbonate levels in the melt. The colour of the melt and of its aqueous solution,
also vary with the quantity of wood pyrolysed. Colours vary from that of the fresh
melt (which is white when solid and colourless when liquid) with a colourless
solution, via a pale yellow, of melt and solution, to a dark brown coloured melt
and solution. The light absorption, of the solution is directly proportional to the
quantity of wood pyrolysed, with a characteristic absorption at 260 nm. The
colouring of the melt is probably due to the organic residue, although the fraction
of this residue in the melt has not, as yet, been reliably quantified.
40
SP
'
30-
20
3 10
100
200
300
400
Wood Added (gramme)
Figure 2
Hydroxide and Carbonate Content of Melt

Against Weight of Wood Pyrolysed
High levels of carbonate and organic residue in the melt lower its
effectiveness as a reaction medium. The hydrogen yield drops as more wood is
pyrolysed (see Figure 3) and the melt becomes more fouled. There is also
evidence to suggest that the wood solution becomes saturated, this being shown
by filtration of an aqueous solution of the melt. When small quantities of wood
have been pyrolysed (less than 50 g wood/ kg of melt) little or no solid filtrate is
produced. However, as the quantity of wood pyrolysed increases, a filtrate of fine
char particles is obtained, the number and size of these increasing with the
quantity of wood pyrolysed.
243
350
4>
300
e
3
5
250
s
MD
>>
s
200
100
200
300
400
Wood Added (gramme)
Figure 3 Hydrogen Yield A gainst Weight of Wood Pyrolysed

This phenomenon indicates that the solution of the wood is being inhibited, so it
pyrolyses, with little or no solution, leaving a char residue.
In order to utilise the same melt in a continuous process, it would be
necessary to regenerate the melt, for instance, by reaction with steam (20):
CO3" (I) + H 2 0 (g) ^
OH" (I) + C0 2 (g)
Attempts to carry out this reaction in the molten salt at up to 750C with a
water partial pressure of 0.3 bar showed it to be very slow. There is, however,
evidence that it takes place in the presence of live steam at a somewhat higher
temperature. This is an area for further investigation.
It has already been shown that the melt may be partially regenerated simply
by heating. Fouled melt was heated to a temperature of 400C and yielded a gas
containing hydrogen and methane. This gas production was considered to be
due to the breakdown of the organic residue in the melt.
Hatt and Iredale (10) suggested the following overall reaction for wood in the
molten hydroxide eutectic:
C 6 H 9 0 4 (wood) + 12 OH" + 2 H 2 0
6 C o f * 12.5 H 2
However, this is a simplification of the process and the range of products

indicates that the actual process is more complicated. A more realistic appraisal
of the reactions occurring may be represented by the routes they proposed for the
molten salt pyrolysis of cellulose (see Figure 4). A gain, however, this is a
simplification, as it does not consider the other main constituents of the wood (that
is lignin and hemicellulose). The range of products formed could be explained
by considering the breakdown of these other components and, in particular.lignin.
244
Cellulose
i
I
S ace hari ic Acids1,2 - epoxides

'poxioes
6 CO + 6 H 2
shift
12 H 2 + 6 CO~
5 CO + C H 4 + 3 H 2
I shift
5 C0|"+ C H 4 + 8 H 2
< 6C
6 C FF lragments
11pyrolysisJ
H 2 / CO"
Figure 4 Proposed Routes for the Pyrolysis of Cellulose in

Molten Sodium/Potassium Hydroxide (10)
5.
CONCLUSIONS
There is considerable evidence that molten salts are potentially valuable
media for the conversion of biomass into useful fuels and chemicals. The work
performed in this project and by other groups has demonstrated the technical
feasibility of this type of process.
The salt employed has been demonstrated to have an important influence
on the process and hence the products. The salt type determines whether it acts
simply as a heat source or as a chemical reagent. Previous work at Aston (21 )
has demonstrated the use of molten salts as liquid phase catalytic reaction
media. It should, therefore, be feasible to select a suitable salt and catalyst
system to produce specific products.
The sodium carbonate melt acts as a heat source causing the wood to
undergo 'normal' pyrolysis, although at higher heating rates than conventional
pyrolysis systems which employ a gaseous heating medium. The suitability of
this system for gasification and combustion has already been demonstrated, its
particular advantage being its ability to absorb contaminants, such as sulphur.
The hydroxide melt system produces hydrogen of high purity and, therefore,
has considerable potential to provide hydrogen either as a fuel gas or as a
chemical reagent, for instance for the upgrading of pyrolytic oils. A potential
problem of this salt system is the fouling of the melt, with carbonate and an
organic residue, requiring the melt to be regenerated. However, there is
evidence to suggest that this may be feasible by reaction of the fouled melt with
steam. Partial regeneration of the melt to recover hydrogen and methane by heat
treatment has already been demonstrated. This heat treatment is believed to
drive off the organic residue remaining in the melt.
245
REFERENCES
(1) Anon., "Guidelines for Safety in Heat Treatment - Part 1 Use of Molten Salt
Baths", The Wolfson Heat Treatment Centre, Aston University B'ham, (1981)
(2) Chong V M, "Coal Gasification Process", US Patent 3 770 399, (Nov. 1983)
(3) Susie M et al., "Coal Gasification in Molten Salt", Glas Sriska Akademija
Naukai Odelene Prirodus Matematickih 48 (1981) 27.
(4) Cover A E & Schreiner W.C., "The Kellogg Molten Salt Process", Energy
Communications 1/2, (1975) 135.
(5) Yosim S J & Barclay M, "The Gasification of Wastes Using Molten Salts",
Preprint, ACS Division of Fuel Chemistry 21/1 (1976), 73.
(6) Moffat J M & Kohl A L, "Gasification of Wood in a Bath of Molten Alkali
Carbonates", in "5th Canadian Bioenergy R&D Seminar", ed. Hasnain S,
Elsevier Applied Science (1984).
(7) Bertolini G E & Fontaine J, "Value Recovery from Plastics Waste by Pyrolysis
in Molten Salts", Conservation & Recovery 10/4 (1981) 27.
(8) Maund J K, Bridgwater A V & Smith E L,"Thermal Conversion of Biomass in
Molten Salt Media",'Energy from Biomass 1', G Grassi & H Zibetta (eds),
Elsevier Applied Science, London (1987)
(9) Maund J K, Bridgwater A V & Smith E L.'Thermal Conversion of Biomass in
Molten Salts", '4th EC Conference - Biomass for Energy & Industry', Orlans,
France, (May 1987)
(10) Iredale PJ and Hatt BW, "The Pyrolysis and Gasification of Wood in Molten
Hydroxide Eutectics", in, "Fundamentals of Thermochemical Biomass
Conversion", Overend RP, Milne TA an<-" iVludge LK (eds), Elsevier Applied
Science, London (1985).
(11) Earp D M and Maund JK, "Thermal Conversion of Biomass in Molten Salt
Media", Third EEC Progress Report - January to September 1988.
(12) Earp D M and Maund JK, "Thermal Conversion of Biomass in Molten Salt
Media", paper presented at, "Energy from Biomass - EEC Contractors
Meeting", Paestum, Italy (1988)
(13) Earp DM, "The Gasification of Biomass in a Downdraft Reactor", PhD Thesis,
Aston University (1988)
(14) Venning NJ, "Fuels from Tyres by Pyrolysis in Molten Salts", PhD Thesis,
Aston University, (1981)
(15) Pitt MJ, "Pyrolysis of Plastics in Molten Salts", MPhil Thesis, Aston University,
(1979)
(16) Maund JK and Earp D M, "Fuels from Biomass by Conversion in Molten
Salts", pp. 542-556 "Research in Thermochemical Biomass Conversion",
eds. A V Bridgwater & J L Kuester, Elsevier Applied Science, (1988)
(17) Yasunishi A & Tada Y, 'Wood Pyrolysis in Molten Salt', Kagaku Kogaku
Ronbunshu, 11/3, (1985) 346.
(18) Tada Y & Yasunishi A, 'Wood Pyrolysis with Molten Salt as Heating
Medium', Kagaku Kogaku Ronbunshu, 13/3, (1987) 376.
(19) Smith EL, Private Communication
(20) Maund JK, "Thermal Conversion of Biomass in Molten Salt Media", paper
presented at Institute of Energy Conference: "Gasification - Status and
Prospects", Harrogate, UK, (May 1988)
(21) Al-Muslih E F, "Oxidation of Organic Compounds in Molten Salts", PhD .
Thesis, Aston University, (1984)
246
FLASH-PYROLYSIS OF SULCIS COAL
L. Conti and G. Scano
Dipartimento di Chimica, Universita1 di Sassari
Summary
F l a s h - p y r o l y s i s of an i t a l i a n c o a l ( S u l c i s c o a l ) has been
i n v e s t i g a t e d in
f l u i d i z e d bed p y r o l i s e r in n i t r o g e n or
methane a t m o s p h e r e and between 600 and 900 C. The
maximum t a r y i e l d s i s o b t a i n e d a t 600-620
C. The
p y r o l y s i s o i l can be upgraded a f t e r w a r d s . Experiments i n
methane a t m o s p h e r e s u p p o r t a p o s s i b l e r a d i c a l i c mechanism
for t h e r e a c t i o n .
1. INTRODUCTION
Continued reduction of crude oil and natural-gas reserves
stimulates the interest of many research groups in coal
conversion to gaseous or liquid products, which can represent
new raw material for the chemical industry.
In our laboratory, research on the utilization of Sulcis
coal as an alternative to direct combustion was started a few
years ago 1 - 2 ; in this connection, we began to study fluidized
bed flash-pyrolysis of this coal.
In the present communication, we report some of the
results obtained in this research.
2. RESULTS AND DISCUSSION
Pyrolysis experiments were conducted in a fluidized bed
stainless steel pyrolyser able to heat coal powder at 10^
C/sec with short residence time (0.3 sec)3. in this way, the
tars undergo only a partial decomposition and can be quickly
removed.
Table 1 reports the approximate and ultimate analysis of
Sulcis coal :
Tab. 1 Analysis of Sulcis coal
Proximate analysis
Moisture (wt%)
7.4
Ash (wt% mf)
10.9
Volatile matter (wt% mf) 45.3
Fixed carbon (wt% mf)
43.8
Ultimate analysis
C (wt% maf)
68.2
H (wt% maf)
4.8
(wt% maf)
1.7
S (wt% maf)
8.7
Fig. 1 reports the yields of total volatile matter, tar,

gas and hydrogen sulphide against temperature in nitrogen
atmosphere; Fig. 2 reports the tar-component yields (A STM
247
A
O
Hydrogen sulfide
C1-C3 hydrocarbons
Tars
Volatile matters

soo
eoe
9oa
IDOO
F i g . 1. Trends of product y i e l d s versus p y r o l y s i s temperatures
BOO
eoo
TOO
eoo
900 1000
F i g . 2. Yields of l i g h t o i l s and c a r b o i d s v e r s u s temperature
248
270075), relative to the original coal, plotted against
temperature.
As can be noted, a maximum tar yield is obtained at
600620 C; the pyrolysis oil presents a satisfactory H/C
ratio and sulphur content and can be upgraded afterwards''.
The characteristics of the tar obtained at 600 C and the
composition of gaseous hydrocarbons are listed in Tables 2 and
3.
Tab.
Characteristcs of tar
C
(wt%)
75.2
H
(wt%)
7.7
(wt%)
1 .0
S
(wt%)
3.6
Asphalt.
(wt%)
41.2
Preasphalt.. (wt%)
32.3
H/C
1 .2
The trends ob served in
mechanism : 3
Tab. 3 Hydrocarbons C|Cz,

CH4
C2H4
C2H6
C3H6
C4H8
C2H2
Fig.
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)
(wt%)
suggest
the
30.5
26.7
9.5
22.8
10.5
traces
following
ils ^^
primary light oils
^ ^ ^ second ary gas
sem icoke ^~
^ residue
carboids ^
Coal
secondary light oils
primary gas
chars
The coal decomposes essentially with a radical mechanism.
The volatiles formed include unreactive substances as well as
reactive ones (carboids). Especially in the intial stages of
decomposition, when free radicals are likely to exist, the
unreactive volatiles (primary light oils and gases) escape
into the atmosphere. Only a part of the reactive volatiles
escape, while the most of them polymerize giving a semicoke;
or decompose into secondary light oils.
In turn the semicoke reacts to gives gas and a solid
residue. The breakdown of the primary light oils, and of the
secondary
ones perhaps, is noticed
at higher
pyrolysis
temperatures (600750 * C ) , as well as an increase in carboids.
The decrease of carboids in the oil produced at 900 C can be
explained by quick decomposition.
A further check of the validity of such mechanism was
provided
by some tests carried out in methane atmosphere. In
our experimental temperature range, methane cracking gives a
high concentration of free radicals5. These react with the
radicals deriving from coal pyrolysis, particularly with the
carboids that are thus quenched, hindering their decomposition
into semicoke and secondary light oils.
Infact,
we
observed
a greater
tar
production
but
especially a variation in composition (light oils/carboids
ratio) in methane than nitrogen atmosphere, as we can be see
249
in Tab. 4.
Tab. 4 Tar
m.a. f. )
yields
at
450
Temp .
N2
Tar
Light oil
Carboid
Light oil/carboid
different
temperatures
600
CH4
13.5 8.7
6.8 3.6
6.7
5.1
1.01 0.70
N2
CHz,
19.521.0
5.0
4.1
14.5 16.9
0.3 0.24
(wt
on
880
750
N2
coal
CH4
15.2 20.2
2.0
1.8
13.2 18.4
0.15 0.10
N2
CHz,
10.8 11.9
4.6
1.5
6.2 10.4
0.74 0.14
References
(1) C. Botteghi, L.Conti and R. Mansani, Boll. Soc. Sarda
Sci. Nat.; 19, 27 (1980)
(2) L. Conti, C. Botteghi and R. Rausa, Tecnologie Chimiche,
4, 38 (1981)
(3) L. Conti and R. Rausa , Fuel Processing Technology,
17, 107 (1987)
(4) S.C. Che, S.A. Quader and E.W. Knell, in "Refining of
Syntetic Crudes". M.L. Gorbaty and B.M. Harney, Editors,
Am. Chem. Soc. Washington, D.C. (1979)
(5) D.B. Anthony and J.B. Howard, AICHE Journal; 22, 625
(1976)
250
RAPPORTEURS REPORT ON SESSION IV
D J O'Neil
Georgia Tech Research Institute
Atlanta
Georgia 30332
USA
Session 4 (Pyrolysis Case Studies) consisted of five papers, with two papers
withdrawn. The Session was chaired by Dr G Grassi assisted by Dr A V
Bridgwater.
1.
Sugars from Cellulosics by the Waterloo Fast Pyrolysis Process

Dr Piskorz
Dr Piskorz of the University of Waterloo (Canada) reported the experimental
results achieved for the production of anhydrosugars and other sugars via
atmospheric flash pyrolysis in a fluidised bed reactor. Pretreatment of the
lignocellulosic feedstocks was a preferred method prior to pyrolysis in order to
maximise the conversion of the cellulose fraction to fermentable sugars.
Conversion efficiency of cellulose to fermentable sugar of 72% was reported.
Sugars were isolated in a water-soluble extract of pyrolyzate with the non-watersoluble fraction producing a "pyrolytic lignin" fraction. Pretreatment with dilute
sulphuric acid had yielded hemicellulose derivatives. Success was claimed in
fermenting the sugar solution to ethanol but no details were provided on
conversion efficiency, ratio, or the need to acclimatise fermenting agents (e.g.
baker's yeast).
A question addressed the method of analysis/characterisation which was
used to identify laevo-glucosan which had been cited as a key pyrolysis product. It
was understood that, while l-glucosan had often been cited as a precursor to
formation of cellulose, it had often escaped detection, at least in earlier studies on
the structure of cellulose. Dr Piskorz explained that, while GCMS and FTIR were
methods of analysis that could be used, he had used standard samples of glucose
(and other sugars) and had used HPLC to correlate the elution times of the
standards with the pyrolysis components. Some of the sugar standards were also
synthesised in his laboratory and were used for HPLC correlation. Additionally, the
l-glucosan was isolated, converted to glucose via hydrolysis and the glucose
product was fermented to ethanol.
The question was raised of the cost of production of sugars via the flash
pyrolysis process in relation to the citation that Brazilian studies had been
unsuccessful in producing sugars from lignocellulosics at competitive rates. Dr
Piskorz replied that they had estimated the cost of sugar production via the
pyrolysis process to be $0.10-$0.15/kg. It was noted that current costs of raffinate
sugars were $0.06-$0.08/kg and that his results were not attractive. Dr Piskorz
cited the fact that he was reporting experimental results and that his costs were
preliminary.
It would appear that the production of fermentable sugars would be at a
disadvantage vis-a-vis the well-established prehydrolysis and dilute hydrolysis
processes which have been developed in the 1980's which retain a higher yield of
fermentable sugars and low levels of toxifying compounds and for which hexose
251
production costs have been reported at $0.07-$0.08/kg. The Waterloo researchers
claim only an advantage over enzymatic hydrolysis which has the greater potential
for maximal production of fermentable sugars from both the hemicellulose and
cellulose fractions assuming further reductions in conversion times. Several
questions remain to be answered before a cost-effective biomass conversion
process could be economic: cost of acid, disposal of acid solutions, degradation ol
hemicellulose and loss of volatile derivatives (furfural-based), fermentation
inhibition (furural, hydroxymethyl furfural, phenols, etc), mass market for "pyrolytic
lignin" residues etc.
2.
Production of Benzols and Active Carbon by Pyrolysls with

Simultaneous Post-cracking of Waste Rubber and Plastic
Material
Dr B Bettens
Dr Bettens reported on a "dual pyrolysis" process for the conversion of waste
tires (rubber) and plastics, with emphasis on the former - a whole tire pyrolysis
process involving two pyrolytic stages, viz (i) depolymerisation (actually
decomposition since a monomer is not the primary product) at a temperature range
of 400-500C, and (ii) a higher temperature cracking process at 700-800C. Olefin
production is characteristic of the first stage and "aromatisation" to BTX (benzene,
toluene xylene) production is characteristic of the second stage. Bettens reported
mass balance and temperature dependence for the principal product groups, i.e.
solid (char), liquids and gases. The liquid phase composition could include 6070% of BTX compounds (naphthalene and higher fused aromatics could be
observed). A simple depolymerisation and aromatisation reaction mechanism was
presented. The effects of temperature and process conditions (including flow rate)
were examined on depolymerisation and BTX formation.
A feasibility study for a 2000 t/d plant (c.1984) was described and a plant
investment of BF 30.4 million was reported (22 million for capital equipment, 0.8
million for assembly, 0.6 million for electricity and 7.0 million for miscellaneous
costs). Raw material (waste tire) costs were reported as 1550 BF/ton (if collected and delivered?) or 600 BF if tires were "turned in" to the plant for payment by
individual delivery. Dr Bettens described a manufacturing process for a 2000 t/d
plant, critical elements of which were a "feed delivery" system for whole autombile
tires (no shredding required), a large first stage direct heating zone (major gaseous
volume expansion allowed), and a smaller adjacent cracking reactor zone.
Activation of carbon residue was cited as a saleable product.
Considerable questioning arose with regard to the practical operation of the
proposed plant. In particular, there was a question on the efficiency and the
method of direct heating and the problem of fouling of heating elements. A
situation was cited from the experience of one of the audience relative to an acute
fouling problem, due to rapid coking of electrical radiant heating elements in a
rubber pyrolyzer with loss of heat transfer and failure of the electrical system due to
overheating. Dr Bettens recapped the process with emphasis on the conveyor
transport system into and through the kiln which was claimed to allow adjustment of
the contact (residence) time, facilitating rapid reactions. They do not stress heat
transfer as being a problem in the first stage - "not a problem". Dr Bettens noted
that a scraping system was included in the design to remove scale (foulants). Pilot
tests had not been run which established the optimum "contact" time for the tires in
the kiln. A condenser system was described for both the first and second stages.
Further work was necessary to balance the take-off (two points) of light fractions
and heavy fractions. This was recognised as a problem. No information had been
252
produced to support the claim of activated carbon production. It was speculated
that a steam activation process would be used but that a subcontractor would be
needed to implement that operation. In summary, basic technical issues remain
before a reliable process is established and before reliable process economics can
be generated.
3.
Low Temperature Conversion of Biomass to Oil

Professor Bayer
Professor Bayer argues from both an experimental and theorectical
standpoint that, in contrast to conventional .widsom on biomass pyrolysis
technology, high carbon-hydrogen organic compounds of low oxygen content need
not only be achievable by high-temperature pyrolysis. Evidence was presented
that fatty acids and a series of aliphatic hydrocarbons (often associated with olefin
analogues) can be produced from biomass which is rich in lipids and proteins.
Sewage sludge, because of the high microbial content, was proposed as a
productive source of pyrolysis products in which C-C bonds would be retained
while heteroatoms (S, , O) may be readily eliminated. Reaction temperatures
were in a low range of 280-400C, with a precaution that temperatures in excess of
380C should be avoided, normally because of the potential conversion of organic
amides (RCONH2) to organic nitrites (or cyanide products) via dehydration.
A principal reaction pathway for formation of hydrocarbons was postulated
as involving conversion of glycerol at 280-330C to fatty acids, followed by
conversion of the factty acids to hydrocarbons via decarboxylation at 300-380C.
The limitation of boiling points of the pyrolysis products was such as to indicate
their practical use as diesel fuel replacements. Sewage sludge was a source of
raw "oil" at yields of 27%. The solid residue was usable as a fuel source for
dewatering. Of considerable interest was the observation that not only
heteroatoms, but also halogen atoms (CI,F), could be removed under non-oxidative
conditions in the presence of inorganic catalysts such as silicates.
One observer noted that the presence of water in the feedstock could modify
the catalyst. Bayer speculated on the role of catalysis and noted that over 200
catalysts had been assessed with the goal of maximising the yield of the higher
value-added olefins. Lipid-rich plants were desirable and easily manipulated. It
was apparent that the aliphatic-to-olefin ratio could be preferentially manipulated to
favour olefin production
To the suggestion that the low-temperature pyrolysis may be more
significantly applied to destruction of organic components, specifically hazardous
waste compounds, Professor Bayer emphasised that it is better, in any event, to
maintain the C-C linkage in the organic compounds, making the point that it was
very costly to build-up/synthesise higher molecular weight organic compounds,
from C-|- compounds, such as methane. He had not addressed the question of the
treatment of PCB compounds, only chlorinated dioxins.
When asked to explain how low oxygen content (3-5%) products were
realised at low and high temperatures, Professor Bayer postulated that his products
(with 85-95% the HHV of petroleum products) were a result of a different chemistry.
At higher temperatures he postulated the formation of stable intermediate products,
such as ketones, which could only be destroyed under the more extreme
conditions. At lower temperatures, the decomposition of carboxylic acids, on the
other hand, could be readily achieved via decarboxylation (-C02). Moreover, the
formation of methane (CH4), depleted the available hydrogen which would be
needed for extensive deoxygenation at higher temperatures.
253
Issues which remain on the practical implementation of the process include
process efficiency (dewatering energy requirements?), rate of reaction (20 minutes
preferred at small-scale), mass and heat transfer requirements, nature and
availability of uniform raw material (process design), cost and efficiency of
catalysts, cost of separation processes and refining to extract narrow fuel fractions,
etc.
4.
Chemicals from Almond Shells by Pyrolvsis in a F luidised Bed

Dr R F ort
The University of Alicante paper focussed on the results of pyrolysis in a
laboratory-scale fluidised bed reactor of impregnated almond shells, a biomass
waste product. The FBR was equipped with a comprehensive sampling train and,
assisted by chemical analysis, product yields and compositional data on oils and
gaseous products could be determined. The investigators report oil yields of 4658% with preferred particle sizes of 0.2-0.3mm.
Several variations on conversion approaches were investigated.
Post-pyrolysis of the dried oil residue, arising from pyrolysis at 610C and
subsequent distillation at 120C, when conducted at 890C yielded a "producer
gas" with high CO/C0 2 content (43%), 1% hydrogen, 6% methane and C 2 - C4.
The balance was not reported. The results correspond to the results of other
investigators.
In perhaps the most interesting aspect of the research the almond shells
were impregnated with acidic compounds yielding substantial quantities of furfural.
Since furfural is produced commercially from oat residues it would be informative to
compare yields under comparable conditions with almond shells to determine the
potential for economic production of furfural from the locally available biomass
resource. Is there a potential for development of an integrated multiple product
(furfural, pyrolysis oil) process which could use the oil, the product gases, or char
as a process fuel? A remaining technical problem, to be investigated, will be the
efficiency of acid impregnation since pore closure has been reported by other
investigators (Roy, Canada).
5.
Biomass Pyrolysis in Molten Salts for F uel Production

Dr J Maund
The application of molten salts as a heating mechanism for the pyrolysis of
wood was reported. A small bench-scale CSTR reactor and condensation train
with gas metering was described. The dissolution of wood in the molten salt was
considered to have been observed though there was scepticism on the part of one
of the audience that wood could be dissolved under non acidic conditions. No firm
evidence was presented to support the solubility claim.
The investigator's preference for a thermal regeneration of hydroxide salts
due to carbonate formation, rather than by the conventional "wet method", was a
judgement based on the avoidance of evaporation costs (high Hv) required by the
latter method, principally. The products were reported to be high in hydrogen in the
gases (potentially the process has produced more hydrogen than was available in
the ligno-cellulosic precursor?), and the condensed phase was mostly water. The
latter result was considered to be significant. However, it would appear that the
researchers might have overlooked quite serious losses of the organic
condensation which, in fact, were observed as aerosols, as smoke and as liquid
products in their gas rotameter Their observations of the latter species very
pointedly express the serious difficulties in oil collection which face any reliable
pyrolysis process. While the problem is solvable, the more significant problem
254
which has not been addressed, and which was raised from the audience, is the
effect of build-up of adventitious impurities (e.g. metals in the wood) which can
radically and rapidly change the rheology of the molten salt system as well as
change the eutectic point or stability of the eutectic mixture. The latter, in turn, will
affect the reaction temperature stability and, hence, the process. The investigators
reported that their runs were not of such a duration that these problems had been
observed.
On a positive note it was suggested to the researcher that he might explore
the use of processes for decarboxylation of waste terephthalate compounds
(polymer production by-products). D r Maund reported that they had used the
process elsewhere for monomer recovery from waste polymers and were currently
investigating the decomposition of glass-reinforced plastic with a goal of recovering
the resin decomposition products (possibly monomer derivation) after dissolution of
the glass in the molten salt. (NOTE: It appears unlikely that -glass and possibly Aglass would dissolve completely without radically altering the composition, reaction
temperature, and rheology of the salt medium).
In summary, a much greater experimental base with the lab-system appears
to be required and it would seem that each process application would have to be
tailored for each feedstock.
SESSION V
257
PERFORMANCE OF A PILOT SCALE FLUIDIZED BED GASIFIER
FUELED BY RICE H
Hartiniati, A. Soemardjo, and M. Youvial

LSDE-BPP Teknologi, Indonesian Energy Research Laboratory
Puspiptek - Serpong, Indonesia.
Sumnary
The performance of a 16 inch fluidized bed rice husks gasifier was
determined for the bed temperatures ranging from 1330 -1600F. The
fuel flow rate was varied from 75 -105 kg/hr. No operational
problems were observed during 36 hours of continuous operation. The
whole study was completed for about 250 hours, and it was found that
the gas quality varied between 650 - 1050 Kcal/Kg (4100 - 6300
KJ/Nm3), depending on the bed operating temperature and/or air to
fuel ratio.
The maximum energy produced was 2920 Kcal-gas/Kg-fuel at the fuel
flow rate of 93 Kg/hr and the bed temperature of 1445F. The lower
heating value of the gas in this condition was 975 Kcal/Kg. Fuel to
gas energy efficiency was found to be 63-67%.
1. INTRODUCTION.
To reduce our great dependence on oil and gas, the biggest commodity
export of Indonesia, since the last decade the government has adopted a
policy to conserve its petroleum reserves and prolong the availability of
an exportable surplus by promoting the development of alternative energy
resources where these can provide an economic substitute for oil. The
development for alternative energy resources then raised our interest in
biomass gasification.
Gasification is a thermochemical process in which the purpose is to
transfer the chemical energy contained in the solid fuel into a gasesous
energy carrier, preferably with a minimum " loss " into thermal energy.
This process creates many possibilities to generate low, medium or high
Btu of gases, depends on the reactor type and the gasifying medium
(3).
In Indonesia, agriculture wastes are abundant in many areas and not
utilized well. It is estimated that about 29 millions ton wastes per year
are produced and as by products, they have a negative value due to the
high cost involved in disposing of them. They should be properly handled
and several concepts for handling and converting these wastes into a
valuable gas fuel have been developed.
To utilize and increase the value of agriculture wastes, the
Fluidized Bed Gasification is one of the most promising conversion
process because of its ability to use a wide variety of fuels.
Since the gas quality produced by a gasifier depends on the nature
of the fuel used and gasifier operating conditions, these conditions need
to be optimized in order to be able to provide data for application
studies.
258
Gasification of rice husks is comparatively difficult due to the
high ash content and the particularly high silica content of the ash.
Major problem of utilizing rice husks is the nature of this feed
stock, i.e.the high ash content ( see table I ), the low bulk density
(100 Kg/m3) and the poor flow characteristics. Morover, processing of
rice husks above 900C is problematic due to ash sintering( 3 ). Table I
presents the characteristic of rice husk used inthe experiment.
2. EXPERIMENTAL
A schematic diagram of 16 inch diameter pilot plant fluidized bed
rice husks gasifier is given in figure 1. A s shown in this figure, a
rotron cyclonair blower supplied fluidizing air to the plenum of the
reactor through an LPG start - up burner which was used to preheat the
bed before commencement of solids feeding. A fter the bed temperature
reached 950 - 1000F the starting burner was then shut off and the feeder
was simultaneously started. The bed material within the reactor is an
aluminum
oxide
refractory
sand having a particle size as shown in
table II. The air passed from the plenum through the distributor into the
bed to react with the rice husks which have been introduced into the bed
via the feeding system.
The rice husks were stored in a surge hopper metered through a
three-screw feeder, directed through a pressure sealing rotary lock
hopper to an injector conveyor, and then injected into the lower part of
the bed,
just above the distributor. Upon entering the reactor,
sufficient amounts of rice husks burn to bring the bed temperature up to
the desired set point temperature. During operation the Barber - Colman
temperature controller automatically set the gasifier air flow rate.
After some initial oscillations in the range of 30F about the set point,
the bed temperature settled down and remain within 8-10F of the set
point. The gas leaving the reactor bed was passed through a double
cyclones in which most of particles were separated from the gas stream.
Subsequently the gas was burned in a dual fuel burner having an array of
LPG/or natural gas and low Btu gas heads. Table II shows the operating
variables used in the experiment.
3. MEASUREMENT. SAMPLING AND ANALYSIS.
Bed operating temperature and rice husks flow rate were the
variables in these experiments, while the air flow rate and the gas
composition were measured. A ir flow rates were measured by means of an
orifice, the solid fuel flow rate was set at the desired set point by
means of switch. The metering feeder was calibrated first before the
experiment began. The flow rate of the product gas was derived from the
known flow rate of nitrogen entering the gasifier with the air and the
nitrogen content of the product gas.
The bed temperature was monitored by a thermocouple penetrating the
fluidized bed. The thermocouple temperature was displayed on a Barber Colman microprocessor based temperature controller having a resolution
of plus or minus 1F.
The train for sampling product gas is illustrated in Figure 2. A
sample of hot gas was extracted from the main gas stream exiting the
gasifier. The gas was passed through a hot filter packed with silica wool
to separate particulates, then is cooled to an ice condensor to remove
condensibles. Subsequently the gas is dried in a dryrite co1umn prior
directing to a GLC unit for its composition analysis.
259
Gas Duct ITc
Cyclones
rluidi'zed Bed
Feeder
Exriaut
Hoppe
Ash
Orurrs
O
ner <-
"
&
Injector
TempXpjTroller
V v
lart Up
Burner P i
>i1ice
^Ftow Control Valve
\d^êr
Figure 1. Schematic Diagram of BPPT gasiti during test at the Puspiptek

Energy Research Laboratory( Serpong.
Hot Filter
(glass wool)
to GLC
\Condensate Flask
Figure 2. Schematic Drawing o1 Gas Sampling System.
260
Table I. Fuel Characteristics
Proximate Analysis
( % weight )
!
!
Moisture content
Ash content
Volatile matter
Fixed carbon
Sulphur
Carbon total
Hydrogen Total
Nitrogen
Oxygen
Heating value
[ = kcal/kg ]
Specific gravity
Ultimate Analysis!
( %'weight )
9,96
20,61
54,68
15,02
0,02
34,94
5,46
0,11
38,86
3220
!
!
!
!
!
1,44
Table II. Operating Conditions
rice husk
0,14 kg water per kg
dry ash free material
1330 - 1600 F
75 - 105 kg/hr
100 - 250 kg/hr
0,3 - 0,4 mm = 26 %
0,4 - 0,6 mm = 45 %
0,6 - 0,8 mm = 29 %
16 inch ( 40 cm )
24 inch ( 60 cm )
Fuel
Moisture content
Operating temperatures
Fuel flow rate
Air flow rate
Bed material
Reactor diameter
Static bed height
Table III. The average gas composition of the

product gas (Vol % dry)
! Temp.
!
!
!
!
1330
1400
1450
1500
1540
1600
H2
3.67
4.74
5.46
5.18
5.04
3.74
CO
8.28
12.23
12.31
10.43
10.14
8.87
C02
13.88
15.04
13.62
14.05
12.18
13.99
N2
CH4
68.73
58.84
61.19
62.34
66.54
67.83
3.63
6.73
5.99
6.17
5.04
3.72
C2H4
1.81
2.42
1.43
1.84
1.06
1.85
LHV !
(KJ/NM3)!
4093
6340
5528
5585
4590
4398
261
4. RESULTS AND DISCUSSION.
The tests were conducted using a 16 inch diameter by 12 feet total
high reactor with bed depth of 24 inches. The parameter study involved
varying the feed rate and bed temperature, then monitoring the gas flow
rate, and product gas composition. For every given fuel flow rate, the
air flow or air fuel ratio increases with rising the bed operating
temperature. In these test the fuel flow rates were adjusted between 75 104 kg/hr. Within the bed temperatures of 1330 - 1600 F, the air fuel
ratio was
found to be 0.30 - 0.48. Figure 3 shows the correlation
between the bed temperature and the air fuel ratio. In all selected
conditions, the
gasifier was steadily and safely operated
for
considerable lengths of time.
As one would expect, the encreasing air fuel ratio tends to angment
the process yield as shown in figure 3 (Process yield is difined as the
ratio of product gas rate to fuel flow rate in dry ash free basis).
Product gas composition.
In agreement with previous results done by else, table III
apparently shows a high carbon monoxide at relatively low temperatures.
This relates to the theory ( 3 ) that at bed temperature below 800 C
(1470 F) the homogeneous water shift reaction seems to be overruled by
pyrolysis reaction, and CO is one of the major gas phase components in
pyrolysis of biomass. Conversely, the hydrocarbons content in the product
gas decline with increasing the bed temperature as a result of thermal
cracking of lower hydrocarbons.
The lower heating values of product gas also decrease with
increasing the bed temperature. This is due to the fact that the higher
the operating temperatures, the more air required per kg daf fuel as more
rice husks have to be burned to get a higher operating temperature level.
As a result of the decline in gas heating valve, the volume of product
gas will increase.
The energy output
For every given fuel flow rate, the energy out put of the gasifier
(Kcal-gas/kg-fuel) as a function of operating temperature is shown in
Figure 4. Energy output was obtained at 2920 Kcal-gas/Kg-fuel for the daf
fuel flow rate of 64.82 Kg/hr,
This maximum value was reached at the operating temperature of 1445
F and air fuel ratio of 34.8%. The lower heating value of the product gas
at this condition was 975 Kcal/kg.
Gasification efficiency.
Figure
5 shows the effect of operating temperature on the
gasification efficiency. The efficiency calculations were made based on
the use of lower heating value of the fuel input and the gas output. In
other words, the gasification efficiency or cold gas efficiency is the
percentage of chemical energy in the fuels that is chemically bound by
the product gas. The experimental result shows that the gasification
efficiency is 63 - 67%. The total heat losses through the wall, ash,
unburned carbon and product gas therefore is 37 - 33%.
5. CONCLUSIONS
The following are the general and
obtained by this study :
specific
overall conclusions
262
100
5,000
A/F Ratio
LHV
Process Yield
poo
0
1,600
TEMPERATURE (F)
Figure 3. LHV,A/F Ratio and Process Yield

as a function of temperature
10,000
Husks (daf) 52.55 kg/h
>cr
0
1,325
1,575
TEMPERATURE (F)
Figure 4. Energy in gas as a function of temperature
263
1.300
TEMPERATURE (F)
1,650
Figure 5. Efficiency of fluidi zed bed gasifier

- For every given fuel flow rate, the air fuel ratio increases with
rising the bed operating temperature.
- At higher operating temperatures the lower heating value of product gas
also decreases due to the more fuel have to be burned to attained that
higher temperature level.
- As another result of rising the operating temperature is an increases
in process yield.
- The maximum energy output of the gasifier was 2920 Kcal-gas/Kg-daf fuel
at the fuel flow rate of 93 Kg/hr and the bed temperature of 1445" F.
The air fuel ratio and the lower heating value of the product gas in
this condition were 0.35 and 975 Kcal/Kg respectively.
- Fuel to gas energy efficiency of the gasifier was 63-67%.
References :
(1) Adiarso Soemardjo, et al, Unjuk Kerja Gasifier Unggun Terfluidakan
skala Pilot dengan Umpan Sekam Padi, LSDE - BPP Teknologi, 1988.
(2) Bing Yan Xu, et al, Design and Operation of a 6.0 inch Fluidized Bed
Gasifier for Rice Hulls, University of Missouri - Rolla, Departement
of Mechanical and Chemical Engineering, Rolla, Missouri 65401, USA.
(3) F.G. Van Den Aarsen, Fluidized Bed Wood Gasifier, Performance and
Modeling, Weerselo, The Netherlands, 1985.
(4) Hartiniati, The potential application of Fluidized Bend Gasifiers as
alternative fuel production Facilities in Indonesia, Seminar on Power
Generation Technology using Biomass, Jakarta, Indonesia, January 1989
(5) American Rice Ine, Biomass Alternative Fuels Program : Final Report
Feasibility Study for Alternative Fuels Production ; Fluidized Bed
Gasification of Rice Hulls, ARI, Houston,Texas 77252, USA, March 1982
264
ELECTRICAL ENERGY FROM BIOMASS
FULVIO FONZI
Italenergie S.p.a. 67039 Sulmona AQ, Italy
Summary
Electric energy is produced by an electrogenerator, using as fuel a
gas of a medium heating value. The gas is produced with a gasifier for
biomass. The biomass used is agricultural and forestry waste products.
The gasifier is built of two concentric fluidized beds, in which the
thermic energy developed by the outer fluidized bed is used to
increase the temperature of the internal
one until complete
gasification of the biomass is obtained. The gas is cleaned, filtered
and cooled, and feeds a gas cylinder engine. The electric energy
produced is used in the factory.
1. INTRODUCTION
1.1.
Aim of the Project
Firstly,
a brief review of the reasons for starting the present
project.
Biomasses represent a source of renewable energy with low sulphur
content, widely available in many areas of the world.
More specifically,
the ligneous and cellulosic wastes produced by
various agricultural and industrial activities constitute energy sources of
particular interest because of their chemico-physical characteristics and
because of their low cost.
We refer, in particular, to timber residues, and waste products of the
wine making, oil pressing, textile and paper making industries.
In Italy, for example, the production of wastes from the timber and
wood-working industries amounts to about 1.5 million tonnes a year. These
wastes are partly used for energy production in the individual enterprises ;
nevertheless, a large portion remains unused.
Lastly,
the coppice is a presently under-used potential biomass
resource which can contribute to energy needs.
The Gasification Process
The gasification process of wood passes through successive phases
which involve drying, pyrolysis, reduction and oxidation procedures. These
phases may be outlined as follows :
1st phase:
Drying:
Damp wood + heat = dry wood + steam
265
2nd phase:
Pyrolysis:
Dry wood + heat = charcoal (carbon), CO , CO, CH ,
organic compound (CnHm, unsaturated and oxygenated
compounds)
3rd phase:
Gasification:
Carbon + Water + heat = CO + H
Carbon + CO
= 2 CO
The feed reactions may, therefore, be indicated as follows:

C
+ CO
= 2 CO
= + 168 kJ/mole
= + 175 kJ/mole
+ H.O = CO + H.
2
2
CO + H.,0
JO = C
CO,
0 2 + H,
H2
H = + 2.9 kJ/mole
+ 2H_ = CCH.
*2 * H 4
= -
75 kJ/mole
The fourth reaction is not facilitated by operating at low pressure and at

high temperature.
The partial oxidation with air of the material to be gasified is the
solution commonly used to obtain the necessary process heat. This method
makes it possible to use a gasification plant of simple design, but has the
disadvantage of producing a gas diluted with the nitrogen contained in the
air. Consequently,
the gas produced has a low calorific value (900 1 200 KcalAg)
This entails a number of disadvantages : the gasification plant must be
directly coupled to the steam generator in order to use the large sensitive
heat of the gas produced at high temperature; the steam generator must
undergo considerable modification to ensure that high efficiencies are
obtained; if the gas is used in internal combustion engines instead of gas
oil or petrol, then the gas must be sufficiently purified and cooled.
If it is necessary to produce gas for subsequent use in the synthesis
of methane ("syngas") , or if it is required to produce a gas of medium
calorific value,
this difficulty must be overcome.
Numerous technical
solutions have been singled out in this respect. For example, the process
heat is generated inside the gasification reactor by partial combustion of
the biomass with pure oxygen instead of with air (1) , or with oxygen
obtained from the thermal decomposition of particular chemical compounds
(2) ; the process heat, generated outside the gasification reactor, is
supplied to the biomass by an inert material circulating between a
combustion chamber and the gasifier (3); lastly, the gasifier is heated from
outside.
The process we proposed uses the last of the possibilities listed
above. In comparison with gasification with pure oxygen, the process has the
advantage of not requiring an oxygen generation plant from the production of
syngas.
The process heat is provided by means of an annular chamber placed
around the gasification reactor; high temperature flue gases obtained by the
combustion of a part of the gas produced with air, pass through this
chamber. In order to facilitate heat transfer from the flue gases to the
gasifier walls, a granular inert material, which is fluidized by the rising
gaseous current, is introduced into the annular chamber. Likewise, the
transfer of the heat to the biomass particles is facilitated by a bed of
266
inert particles fluidized by recycling to the gasifier a part of the gas
produced together with some superheated steam.
The composition of the gas produced depends, apart from the reaction
temperature, on the rate of heating of the wood particles and on the period
during which the reaction products remain at a high temperature. The concentration of methane and of oxygenated and unsaturated organic compounds drops
if the gasification is made at high temperature and for prolonged residence
time of the reaction products. For economic reasons, and in consideration of
the behaviour of the materials, the gasification temperature in our process
has been fixed at 730C. In our operational conditions, the heating time of
the wood particles is very short (in the order of seconds), and the average
time the reaction products remain at a high temperature is much longer (in
the order of minutes).
Under these conditions the gas contains an elevated percentage of
methane and other low condensing hydrocarbons, which are undesired when the
gas has to be used as synthesis gas for methanol production. In this case it
is necessary to heat up the gas in a further step. Therefore a second
gasification step is foreseen where a partial combustion with oxygen takes
place in order to achieve a temperature of 1300C, which is necessary to
crack the hydrocarbons into CO and H . This treatment indeed reduces the
advantages of the total independence of oxygen but, nevertheless,
the
consumption of oxygen is still much less in comparison to the classic oxygen
gasification.
Preliminary Design
The preliminary design of the plant is shown in Figure 1.
Biomass with a moisture content of 20% is fed into a fluidized bed
with a screw feeder. The gasifier is heated up with heating pipes containing
inert fluidizing material. Heat is produced by combustion of a part of the
gas produced and the combustion takes place inside the pipes.
Char and ashes are cleaned from the gases leaving the gasifier by two
cyclones, and the separated char is fed back into the gasifier. One part of
the cleaned gases is used as flushing gas and is recycled to the gasifier by
a hot-gas blower. The temperatures in the different sections of the plant
are as follows :
fluidized bed of biomass
fluidized bed of heating pipes
cracking chamber
730C
930C
1100C
The gases leaving the cracking chamber have to be cooled down to 240C
in a first stage. After this, fine solid ash-like particles are separated by
a fine mesh filter. In a second cooler the syngas will be cooled down to
450C.
2. DESCRIPTION OF THE PLANT
2.1
Biomass Charging System

The biomass charging system consists of the following main units :
incoming biomass storage van of a capacity sufficient to ensure two
days' work for the gasifier (30 tons of biomass volume 80 m c ) ;
biomass transfer and weighting system, consisting of conveyor belts,
elevators, granular materials scale, separator of ferrous foreign
oygan
F i g . 1 . The Vood G a s i f i c a t i o n P l a n t , December '87
to atmosp.
LOADING SYSTEM; 2. GASIFIER; 3. CYCLONES; 't. CRACKING CHAMBER; 5. QUENCHER; 6. STEAM SUPERHEATER; 7. STEAM GENERATOR;
8. SCRUBBER COOLER; 9. FLARE SYSTEM; 10 EJECTOR; II. COMBUSTION CHAMBER;
FLUIDI ZED BED
TEMPERATURE
OPERATION
DATA
BIOMASS
FLOW RA TE
12. AIR PREHEATER;
SYNGAS
FLOW RA TE
N2:33.5 C2:3.0
700 * 750"C
100300 kg/h
830 8B0*C
CH4:13.3
10O250 Nm/h
CO. 24.9
DECEMBER '87
13. ID FAN; . AUXILIARY BOILER
GAS COMPOSITION C D
DRY BA SIS
0j:0.05
C02:21.9
N2.2.45
268
materials, hoppers, etc. in order to guarantee the feeding of the wood
chips to the gasifier at a variable rate from 100 to 1 000 kg/h.
2.2
System for Producing Gasifier Heating Fluid
As previously stated, the reaction that occurs in the gasification of

the biomass is endothermic; the heat is supplied to the system by means of a
fluid which heats the outer walls of the reactor. This fluid consists of
flue gases obtained from combustion of a part of the gas produced in the
gasifier with excess air.
As will be described in section 2.3, the amount of heat to be supplied
to the reactor, under the assumed operating conditions, amounts to 300 000
Kcal/h. Because of the behaviour of the materials, the maximum temperature
of the flue gases is fixed at 1 250C; the temperature difference between
the entry and the exit of these flue gases from the reactor is fixed at
400C. Under these conditions, the rate of flow of the flue gases amounts to
2 500 kg/h. The air fed to the combustion chamber is preheated in a heat
exchanger from the flue gases coming from the gasifier, cooled down from
850C to 340C. In this experimental plant, these flue gases are no longer
used, and are discharged directly into the chimney stack.
It is obvious that in an industrial plant the residual heat would be
recovered and used, for instance, for drying the biomass or for generating
electric power to serve the plant.
On starting up the plant, when the production of gas from the biomass
has not yet begun, or is insufficient, the production of the heating fluid
is assured by auxiliary fuel.
A fan,
mounted downstream of the combustion chamber and of the
preheater, ensures the described flow rate of hot flue gases through the
gasifier heating chamber.
Adequate instrumentation prevents the maximum temperature of the flue
gases, fixed at 1 250C, from being exceeded, and acts in such a way as to
ensure that the gasification temperature of 730C is maintained in the
reactor.
This is performed by acting on the air and combustible gas flow rate.
2.3
Gasifier
The system consists of a reactor, cyclones for the separation of the

solid products from the gas, and a compressor for recycling the fluidizing
gas.
The gasification of the biomass, through heating and reaction with
steam, occurs in the inner chamber of the reactor. On fixing the hourly flow
rate of the biomass (500 kg/h) and the steam biomass ratio (0:4) , the
calculated hourly quantity of heat that has to be supplied amounts to about
200 000 Kcal/h. In order to allow for the heat losses through the surface of
the equipment, and to ensure an adequate safety margin, the quantity of heat
to be provided to the gasifier has been estimated at 300 000 Kcal/h.
To meet the first requirement, the side wall of the gasifying chamber
has been constructed of corrugated sheets ; the necessary exchange area is
thus obtained with a smaller height of the gasification chamber. Considering
an average diameter of 1 200 mm for the gasification chamber, the exchange
area of 4 m2 is obtained with a 700 mm high fluidized bed. If the dynamic
pressure supplied to the fluid bed process gas by the fan is 800 mm of
water,
the density of the bed in static conditions must be less than
1.15 kg/dmJ . In practice, allowing for the pressure losses due to the
diffuses and to the pipe circuit, the apparent density of the bed must not
exceed 0.8-0.9 kg/dm3 .
269
This is why 1-2 mm diameter spheroidal particles of aluminium oxide
with a density of 3965 kg/m3 have been chosen as inert material to
constitute the fluid bed. Laboratory tests have shown that this material has
good mechanical strength and a modest erosion effect on the metal walls.
It is hard to predict the behaviour of the biomass in the fluid bed of
alumina particles under the operating conditions. Since the biomass is fed
from above, it is very probable that the mixing of the wood chips with the
alumina particles would be restricted to the superficial layers. According
to this assumption, two overlapping beds would be obtained, one of alumina
particles and one of wood chips, mostly heated by the gas flow which in turn
has received heat passing through the inert fluidized bed.
Since the volume of the gasification chamber is 1 700 litres,
850 litres of which are taken by the inert material, the biomass (600 kg/h,
apparent density 300 kg/m 3 , equivalent to 2 m 3 /h) has an available reaction
volume of about 850 litres which allows a gasification time longer than the
experimental one (20'),
determined by the laboratory tests in the same
temperature conditions (730C).
Therefore the wood particles should be pyrolyzed in less than a minute
into char and later there will be the gasification of the char because of
the action of the CO and of the steam present in the fluidifying gas. The
solid particles will be entrained by the gas outside the gasification
chamber only when they have attained a very fine grain size, in the order of
microns.
The first cyclone is, however, designed to separate from gas all the
solid particles with grain size over 500: it is presumed that these
particles are still made of char and consequently they are recycled to the
gasification chamber.
R = 96
Fig. 2. Double bed gasifier - cross section
270
Two further cyclones separate the finer particles,
which are
considered to be made of 'ash'; the latter particles are discharged from the
plant and collected in an appropriate container. Naturally, these 'ashes'
will contain a part of fine-grained char, which has not reacted. The flow
rate of the ashes has been estimated at 3.8% of the biomass introduced, i.e.
23 kg/h.
3. MASS AND ENERGY BALANCES
By feeding 600 kg/h of wood chips, containing 20% of moisture by
weight, and 240 kg/h of superheated steam to the gasifier, 827 kg/h of gas
is obtained, of which 185 kg/h is used to obtain the heating process and
632 kg/h is sent for successive treatments. In addition, 23 kg/h of ashes is
produced. According to estimates based on the chemical equilibrium, the gas
produced has the following composition :
(% by volume)
= 32
11
= 22
co2
II
= 15
II
= 23
II
2
CO
CH
The calorific value of this gas is 2 700 Kcal/kg; it may, therefore,

be considered as gas of medium calorific value and, as such, can be used
directly for the generation of steam and/or electric power as a substitute
for natural gas.
The addition of 98 kg/h of oxygen and the resulting temperature
increase of the gas in the cracking chamber permits the almost quantitative
completion of the reaction:
CH 4 + H 2 0 = CO + 3 H 2
In this way, the reduction of the methane content in the gas produced
is accomplished, and 730 kg/h of syngas with the following composition is
obtained :
H
(% by volume)
= 31
CO
"
= 24
CO
"
= 14
H20
"
= 30
CH
"
= 1
The process then provides for cooling the gas by direct injection of
water,
and utilization of its sensitive heat for the production of
superheated steam. As a result of this treatment, a large part of the steam
present in the gas is condensed, the remaining 543 kg/h of gas having the
following composition :
H
(% by volume)
= 44
CO
"
= 34
C02
"
= 16
H20
CH
"
4
= 2
271
This should, then, meet the specification required for a gas assigned
to the synthesis of the methane.
This balance shows that from the
1.98 Gcal/h introduced with the biomass into the gasifier, 1.47 Gcal/h is
obtained from the system in the form of syngas. This corresponds to an
efficiency calculated at 74%.
This balance does not make allowance for the thermal leakages through
the surface of the pieces of equipment and for sub-actions and the
consumption of energy necessary for working the pumps, the fans,
the
instruments, etc. However, it should be noted that since we are dealing with
an experimental plant the possible energy recoveries have not been
optimized; for example, the sensitive heat of the flue gas discharged into
the stack at a temperature of 340C can be used for drying the biomass.
4. DATA GATHERING CAMPAIGN
We carried out some modifications of the plant. The most important was
the replacement of the hot gas blower with an ejector. These modifications
allowed the final data gathering and test-run to be planned on a sufficiently reliable basis. They also improved the plant safety. Particular care
was devoted to :
check of the new equipment installation and the plant status in cold
condition;
testing of the individual equipment in no-load condition;
heating up of the process circuit;
running and test of the plant for five days of continuous operation;
data collection, elaboration and analysis.
The new equipment was in good condition. The installation of the
superheated steam line (2", sch. 40) for ejector feeding has been completed,
as well as the new 8" line for recirculation syngas and the flow control
butterfly valve.
Some problems occurred during the single machinery tests. We had
interlocking problems for the char discharging system.
Furthermore, we
decided to replace the stored wood chips with new green beechwood because
the stored biomass was a mixture of beechwood and sleeper chips partially
fermented.
The aim was to avoid toxic product formation during the
gasification due to the sleeper treatment containing creosote.
After the interventions and substitutions mentioned, the plant was
ready.
Problems were noted during the heating up of the plant.
It is
important to point out the following:
the pressure safety valves, located on the steam drum, had to be
revised because of tightening problems;
so we had to repeat the
calibration of the valves ;
transformer failure of the motor control centre; it was replaced by
another transformer of higher capacity;
controller failure of the auxiliary boiler burner; it was replaced
after three boiler shutdown;
check
and calibration
of all
handling
and
feeding
systems ;
particularly the platform scale;
the heating up rate was very low to avoid problems caused by
ungasified coal deposited inside the gasification circuit. During the
previous heating up, it was necessary to clean the plant to avoid
burning of these deposits.
In this case we had only localized
combustion;
272
when the gasification circuit was about 400C (inner bed temp.), the
auxiliary recirculation fan was replaced with an ejector system;
during this operation it was necessary to take care of the main
equipment to avoid problems related to the several thermal expansions
of each system.
When the process temperature into the inner bed was reached,
the
gasification circuit was recirculated with nitrogen to substitute the hot
air used during the heating up. Biomass feeding started only when oxygen
content was less than 0.05% (by volume) into the circuit. The feeding system
had mainly two problems: clogging and sealing.
In order to assure a good seal of the screw feeder, special attention
was devoted to keeping it constantly full of biomass. In this way a good
sealing was obtained to prevent the syngas leaking. The analyser showed some
problems when the water content was high and, in these conditions, special
precautions were required to assure reliable results. However, at the same
time many samples were sent to the laboratories for check analysis.
The data collected from the tests were acceptable and satisfied the
heat and material balance. These gasification tests prove the innovative
concept on which the gasification plant is based;
indirect heating by
fluidized bed. In addition, the possibility of obtaining a medium Btu gas
without using oxygen has been demonstrated.
From the data obtained, we
calculated a heat transfer coefficient figure of about 200-250 Kcal/h m2 C.
The certified
gas analysis
coming from different laboratories
confirmed the expected figures.
The main data are :
fluidized bed temperature
: inner bed 700-750C
biomass flow rate
: 600 kg/h
syngas flow rate
: 500 Nm3/h
outer bed 830-880C
syngas composition (% vol)
CO
: 21 9
: 33 5
co2
: 24 9
CH
: 13 3
2H6
0 30
2H4
2 70
2 45
0 05
syngas LHV
3480 KcalAg
( 14 6 M J A g )
electrical energy
505 kWh/h
5. CONCLUSION
We can say we have demonstrated the feasibility of the process on an
industrial plant, even though at prototype level. The reactor confirmed the
expected high heat transfer performances. The know-how obtained and the
figures accumulated in the running period will allow us to design new units,
the costs of which we estimate will be lower by about 30%. The test has
273
enhanced the possibility of using this reactor to gasify pellets obtained
from organic urban wastes.
The cost of electrical energy production is still very high for the
present demonstration plant.
The cost for electricity per kWh is not
competitive with that of the national grid, at least with this present
demonstration plant.
However,
with a new unit it is possible that a
competitive performance can be reached.
In any event, the plant can produce electrical energy at a competitive
cost where the electrical energy cost is about 300 Lit/kWh, as is the case
in many developing countries (which are very rich in biomass and forest
wastes) and where the electricity is produced by big diesel generators.
ELECTRICAL ENERGY FROM BIOMASS

PLANT CAPACITY
SUPERHEATED STEAM
GAS PRODUCED
HEAT TRANSFER COEFFICIENT
GAS LHV
GAS DENSITY
THERMAL ENERGY FLOW
ELECTRICAL ENERGY PRODUCED
THERMAL EFFICIENCY
GAS COMPOSITION: (% vol.
H
33.5
CO
21.9
CO
24.9
CH
13.3
C H
0.30
C H
2.70
2.45
0
0.05
600 kg/h biomass with 20% moisture

240 kg/h
500 kg/h
220-250 KcalA g
3480 Kcal/kg (14.6 MJ/kg)
1.0 kg/Nm3
1*740.000 Kcal/h =
= 2.018 kWh/h
505 kWh/h
74%
(CALCULATED)
(32)
(22)
(15)
( 8)
ELECTRICAL ENERGY COST: 300 Lit/kWh
Heat transfer coefficient calculation

= Q/S / *) (filling coefficient)
1.
Considering S.. = 6.03 m2
2.
=
=
188000/6.03/100/ * 0.8 = 249 Kcal/m2hC

390 Kcal/m2hC
Considering S
H2
=
=
9 . 4 5 m2
1 8 8 0 0 0 / 9 . 4 5 / 1 0 0 0 . 8 = 159 K c a l / m 2 h " C
250 K c a l / m 2 h C
274
FLUIDIZED BED GASIFICATION OF WOOD : PERFORMANCE OF A

DEMONSTRATION PI ANT
K. MANIATIS+, A.V. BRIDGWATER*, A. BUEKENS+
+ Department of Chemical Engineering and Industrial Chemistry, Free
University
of Brussels, Pleinlaan 2,1050 Brussels, Belgium
* Department of Chemical Engineering, Aston University, Birmingham B4, UK
Summary
A Process Development Unit fluidized bed gasifier of 0.8 m and 1.6 m
diameter respectively for the bed and freeboard section, was built and
tested with the air gasification of chopped wood.
The results were
correlated with the air factor and were compared with thermodynamic
predictions and published data. Reasonably good agreement was found
between experimental, published and thermodynamic data. The higher
heating value of the gas varied in the range of 4 - 7 MJ/Nm^ under normal
operating conditions while the bed temperature varied in the range of 750 900C. It was found that the best performance was achieved in the air
factor range of 0.20 - 0.4. The gas yield Increased with higher values of
air factor but in the region of interest it was about 2.5 kg gas/kg feedstock
MAF. It was also concluded that constant feedstock flowrate was a
prerequisite for efficient operation, and constant performance.
1.
INTRODUCTION
Since the energy crisis of the seventies, research on biomass conversion
focused on producing a fuel gas for energy purposes and several
R & D
programmes on biomass gasification were initiated. Soon It was realised that
fluidized bed reactors offer significant advantages over other types of gasifier
configurations such as isothermal operation, simple scaling up procedures, high
(industrial) capacities a good turn down ratio and multi fuel operation as long as
feed size restrictions are respected. Their versatility helped to establish them as
the reactor configuration of choise and several R & D projects were initiated in
the Universities (eg. 1 - 5) as weel as private companies such as Omnifuel (6) of
Canada and Vyncke N.V. of Belgium (7).
In 1980 an R & D programme was initiated between Vyncke N.V. of
Harelbeke Belgium - a boiler manufacturer - and the Department of Chemical
Engineering and Industrial Chemistry of the Free University of Brussels (V.U.B.).
The programme was financed by the Institute of Scientific Research for the
Industry and Agriculture and aimed at the commercial production of downdraft and
fluidized bed gasifiers. Initially a co-current downdraft moving bed gasifier was
designed, built and tested and since 1983, this type of gasifier has been marketed
by Vyncke N.V. In 1982, a fluidized bed gasifier process development unit (PDU)
was designed by the V.U.B. on the basis of a laboratory scale pilot plant (8) and
built at the Vyncker N.V. workshop. The unit was subsequently commissioned and
an extensive experimental programme was executed to identify the influence of all
275
major paramaters of the air gasification of wood in a large scale experimental
reactor and the effect of scaling up on the performance of the reactor. The
purpose of this paper Is to report some results concerning the performance of the
fluidized bed gasifier.
2. EXPERIMENTATION
It was envisaged that the fluidized bed would be operated under different
conditions and with a variety of feedstocks.
In order to provide for every
possible experimental condition the reactor was provided with 2 feeding ports
(one above the surface of the bed at fluidization conditions and the other 0.1 m
above the distributor), 2 ports for overbed preheating burners, several measuring
ports for thermocouples and pressure gauges and 2 observation ports. Special
consideration was given td the distributor configuration which should allow the
passage of heavy and/or bulky material such as stones and conglomerated inerts.
It was decided to use a pipe grid distributor which has such capabilities. A layer
of refractory bricks forms the inner linning of the shell to give a finished diameter
of 0.8 m at the bed section and 1.2 m at the freeboard section. The fluidized bed is
shown in Figure 1.
The pilot plant consists of a feeding system (a hopper equipped with a
variable speed screw for metering the feedstock, a rotary valve and a conveyor
screw), the fluidized bed reactor, air compressor, preheating burner, a flare, a
control cabin and a gas sampling system. The latter consists of a cyclone, a
cooler (tube and shell), a filter, a gasmeter and a suction pump. Gas samples were
taken directly from the gas collector of the flare and were analysed locally by gas
chromatography In the control cabin and field laboratory.
The gasification process is depicted in the process flowsheet, Figure 2.
The feedstock was delivered by a particle board manufacturer in closed
containers. A front end loader transported the feedstock to the conveyor belt for
loading the hopper. The feedstock flowrate was calibrated by direct measurement
of the weight through an opening below the rotary valve. It entered the reactor
above the surface of the bed. A compressor supplied the air required to fluidize
the bed, while the air flowrate was measured by a rotameter. The air was fed
through the preheating burner to the collectors of the distributor and from there it
entered the bed. The feedstock pyrolysed as it fell into the fluidized bed to
produce pyrolysis gases and char. The char was gasified by steam and carbon
dioxide and partially combusted by oxygen, while the pyrolysis gases participated
in secondary reactions. The product gas and fly ash were led to the flare were the
gas was burned.
A small fraction of the gas (about 20 % by volume) was removed from the
product gas burner and passed through the cyclone to remove the fly ash and
through the cooler to condense the steam and tars. The experimental procedure as
well as the feedstock properties has been described in detail esewhere (9).
The results were correlated with the air factor, (defined as the ratio of the
amount of air supplied in the reactor divided by the amount of air required for
stoichiometric combustion) and with the bed temperature.
3.1. THE AIR FACTOR
The air factor has the strongest influence on the performance of a gasifier
since it strongly influences the bed temperature, the gas quality, the thermal
efficiency and in practice all experimental parameters. As the air factor is
276
jt
,600
1200
o
o
o
800
o
o
o
All units in mm
F i g u r e
1 : The fluldized bed reactor
Flare
- To gas analysis
Cooler
Wood
Cyclone \ p
Ash
Fluidized bed
Compressor
Figure 2:
Process flowsheet
Gas
277
increased after a steady state has been attained, the amount of oxygen supplied in
the reactor increases and hence the degree of combustion. Since more heat is
liberated the bed temperature Increases (see Figure 3) while the gas quality falls
due to higher concentrations of CO2 and H 2 0 . This is illustrated in Figure 4 which
also compares the results of the PDU to results obtained at the laboratory scale
fluidized bed gasifier at the V.U.B. Due to the higher degree of combustion, the
gas yield also increases with higher values of air factor as shown in Figure 5,
which also compares data with the bench scale plant at the V.U.B. Figure 6 shows
the influence of the air factor on the thermal efficiency (defined as the chemical
energy of the gas divided by the chemical energy of the feedstock at moisture, ash
free basis).
In general there is good agreement between data obtained from the two
plants although the scale up factor was in the order of about 100. Data from bark
gasification show consistantly a lower performance but this is due to the very
high ash/in erts content (24 wt %) of the bark which resulted in gas of inferior
quality. Nevertheless the trend is the same for all parameters and feedstocks. A
carefull examination of Figures 4-6 reveals that the best performance was
achieved in the air factor range of 0.2 -0.4.
3.2. THE BED TEMPERATURE
From Figure 3 it can be seen that the bed temperature was varied in the
range of 680 to 975C. Operation above 900C resulted in sand agglomeration,
due to the formation of low melting alkali metals euteclics with silica found in the
ash of the feedstock and the sand respectively. Loss in fluidization never occured
since the agglomerated particles segregated below the distributor due to their
larger size. This behaviour was expected but it was decided to perform the
experiments at high values of air factor in order to test the operating limitations
of the PDU. It was concluded that with a pipe grid distributor it is possible to
operate at temperatures above 900C for short periods of time as long as
provisions of sand replenishment are made.
The influence of the bed temperature on the gas composition is shown in
Figure 7 for experiments performed in a close range of feedstock flowrate (about
225 kg/h) and of air factor (about 0.3). It is shown that the volume percent
concentration of carbon monoxide and hydrogen pass through a maximum at about
820C, while the concentration of carbon dioxide has a minimum at about the same
temperature. Methane has practically a constant concentration of about 5% till
820 C and drops thereafter. Ethylene and ethane have constant concentrations till
about 780 C and fell thereafter to concentrations below 0.5 and 0.1 vol. %
respectively. A similar behaviour is presented by the higher heating value of the
gas, which has an average value of 6 MJ/Nm 3 till about 820C but drops at higher
temperatures.
The decrease in the concentrations of carbon monoxide and hydrogen below
800C can be tentatively explained by the assumption that below this temperature
the pyrolysis products (tars and condensable organic vapours) predominate due to
the lower temperature and hence the rate of the cracking reactions (which could
transform the pyrolysis products to lower hydrocarbons) Is very slow.
Above 830 C however, more feedstock has to be combusted to maintain
the temperature of the bed at that high level and thus the concentrations of the
gasification products decrease, while the concentration of carbon dioxide
increases.
278
1200
Thermodynamic prediction
1000
o
800
4>
*> 600
400
Figure 3: Bed temperature vs the air factor
1. Wood shavings
2. Bark
3. Refuse derived fuel
5
41
Experimental data
>
to
0.1
0.2
0.3
0.4
0.5
Air factor
0.6
0.7
0.8
Figure 4: Higher heating value of the gas vs the air factor
0.9
1.0
279
1.0
Air factor
Figure 5: Gas yield vs the air factor
0.4
0.6
.8
Air factor
Figure 6: Thermal efficiency vs the air factor
1.0
280
cr
>
8
6 g
<
4 SL
c
o
800
700
Bed temperature
Figure 7: Gas composition vs the bed temperature
3.3. OPTIMUM PERFORMANCE

In the air factor range of 0.2 0.4 the performance shown In Table 1 was
attained repeateally.
Table 1. Optimum performance
Bed temperature
Higher heating value
Gas yield
Thermal efficiency
C
MJ/Nm 3
kg gas/kg feed MAF
%
820
6.5
2.5
65
4. CONCLUSIONS
The PDU fluldized bed gasifier was scaled up by a factor of about 100 from
a Denen scale plant successfully.
Under similar operating conditions the
performance of the PDU was better than that of the bench scale plant.
281
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
R.S. Burton and R.C. Baillie, Fluid bed pyrolysis of solid wastes materials,
Combustion, 13-19 February 1974.
P.T. Raman, W.P. Walawender, V. Shimizu and L T . Fan, Gasification of corn
stover in a fluidized bed : effects of superficial gas velocity and feed size
fraction, Fuels from biomass and wastes, eds. D.L Klass and G.V. Emert,
Ann Arbor Science, 1981.
M. Findely, V. Flanigan and H. Sineath, Phase II, GROW Project, Proc, 13th
Biomass Thermochemical contractors meeting, Arlington, Virignia, October
1981
F.G. van der Arsen, A.A.C.M. Beenackers and W.P.M, van Swaaij,
Performance of a rice husk fuelled fluidized bed pilot plant gasifier,
Proceedings, 1st International Producer Gas Conference, Sri Lanka,
November 1982.
J. Schoeters, K. Maniatis and A. Buekens, The fluidized bed gasification of
Biomass : Experimental studies of a benchscale reactor, in print with
Biomass.
G. Gurnik, K.O. Luke and D.C. Pollock, Application of a fluidized bed gasifier
to conversion of forest biomass to an energy source, Report to ENFOR
1980.
K. Maniatis, J. Schoeters and A. Buekens, Fluidized bed gasification of
biomass, Reports 1-4 and 8. Reports to Vyncke N.V.
J . Schoeters, K. Maniatis and A. Buekens, Fuel gas from agricultural
residues in a fluidized bed reactor, Proc. 2nd World Congress of chemical
engineering, Montreal, October 1981.
K. Maniatis, A.V. Bridgwater and A. Buekens, Fluidized bed gasification of
wood" Proceedings, Research in Thermochemical Conversion of Biomass,
Phoenix, 1988.
282
NATIONAL PROGRAM ON IMPLEMENTA TION
OF BIOMASS GASIFTCATTON PROCESS TN INDONESIA.
Scenario. Progress and Economic Evaluation
Herri Susanto and Soehadi Reksowardojo
Dept. of Chem. Eng, ITB, Jalan Ganesha 10 Bandung, Indonesia
ABSTRACT
Biomass gasification process has received a great
attention in Indonesia, and it shall be a national asset
in the near future. Essential steps to be considered in
realizing this program are (a) making the existing field
test units as a nucleus for the dissemination and culti
vation, (b) establishing necessary local institutions for
monitoring and technical assistance, (c) building up an
infrastructure in the regions concerned in order to pro
vide repair, maintenance as well as production fasili
ties, (d) creating a funding or credit system for the
investment of a gasification unit.
Factors affecting the success of the implementation
of biomass gasification process, however, are not only
the process reliability, but also a short term profit for
the user, motivation of persons involved in the program,
supply and preparation of the feedstock, the local mana
gement and the financial support during the introduction
period.
1. INTRODUCTION
Gasifications of various type of biomass including wood,
coconut shell, palmnut shell, corn corb and rice hulls have
been tested at ITB. Intensive studies on the gasification of
wood and of rice hulls have been done at our laboratory and
reported eg. in [1,2,3]. Field tests have also been conducted
in several places, in Java Island. Performance of 15 kW wood
gasification in Balong, Middle Java, was reported already in
[4,5,6]. This unit has now an operating record of about 12000
hours. Experiences in the field operation of rice hulls gasi
fication are presented in [7].
In our experiences, the
producer gas is used as an oil substitution upto 80% for
diesel engines. The choice of diesel engine instead of gas
engine is due to the fact that the diesel engine has been
introduced since the sixties, and hence its infrastructure has
already been established.
Based on our previous field experiences and on an econo
mic analysis, the implementation of biomass gasification pro
cess in Indonesia needs a scenario regarding to the direction
and the way of further development, so that the biomass gasi
fication shall become a national asset, and its benefit and
usefulness are felt in the social dan economic life of the
Indonesian people. A proposal and a progress of the scenario
for the implementation of gasification technology are describ
ed in this paper. A short discussion on the economic of the
gasification process is also presented.
283
2. THE PRESIDENTIAL PROJECT
Being aware, that the Indonesian nation will face hardships when its oil, gas and coal resources have been pumped
out completely, the National Energy Coordination Board has
pointed out the need for diversification of energy resources.
The biomass gasification process being one of many alternatives, has become a national issue and topic, as at least six
Ministries
engange in the activities concerning with the
biomass gasification. This 'political will' of the government
has been responded with research and development conducted by
many research institutes, universities and industries. Even
foreign parties with various motivations and various ways have
taken part in the introduction of the biomass gasification
technology. By the end of 1986, the President personally launched a promotion project of the gasification, which in essence
constitutes a campaign for the cultivation of biomass gasification process.
In this Presidential project, five wood gasification
units with a capacity in the range of 15 - 100 kW and a rice
hulls gasification unit with capacity of 40 kW were installed
in six provinces (see Appendices A and B ) . This promotion
program is also the last part of our program in research and
development of the biomass gasification process within the
frame of Project JTA-9A. The objectives of this program are :
- promotion and demonstration of biomass gasification as an
alternative energy resource
- dissemination of the biomass gasification technology
- development of a self supporting energy system in rural
areas
- improvement of efficiency and effectiveness of utilization
of wood and other agricultural wastes,
- collecting information for further studies, research and
development of the next implementation program.
3. SCENARIO and PROGRESS OF THE IMPLEMENTATION
A picture of the real conditions of biomass gasification
program in Indonesia can be summarized as follows :
a. there are serious political wills of the President and the
government,
b. there are activities by many institutions which have
successfully established gasification diesel engine systems
in various regions in Indonesia,
c. but there exists limitations on the production, supply, and
use of gasification process as an alternative energy
resource.
The limitations are probably due to various constraints,
such as :
a. the process is relatively new, and the field experiences
are only in Java,
b. the gasification units must be operated in proper ways,
which requires high dicipline operators,
c. there is no infrastucture in the regions for technical
training and assistance, as well as repair, spare parts and
after sale services,
To overcome the present limitations, it is necessary to
establish a Monitoring and Technical Assistance Team
in
284
the region of the Presidential pronotion units for a certain
introduction period. The tasks of this team are :
a. collecting and evaluation of sociotechnoeconomic field
data, the data could then be used for :
determining whether the installed units meet the tech
nical, operational and economical expectation of the
local users,
identification of the operating conditions to ensure a
successfull implementation of the biomass gasification,
determining a standard gasification technology that is
accepted by the users
identifying technological aspects that requires an addi
tional research and development,
defining a scope of application of the biomass gasifi
cation in a spesific area,
b. technical and operational support, so that the existing
units can be operated properly as a demonstration and
promotion one,
c. improvement of the unit, so that it achieves better re
liability,
d. transfering the technology from the innovator to the local
parties.
The Monitoring and Technical Assistance Team consists of :
a. local scientists, technologist and industrialists,
b. officials from region institutions and authorities,
c. management of local users of the gasification unit,
d. central coordination by Project JTA9A, ITB.
The execution of the promotion program is divided into
two main phases, settingup the field units and monitoring of
the real operating performance at least for one year after the
installation. Table I shows the activities and contribution of
parties involved in this promotion program. Many institutions
have been taking part in this activity for the financial and
technical supports, as well as the social and economic
aspects, (see also Appendix A ) .
Appendix shows the technical data of the six promotion
units. During the second main phases, the daily operation data
is recorded by local operator, who have been trained for
operation, maintenance and monitoring. The local supervisors
will then communicate the data and the technical problems to
Project
JTA9A/ITB as a central coordinating agent.
A
technical meeting is planned at the end of the monitoring
program.
After about one year installed in sites, we found that
the local conditions have influenced very much on the progress
of the promotion project. The villagers or the users usually
have not yet understood the goal of the project completely.
They suppose that this project is as a rural electricity,
rather than a self supporting energy with the use of biomass.
As a result, they operate the unit with diesel oil, which is
furtunately available everywhere, in this time.
The lack of maintenance such as cleaning of the gas
piping, periodical ash removal from the ash bin the bottom of
the gasifier, and preparation of proper size and moisture
content of the feedstock often caused serious technical
problem. Since the operation of the gasification unit is
285
cumbersome, the operator often run away from their job, so
another training for new operators was necessary. Many other
non-technical problems, such as the lack of working capital
and mis-management were found to be decisive factors to the
the success of the promotion project.
Despite the above problems, Scientific and Industrial
Agents have been set-up for the implementation of the biomass
gasification process in the future. Institute of Technology in
Surabaya and PT BBI, an engine manufacturer will cope the
implementation for instance on Java and Small Sunda Islands,
including Sumbawa and Timor Islands. The implementation in
Kalimantan will be taken by PT Pupuk Kaltim, a fertilizer
company. While PT Pupuk Sriwijaya and University of Sriwijaya
will carry out the implementation in Sumatra, etc.
The tasks of this Scientific and Industrial Agent are
more or less the same as the Monitoring and Technical Assistance Team mentioned previously. But the Scientific and
Industrial Agent may also act as a clearing house for credit
facilities as the use of gasification unit needs additional
investment.
Table I : Setting-up the promotion
phases/activities
central coordinator
local parties
prem. study
and design
-gasification units
-diesel-genset
-sites selection
-capacity
-fuel supply
installation
-gasification units
-diesel-genset
-auxiliary equip's
-electric transmisin
-electric distribution
-power house
operation
-technical ass.
-training
-operators
-local management
-local supervisor
-operating cost for

first three months
-self operation
in following months
monitoring
-coordination
dissemination
and further
promotion
-national program
-operators
-local supervisor
-government promotion
-private interest
-local manufacturing
4. ECONOMIC EVALUATION
The real economic evaluation of six Presidential promotion units could not been evaluated yet, since the units have
not been operated in regular and commercial bases. Taking the
investment cost of the gasification unit into account, the
operation of a gasification unit for the oil substitution in a
diesel genset, usually saves only a marginal amount of money.
The difference of the diesel oil price and the gasification
feedstock is apparently not big enough in this moment to com-
286
pensate the additional investment. Rough economic evaluation
showed that this additional investment for the gasification
unit should not be more than USD 200 - USD 350 per kW depending on the capacity. Reduction of the investment cost seems
possible, if manufacturing of a standardized gasification unit
is applied in a commercial production.
The transportation cost of gasification unit must also be
taken into consideration in the economic evaluation of the use
of gasification process for rural electricity outside Java. As
the gasification unit is technically rather simple, manufacturing of gasification units close to the user is considered to
be a good solution to reduce partly the additional cost. By a
proper arrangement of the transfer of gasification technology
from the innovator to the local workshops or industrialists,
the implementation of the biomass gasification process would
become more feasible. Building up a Scientific and Industrial
Agent discussed in the previous section is considered to be a
prospective way to realize the local manufacturing of gasification unit in the future.
Our previous field unit in Balong, Middle Java (Appendix
C, [7]) has shown, that the life time of a gasification unit
upto 8 years could be expected, if the maintenance and operation procedure were carried out properly. But the operation of
six promotion units outside Java for about one year have indicated unfavourable conditions with respect to the gasification
unit life time. Repair and maintenance cost have also increased due to improper operation of the gasification unit.
5. CONCLUSIONS
The biomass gasification being as one of prospective
alternative energy resources has been promoted widely through
out the country. This promotion should be followed by a national monitoring program in order to obtain a reliable data for
defining the adaptability of the biomass gasification technology. Tranfer of the gasification technology to local scientists and industrialists is necessary in a country like Indonesia for setting up a local network.
Acknowledgements
The authors gratefully mention the contribution and
cooperation of the Ministry of Forestry, BBI-diesel engine
manufacturer, and all parties involved in this promotion
program.
Literature
1. Ghazali, S, D. Sasongko and S. Hardjosuparto, "Experiences
in using Rubber-tree Wood and Teak Wood as Feedstock for
Producer Gas Generator", paper presented in the Second
International Producer Gas Conference, Bandung, March 1985.
2. Manurung, R, and A.A.CM. Beenackers, "An Open Core Rice
Husk Gasifier for Small Scale Application", paper presented
in the Second International Producer Gas
Conference,
Bandung, March 1985.
3. Sasongko, D, S. Ghazali and S. Hardjosuparto, "Maximum
Capacity of A Cocurrent Moving Bed Gasifier", paper presented in ASEAN Workshop on Thermal Conversion of Biomass,
287
Hatyai, Thailand, September 1988.
4. Sudarno H and A. Koopmans, "Balong Demonstration Gasifi
cation Unit, A Field Experience Report", paper presented in
the Second International Producer Gas Conference, Bandung,
March 1985.
5. Susanto, H, A. Koopman, and Sudarno, H, "Field Experience
of 15 and 60 kW Wood Gasification for Rural Electricity",
paper presented in ASEAN Conference on Energy from Biomass,
Penang, October 1986.
6. Manurung, R, H. Susanto and Sudarno H, "Experiences in the
Operation of Rice Husk Gasification for Rural Electricity",
paper presented in ASEAN Conference on Energy from Biomass,
Penang, October 1986.
7. Susanto, H, "Field Experiences on the Operation of 15 kW
Gasification System for Rural Electricity", paper presented
in ASEAN Workshop on Thermal Conversion of Biomass, Hatyai,
Thailand, September 1988.
8. Groeneveld, M, J, "The Cocurrent Moving Bed Gasifier". PhD
thesis, T.H. Twente, 1980.
9. Kjellstrom, B, "Practical Design of Producer Gas Systems",
a
lecture note in Producer Gas Course, the
Second
International Producer Gas Conference, Bandung, March 1985.
Appendix A : Location of the Presidential promotion units
1. Irian Jaya Unit
location: Desa (village) Arso III, transmigration site
Jayapura
fuel : wood wastes collected from the surrounding
local supervisor : Ministry of Transmigration,
Univercity of Pattimura, Ambon
end use of energy : rural electricity, at 6 12 p.m.
2. Maluku Unit
location : Desa Kaibobo, Seram Island
fuel : wood wastes from a nearby playwood industry
local supervisor : Ministry of Forestry,
University of Pattimura, Ambon
end use of energy : rural electricity, evening
100 houses with 100 W and 90 houses with 60 W
cost of electricity Rp 2500 3000/housemonth
(vs. to Rp 7000 using pressurized kerosene lamp)
3. Kupang Unit
location : Desa Nonbes and Oekabiti, Kecamatan Amarai
Kupang, Timor Island
fuel : wood (ipilipil) from regular land clearing
for traditional farming
local supervisor : Ministry of Forestry,
100 houses out of 300 planned
4. Sumbawa Unit
location : Desa Berra, Kecamatan Lape, Sumbawa Island
fuel : rice hulls
local supervisor : Centre for Enviromental Study of
University of Mataram, Mataram
288
325 houses
Samarinda Unit
location : Desa Segihan, Recamatan Sebulu,
Tenggarong, East Kalimantan
fuel : wood wastes from wood industry
local supervisor : PT. Pupuk Kaltim
(fertilizer company)
Institute of Technology in Surabaya
end use of energy : electric power for wood industry
rural electricity in the evening
Palembang Unit
location : Desa Sungai Buaya, Palembang, South Sumatra
fuel :wood wastes from house components industry
local supervisor : University of Sriwijaya,
PT PUPUK Sriwijaya (fertilizer comp,
end use of energy : electric power for wood industry
Appendix R : Technical Data the Presidential Promotion Units
Table II : Summary of technical data
Capacity
Type of gasifier
15 kW
65 kW
100 kW
co-current down draft

conventiona 1
Type of feedstock
small block of wood
3 - 6 cm
Capacity of bunker, litre
100
.350
350
Throat diameter, m
0.11
0.17
0.20
Height of red. zone, m
0.25
0.30
0.30
Diesel genset
BBI (Deutz Lisence), air
Number of cylinder
3
8
12
Cylinder volume, litre
2.827
12.763 19.144
r
Compression ratio =
1/17 ; Rev.per minute
Nomimal power output, kW
24
117
176
App. maximum power output
in dual fuel mode, kW
120
18
80
Gen. nominal output, kVA
25
125
180
(220/380V, 50 Hz, 3 phases)
40 kW
opencore
ricehulls
100
no
0.30
cooled
6
5.655
1500
51
40
50
The wood gasification unit is of a conventional system

[8,9]. The oxidation and reduction zones are lined with refractory. The throat is made of stainless steel plate with 12
mm thickness. The rice hulls gasifier is an open core type,
that has been developed at ITB and the University of Twente
[2], and also in the fields in Majalengka for rural electricity [6] and in Mojokerto for a rice milling.
In the 40, 65 kW and 100 kW units, the gas cooling is
accomplished by a forced air-cooled pipe heat exchanger. While
in the 15 kW units, the gas is cooled down in a natural draft
air-cooled horizontal pipe. The gas filter was filled with a
low cost filter medium which may be locally available such as
rice hulls and coconut fiber.
In the large units of 65 kW and 100 kW, a blower is used
to drive the producer gas during start-up for 5 - 1 0 minutes.
289
In the smaller units, a gas ejector activated by the engine
exhaust gas is used to suck the gas during the start-up in
place of the blower. The gas/air mixing device is a simple "T"
connection.
Appendix C : Balong Field Unit (Middle Java)
Balong unit with a capacity of 15 kW electric has been
operated for rural electricity since Februari 1984. Its daily
operating hour is about 6 - 8 hours, and now it has a total
operating hour of more than 14000 hours. The gasification
feedstock is rubber wood waste. The average diesel oil replacement by the producer gas is about 80%. The following table
show the operation cost, excluding investment.
Table III : Operating and Economic Data (successive 4 months)
month
operating hours :
in dual fuel
in full oil
diesel oil cost, Rp lOOOx
1
231
0
28.6
(147.)
206
18
40.0
(117.)
(407)
wood cost, Rp lOOOx
14.0
(77)
(17.)
(47)
wood preparation, Rp lOOOx
51.7
55.3
45.0
(257)
engine maintenance, Rp lOOOx

gasf.unit maintnce, Rp lOOOx
Rp lOOOx
(197)
4.0
(27)
29.7
(147)
(B7)
(77.)
(07)
(77.)
150
15.0
15.0
(67)
(77.)
72.5
89.4
20.0
75.2
207
('
(407)
97.5
(267)
0.0
(277)
24.7
(367)
t o t a l ,
(157)
10.0
141
0
56.7
17.5
(107)
operators' salary, Rp lOOOx
5.0
146
32
93.9
(307)
372
236
1 O O 7
15.4
(437)
210
.)
*/ number in parenthesis is percentage to total op. cost

/ wood purchase in a respective month
/ transportation and cutting into small block (3x3x8 cm )
/ lubricating oil and its filter, air filter etc.
/ rockwool filter, nut, bolt, packing, welding etc.
/ one technician and two low skill operators
exchange rate : 1 USD = Rp 1650
(May 1989)
For comparison, annuity vs annual operating
diesel genset (15 years life time)
gasification unit (8 years)
power house and electric distr. (15 years)
cost :
= Rp 1900000,= Rp 1610000,= Rp 520000,-
total operating cost (see the above table) = Rp 3000000,-
290
GASIFICATION AND PYROLYSIS OF STRAW - RESEARCH IN DENMARK
G. Olsen, P.H. Pedersen, U. Henriksen and E. Kofoed
Laboratory for Energetics
Technical University of Denmark
SUMMARY
Straw has been pyrolysed and gasified in batch and continuous reactors. The effect of dolomite as a tar cracking
catalyst has been studied and experiments with other
catalysts will be performed in the future.
The termal
cracking of pyrolysis tar and the effect of residence time
in the cracking zone has been studied. The heat transmission in straw of various densities formed the basis of
dimensioning of a continuous reactor for pyrolysing straw.
A continuous reactor for gasification of loose straw has
been developed.
Superheated steam has been used as the
gasifying agent.
Future gasification experiments will
include C0 2 and air as gasifying agents.
BACKGROUND
In - 1986 the Danish Ministry of Energy decided that
future small scale combined heat and power stations should
be based on domestic energy sources like natural gas,
wastes and biomass.
Additionally the field burning of
straw has been banned from 1990, which increases the
interest in discovering alternative applications for straw.
For smaller combined heating and power plants, the
energy efficiency would improve if an engine was used
instead of a steam turbine to deliver the mechanical energy
to the generator.
For this reason a research and development program has
been started regarding pyrolysis and gasification of
biomasses, mainly straw.
The research at the Laboratory
for Energetics started in February 1988, and has the object
of making the Laboratory a center of knowledge in Denmark.
The collection of data is obtained by literature studies,
through visits to institutions and departments having R&D
in gasification of biomass and especially by experimental
work. The Laboratory has also participated in the develment of a pyrolysing unit in co-operation with a consulting
engineering company.
The experiments in this paper are
only concerned with the research performed at the Laboratory for Energetics.
The research has been split up into 5 main subjects:
291
1.
2.
3.
4.
Know-how.
Gas from straw as fuel in small co-generation plants.
Gas purification.
Tar products used as fuel in internal combustion
engines.
5. Gas from pyrolysis and gasification of straw as fuel in
gas engines.
1. TEST EQUIPMENT AND EXPERIMENTS
1.1 Batch
The experimental work started with small scale batch
experiments.
Batches of 50 g straw were pyrolysed by
external heating in a cylindrical reactor with a heating
rate of 10C per minute. The condensate was collected in a
cooling trap (Figure 1).
Pyrolysis reactor
Gas outlet
&S
Ice bath
Figure 1: Pyrolysis - batch.

The same experiments were carried out with a second
reactor, of the same dimensions as reactor no. 1, installed
after - the first reactor so that the pyrolysis products
were fed immediately through the second reactor.
The
external heating of the second reactor was independent of
the heating of the first reactor (Figure 2).
IS
Pyrolysis
reactor
Second reactor
X
Gas outlet <
Figure 2: Pyrolysis - batch - second reactor.
292
The tar cracking effect of different materials such as
CaCC>3, dolomite and stainless steel chips was studied at
various temperatures(1). The CaC03 and the dolomite were
precalcinated at 850C and the experiments were compared to
experiments with an empty second reactor at the same
temperature. Only dolomite was found to have an effect on
the amount of tar produced, as experiments with a second
reactor temperature of 900C showed a colourless, transpa
rent condensate and a clean gas.
The dolomite turned
black during the experiment, which was explained as deposit
of carbon black on the dolomite particles arised from the
tar cracking process.
The experiments were repeated with addition of super
heated steam as gasifying agent and it was shown that 50g
of char was completely gasified in one hour, and that the
carbon deposit on the dolomite was gasified.
Studies of heat transfer in straw of various density
have been performed in reactors of two different diameters.
Both reactors were cylindrical and the temperature in the
straw was measured from the center and out to the wall
during the heating from 20C to 900C. The gas outlet was
varied from a central outlet to peripheral outlet.
High density of straw shows a delay in temperature
increase and also a delay in reaching the final tempera
ture, but the heating rate is very dependent on the gas
outlet position (Figure 3 ) .
Time (minutes)
Centre 160 (kg/n3)

3
+ Centre 240 (kg/m )
Figure 3:
O Periphery 160 (kg/m3)

Periphery 240 (kg/m3)
Heat transmission in straw.
293
Recently the batch experimental equipment has been used
for pyrolysis data experiments where the gas produced is
collected in small cylinders according to the pyrolysing
temperature (Figure 4 ) .
Each cylinder contains gas
produced in 50C pyrolysis temperature intervals. The gas
is analysed and the amount is measured. The condensate is
measured volumetrically as a function of pyrolysis temperature.
The experiments have not been completed and the
results are yet to be published.
Pyrolysis reactor
Second reactor
JU
ill
ill
Gas c o l l e c t i n g
cylinders
Figure 4 : Pyrolysis data experiments.

1.2 Continuous
Two continuous reactors have been developed. One is a
downdraft gasifier which by means of a piston introduces
loose straw into a cylindrical, vertical reactor (Figure
5).
The gasifying agent is introduced into the reactor.
Ashes are accumulated in the reactor and gas is taken out
at the bottom from where it can be fed to a tar cracking
catalyst if desired.
So far, this reactor has only been
used for observations of the continuous gasification
process and the equipment still needs to be improved.
The second reactor, which in principle is similar to the
one just described, is mainly for pyrolysis of loose straw.
The experiments carried out with this equipment are described in the next paragraph.
294
Gasifying agent
Gas outlet
Figure 5: Continuous reactor.

2. TAR
One of the main problems in pyrolysing/gasifying straw is
the tar produced by the process. The gas produced by the
gasification gas must be suitable for a gas engine. Tar
will then be a problem as it is known to cause valves and
piston rings to stick when the engine is shut down.
The tar can be cracked thermally or catalytically to
gas and carbon black.
The thermal cracking of pyrolysis
tar has been studied as a function of cracking temperature
and residence time in the cracking zone.
The pyrolysis
products were passed through a chamber of varying size and
temperature ranging from 1.5 1 to 10 1 at respectively
600C to 1100C. The gas was then cooled in a condenser
and led through four gas washing bottles containing acetone
(Figure 6 ) .
Second reactor
Condenser
Four gas washing

bottles in series
Collection of char
Figur *: Thermal cracking of pyrolyaio tar.
295
The experiments showed a decrease in condensate when the
temperature was increased. No significant effect regarding
the amount of condensate was observed when the residence
time was prolonged.
The gas production, though, is
slightly increased by increasing residence time and also by
increasing temperature.
The gas composition is only
dependent on the cracking temperature and the heat of
combustion of the gas has its maximum at 800-900C (1).
The catalytic cracking of tar has been successfully
performed using precalcinated dolomite.
Commercially
available catalysts are yet to be studied.
REFERENCES
1. Rensfelt, E., C. Ekstrm: Fuel gas from municipal waste
in an integrated circulating fluid-bed gasification/
gas-cleaning process. Energy from biomass and wastes
XII, New Orleans, Feb. 1988.
2. Olsen, G.: Research in tarcracking and applications of
tar. Presented at the international conference:
Pyrolysis and Gasification, Luxembourg, May 1989.
296
AN INVESTIGATION INTO THE GASIFICATION OF LOW QUALITY

COAL WITH OXYGEN ENRICHED AIR IN A FIXED BED GASIFIER
A D ENGELBRECHT
Division of Energy Technology
CSIR, Pretoria, S A
Summary
The performance of air and steam blown gas producers
deteriorate rapidly when low quality high ash coals
are used as feedstock. An investigation was carried
out to determine to what extent gas quality and gas
output can be improved when the blast air is enriched
with oxygen. Extensive testing was done on a small
industrial scale gas producer plant (5 GJ per hour
output). Using the data obtained, a techno-economic
study was done to determine the optimum level of
oxygen enrichment to be used for various
coal
qualities. The investigation showed that enrichment
of air with oxygen was economically attractive based
on both capital expenditure and running costs.
1. INTRODUCTION
In South Africa approximately 1 million tons of coal
is consumed in gas producers annually. In these units the
coal is gasified with air and steam to produce a low Btugas mainly from bituminous coal and some anthracite. The
gas is used in industries where cheap heat is required,
such as the brick-making industry for the firing of brick
kilns, calcination of calcium carbonate in the paper and
board industry and for steam raising in boilers originally
designed for oil-firing. In certain heating applications
such as the manufacture of refractory materials, furnace
temperatures in excess of 1600 c 3 a r e required. Due to its
low calorific value (+-6 MJ/NM ) it is difficult to
achieve these temperatures with producer gas alone, and it
has to be enriched with expensive fuels such as Sasol gas
or LPG.
Another disadvantage of standard air and steam-blown
gas producers are their low thermal output to diameter
ratios. This is due to large amounts of inert nitrogen
that passes through the system. This leads to lengthy
payback periods on capital.
It has been suggested that oxygen enrichment (see
Appendix 1.2 for definition of oxygen enrichment as used
in this paper) of the blast air to a gas producer can in
the first place produce a cold clean gas to give flame
297
temperatures in excess of 1600 C, and in the second place
better thermal
output
to diameter
ratios.
Oxygen
enrichment has been attempted on some industrial gas
producers. These attempts have been mainly unsuccessful
due to a lack of understanding of the processes that occur
in a gas producer, and the relationship between blast
saturation temperature
and oxygen
enrichment.
(For
definition of blast saturation temperature see A ppendix
1.1).
When the blast
reaction,
C + 02
is
enriched with
>
CO
oxygen
the
oxidation
405.8 MJ/kg mol
occurs at a more rapid rate and more heat is generated in

the oxidation zone. To prevent the temperature in the
oxidation zone going above the ash fusion temperature of
the coal more steam is injected to cool the bed down by
the endothermic steam char gasification reaction,
C + 0
>
. + CO + 119.1 MJ/kg mol
the other gasification reaction,

C + C0 2
>
2CO
+ 160 MJ/kg mol
also occurs at a more rapid rate due to more C0

production by the oxidation reaction. From the above
reasoning it seems that the output and calorific value of
the gas will increase. It is, however, difficult to reason
quantitatively in this way because of the many complex
processes occurring simultaneously in the gasifier. A
mathematical model taking into account rates of chemical
reaction,
physical
transport
processes
and
the
thermodynamic relations can cast some light on
the
subject. Using this method to predict optimum operating
conditions and plant results could be risky because of the
lack in available kinetic data as well as heat and mass
transfer coefficients. It was, therefore, decided to use a
singlestage pilot gas producer to investigate the effect
of oxygen enrichment on plant operation and results. It is
felt that the results obtained on this singlestage unit
will also be applicable to a twostage gas producer. The
reason being that the processes of interest occur in the
oxidation and gasification zones which are similar for
both types of producer.
A prominent oxygen supply company was responsible for
the oxygen supply to the plant. The project was carried out
with their collaboration. Pure oxygen was added to air to
produce oxygen enriched air to the desired level. Pressure
swing adsorbtion processes to produce oxygen enriched air
298
are on a steep development curve and could become
economical than addition of pure oxygen.
more
2. GAS PRODUCER PLANT LAYOUT AND GASIFIER DIMENSIONS

The gas producer plant modified to incorporate oxygen
enrichment is given in Fig 1. The gasifier is a 0.83 m
internal diameter firebrick lined vessel. The gasifier
dimensions are given in Fig 2.
The gasifier is of the fixed bed type with coal being
charged at the top and ash being removed at the bottom
below the grate. The reactants (air, steam and oxygen) are
introduced into the bottom of the gasifier and flow
upwards countercurrently to the fixed bed of coal that
moves downwards. The gas that is produced is removed from
the top of the gasifier. A fixed bed gasifier can be
divided into 3 zones. At the bottom of the bed the
oxidation reactions occur to provide heat for endothermic
reactions in the gasification zones above it. At the top
of the bed the volatile matter of the feed coal is driven
off by the hot gases moving upwards. This zone is referred
to as the devolatilization zone.
The gasifier has pokeholes at the top and bottom so
that any large clinker that is formed can be broken up.
The pokeholes are also used to determine the height of the
coal bed and the position of the fire zone that has to
remain fixed.
3. RESULTS
To investigate the effect of oxygen enrichment on gas
output and thermal output the total volumetric blast rate
was kept constant at each level of enrichment. Only the
proportion of 0_, N_ and steam were altered to give the
required
oxygen
enrichment
and
blast
saturation
temperature. The above approach was followed since the
total volumetric blast rate effects the gas output and
thermal output at constant levels of oxygen enrichment and
blast saturation temperature.
Before the tests on oxygen enrichment were started, a
datum test was done using air (ie. 0% oxygen enrichment).
This test was done to measure the improvement that oxygen
enrichment has at each level. Results of tests
at
different levels of oxygen enrichment are given in Table
1. To get a good average result, the duration of each test
was 18 hours. Fig 3 and Fig 5 show the increase in
calorific value and thermal output at different levels of
oxygen enrichment. It can be seen that at 9.9% oxygen
enrichment, the calorific value of the gas had increased
by 42% and the thermal output by 64%. Fig 4 shows the
variation in gas composition at different levels of oxygen
enrichment.
4. DISCUSSION
From an operational point
of view oxygen
enrichment
299
has given no problems. This is due to careful operation at
correct blast saturation temperature at each level of
oxygen enrichment. At the
higher levels of
oxygen
enrichment (6%, 8%
and 10%)
the blast
saturation
temperature had to be controlled within +- 1.5 C. In the
case of air operation the margin of error was +- 3.0
C.
If the BST was allowed to drop too low the maximum
temperature in the gas producer rose above the ash fusion
temperature of the coal and large clinkers were formed. If
the BST rose too high the gas quality decreased and carbon
burn-out deteriorated due to a cool fire zone.
The required accuracy in blast saturation temperature
can easily be achieved with a fairly cheap control system.
It is felt that a lot of problems encountered
on
industrial gas producers using oxygen enrichment were
caused by operation at too high a BST.
From Fig 4 it can be seen that the CO- concentration
increased with an increase in oxygen enrichment. Because
more oxygen is injected into the gasifier more CO- is
formed from the oxidation reaction C + 0_
> CO.
Because of the slower kinetics of tne C + CO>
2CO reaction, the rate of CO conversion is not as rapid
as the CO- formation. This results in higher levels of COin the product gas at higher levels of oxygen enrichment.
This effect makes it unattractive to go to higher levels
of oxygen enrichment since the additional oxygen is
converted to CO- and not to useful gas.
The amount of steam that can be converted by steam
char gasification reaction
C + H-O
> CO + H-
is limited by the maximum temperature in the reactor and

the rate constant of the above reaction. At higher levels
of oxygen enrichment most of the additional steam only
acts as a dilutant
and passes through the
system
unconverted.
REFERENCES
(1)
(2)
(3)
(4)
CLARK, D., The current status of coal gasification in

South Africa and its prospects for the future.
HOWELL,
A.N.,
Gas
producer
economics.
Coal
Gasification Symposium, Wanderers Club, Johannesburg,
9 June 1982.
Gas producers Symposium,
Transvaal Coal
Owners
Association, South Africa, 1974.
PAREKH, D., Handbook of gasifiers and gas treatment
systems, DOE/ET/10/59 - T24.
Oi
o
o
Rotameter
Water seals
Tar extractor
Tar separator overflow to ponds
Fig. 1. Gas producer modified for pressurized operation and oxygen enrichment
301
LEVEL OF ENRICH
MENT OF BLA ST(X)
0.0
l.B
4.1
6.0
B.O
7.9
COOL FEEORATE(KB/H)
69.0
72.7
7B.7
B9.2
103.2
llO.O
0.0
3.3
7.3
9.6
12.4
14.
103.6
OXYGEN FLOWRATE(NH3/H)
AIR FLOHRATE (NM3/H)
14B.B
143.2
130.7
119.
110.9
STEAM FLOWRATECKB/H)
26.3
30.3
33.2
37.7
39.1
42.3
BLAST SAT. TEMP.(C)
33.4
SB.2
60.4
63.7
63.1
66.9
GAS OUTPUT (NM3/H)
229.7
223.1
23B.9
247.3
269.O
CALORIFIC VALUE(MJ/NM3) 3.9

(BTU/NCF) 137.6
6.0
162.4
6.9
IBS.3
7.6
203.6
B.l
217.6
GAS TEMPERATURE (C)
357.6
33B.1
306.3
333.2
364.0
HOT RAU BAS EFF.()
B3.1
BO.O
B7.7
BS.6
BB.l
B2.7
HOT DETARRED BAS EFF(X) 73.0
73.2
BO.7
BO.4
79.3
74.2
COLD CLEAN BAS EFF(X)
6B.0
76.3
73.
73.1
70.3
69.3
8.3
223.4
Steam out
^y\
Anular boiler
0.92 m
* Gas outlet
Insulation
material
Firebrick
lining 0.15 m
I.D.
Coal bed
Depth 1.51 m
*0.83 m
Pokehole
B l a s t pipe 0.15 m
Steam + oxygen
oxyge + a i r
Fig.
'
2. Gas p r o d u c e r d i m e n s i o n s
302
i
Fig. 3. Effect of oxygen

enrichment on the
calorific value
of gas
9'
7
6
>
V
U U
U
i*j
5"
4
Iti
4
U O

3
2
I

5 6 7 9 10
2 3
Oxygen enrichment (%)

enrichment on gas
composition
V
in
2,501
2,23

enrichment on thermal
output at a constant
blast rate
2,00
1.75
1,50
1,25
3 4 5 6 7 8 9
10
303
APPENDIX 1
1.1 Explanation of the term "blast saturation temperature"
(BST) .
Blast saturation temperature refers to the amount of
water vapour present in the air blast. The air is
saturated with water at the particular temperature
(BST) and from the partial pressure of water at this
temperature and the total pressure the AIR/HO ratio
can be calculated. The blast saturation temperature
is a convenient way of measuring the ratio of air
flow to steam flow since it requires the measurement
of only one patrameter (BST) and of the determination
of both flows separately.
In the case of oxygen enrichment the blast saturation
temperature refers to the ratio of water vapour to
enriched air. It can, therefore, be used just as in
the standard air blown case to control the 0/H_0
ratio of the blast.
The blast saturation temperature will not give a
consistent indication of the 0_/H_0 ratio if the
blast is oversaturated or undersaturated. For the
blast to be just saturated the air and steam have to
meet the following requirement before mixing.
For blast saturation temperatures in the range
10 C
100 C
<
<
5070
A ir temperature < 35 C
Steam temperature < 125 C
1.2 Definition of oxygen enrichment

The percentage oxygen enrichment used in this paper
is the
difference
between
the
enriched
air
concentration and 21. For example:
(AIR FLOW).(0.21) + 0~ FLOW
% 0 enrichment =
100 21
AIR FLOW
0 FLOW
1.3 Coal composition used for O,. enrichment trials

Proximate analysis
ultimate analysis
Calorific value(MK/kg) 27.5
Carbon(%)
68.2
Ash(%)
15.18
Hydrogen(%)
4.20
H20(%)
2.70
Nitrogeni %)
1.70
Fixed carbon(%)
53.50
Sulphur(%)
0.80
Volatile matter(%)
28.70
Oxygen(%)
7.40
304
PRESSURIZED FLUIDIZED BED GASIFICATION OF PEAT
E. KURKELA, P. STHLBERG, W. MOJTAHEDI & M. NIEMINEN
Technical Research Centre of Finland (VTT)
Laboratory of Fuel Processing Technology
SF-02150 Espoo, Finland
Summary
An experimental research project on pressurized buildized-bed gasification of peat and wood waste was initiated at the Technical Research
Centre of Finland (VTT) in 1986. This research is related to the development of Gas Turbine Power Plants based on air gasification and hot
gas clean-up.The first test runs with the pressurized gasifier were
carried out in summer 1988. The gasifier was operated at pressures of
up to 10 bar and the maximum thermal input with peat was 400 kW. Air
and steam were used as gasification agents. During 175 hours of operation 11 tons of peat was successfully gasified. The effect of
operating conditions on gas composition, tar formation and fines
elutriation was investigated. Carbon conversion without cyclone dust
recycle was 75 - 85 % and the calorific value of the gas (LHV) ranged
4 - 4 . 5 MJ/Nm3. Alkali metals release in fluidized-bed gasification of
peat was investigated experimentally and theoretically. Samples were
taken from various points and analyzed for the alkali metal content.
The results are compared with the theoretically predicted values.
1.
INTRODUCTION
Power production from coal with Integrated Gasification-Combined
Cycle (IGCC) is becoming an increasingly promising technology for the
1990s. Processes based on oxygen gasification and cold gas cleanup offer
an environmentally acceptable alternative for coal utilization. These
IGCC processes can already now be considered commercial. Oxygen
gasification, however, is not economically competitive in small and
medium-size scale power plants. Hot gas cleanup is also an alternative
which has potential for increasing the efficiency of power generation
significantly IM.
Using air gasification and hot gas cleanup seems to
be a promising method for simplifying the IGCC process.
A joint research project to study Pressurized Fluidized Bed Combustion (PFBC) and pressurized gasification was initiated in 1988 in Finland in which IVO Oy (the largest utility company in Finland), Helsinki
University of Technology and VTT are cooperating. This project is part
of the National Combustion Research Program "Liekki", which is financed
by the Finnish Ministry of Trade and Industry.
The main emphasis of this research project is on the utilization of
peat and wood wastes, which are the only important indigenous solid
fuels in Finland. The project was started by designing and constructing
the PFBC/G test rig, capable of operating at pressures up to 10 bar. The
test rig was commissioned in summer 1987 and it is located at the Laboratory of Fuel Processing Technology of VTT. During 1987 the test rig
was used for studying fluidized bed combustion /2, 3/. This paper pre-
305
sents some of the results from the first gasification test period in the
summer 1988.
The goals of the first phase of gasification experiments were:
a)
to study the effect of operating conditions on gasifier performance
(carbon conversion, gas composition),
b)
to generate basic data on gas impurities, which are released in peat
gasification and might cause problems in gas turbines (alkali
metals, particulates) or in high-temperature filters (tars).
One of the most important research topics in this project is the behaviour of alkali metals in gasification. There are very little measured
data available on alkali metals release in coal gasification and no data
at all on peat or wood waste gasification. Thermodynamic projections /k,
5/ however show that alkali metals volatilization might be a severe
problem in IGCC systems applying hot gas cleanup. Vapor phase alkali
metals cannot be removed by hot filtration and the conventional
standards for gas turbines typically limit the alkali levels to below
0.1 ppm (w) in flue gases entering the turbine.
2.
EXPERIMENTAL
A schematic diagram of the Pressurized Fluidized Bed Gasification
(PFBG) test facility is shown in Figure 1 and some of the technical data
for the rig are presented in Table I. The heart of the facility is the
reactor, which is a 5.6 m high pressure vessel of 0.6 m in indiameter.
Its inside is refractory-lined to provide a bed diameter of 0.15 m and
freeboard diameter of 0.25 m.
Primary gasification air and steam were introduced to the reactor
through a multiorifice plate distributor. Secondary air was introduced
above the fluidized bed to increase freeboard temperature in order to
crack tars and improve carbon conversion. Hot gases leave the freeboard
and pass first through two cyclones operating at high temperature (e.g.
800 C)and then through a third cyclone operating at reduced temperature
(e.g. 300 C). Finally, after the pressure let down, the product gas is
burnt in an atmospheric combustion chamber. The elutriated fines captured in the cyclones were collected and weighed. Recirculation of fines
was not effected in these experiments .
The test rig included a wide range of measuring devices and sampling
systems. The gas analysis included on-line measurement of the major gas
components (CO, C0p, Hp, CHjj) as well as sampling systems for chromatographic analysis (Cj-Cc hydrocarbons, H2S). For the determination of
tars and NHo a gas slipstream was led through heated lines into gas
washing bottles filled with dichlormethane (for tars) or an aqueous solution of 5 % H2S0ij (for NHo). Detailed description of sampling methods
for both gas and tars as well as analytical techniques are described
elsewhere /6, 7/.
Particle measurements were based on isokinetic sampling. Samples are
extracted from the gas duct after the second cyclone. Particle concentrations were determined using an absolute filter, which was placed
in an electrically heated casing. The size distribution was measured by
coulter counter from collected samples. A detailed description of particle measurements is given in /8/.
For the determination of the concentration of vapour phase alkali
metals in product gas a sample was led through an absolute filter into
gas washing bottles. The sampling lines and the filter were electrically
heated to the same temperature as the gas exiting from the gasifier. The
sodium and potassium concentrations in the washing liquid samples were
determined by atomic absorption spectroscopy.
The gasification experiments were carried out using crushed peat
306
Gas analysis
Particulate
t sampling
Rue gas
Tfb(min)
3rd CYCLONE I
Secondary air
PRESSURE
LETDOWN ll
Waste
water
Dust removal
COMBUSTOR
Primary air
Dust removal
Steam
t Bed removal
Figure 1.
Schematic diagram of the pressurized fluidized bed

gasification test facility.
Table I. Technical data of the Otaniemi PFBG test rig.

Thermal input
Fuel
Operating pressure
Bed temperature
Free board temperature
Fluidizing velocity
Gasification agents
Product gas flow rate
Bed diameter
Freeboard diameter
Effective height of the reactor
Gas cleanup
400 kW
peat, wood, brown coal
4 - 1 0 bar (abs)
750 - 850 C
750 - 1000 C
0.6 - 1.5 m/s
air and steam
90 - 220 Nm3/h
0.15 m
0.25 m
3.5 m
two cyclones, ceramic
filter unit (1989-)
pellets as fuel. Peat pellets of 15 - 25 % moisture were crushed in a

hammer mill. Two particle size ranges were used in the tests, 0 - 3 mm
and 0 - 5 mm. The properties of raw material (feedstock) is shown in
Table II. The moisture, the ash, the volatile matter and the sulfur
contents of solid samples were determined by routine methods (DIN 51718
- 51820, and A STM D 4239 respectively). The C, H, and contents were
determined with a LECO CHN-600 instrument. The Na and K-contents of
307
Table II. The properties of gasified peat.
Particle size range
Bulk density
Moisture content (wet basis)
Volatile matter (dry basis)
Dry matter analysis
C
H
0
S
Ash
Nacontent of ash
Kcontent of ash
Lower heating value (dry basis)
0 _ 5
mm
575 25 kg/m3
% w/w
20 5
67.5 1.5 % w/w
55.5
5.6
1.8
32.4
0.18
4.5
0.67
0.93
20.5
1.5
0.2
0.4
1.5
0.04
0.5
0.03
0.03
0.5
% w/w
% w/w
% w/w
w/w
% w/w
% w/w
% w/w
% w/w
MJ/kg
solid samples were analyzed by atomic absorption spectroscopy for ashed

samples which were prepared according to DIN 51070.
3.
RESULTS AND DISCUSSION

A total of 13 tons of peat was gasified during 175 hours of opera
tion. The test runs were conducted at three different pressures and with
different air to steam ratios, totaling 13 different operating set
points. Some of these results are shown in Table III. The H2O content of
the product gas was calculated from hydrogen balance and the fuel gas
flow rate from nitrogen balance. Carbon conversion efficiencies were
calculated as carbon in products/carbon in gasified peat. Other figures
in Table III are average values of the measured data.
The gasification pressure (in the range of 5 10 bar) did not seem
to have a significant effect on the carbon conversion. Figure 2 shows a
carbon balance for a typical set point. The most important carbon loss
was in the form of elutriated fines, which contained 12 20 weight of
the feed carbon. A dding secondary gasification air to the freeboard and
increasing the steam feed improved carbon conversion which was, in the
best set points, in the range of 80 85 .
Approximately 80 90 wtJ of the elutriated fines were captured by
the first cyclone and the dust concentration in the product gas after
the second cyclone was 4 8 g/Nm3 with a particle size range of 0 20
pm.
The net calorific value of the product gas was 3.8 4.5 MJ/Nm3 (wet
gas) and the tar content generally ranged 4 6 g/Nm3, which represents
2 4 % of the energy input of the gasified peat. The major part of tars
were light oils like benzene, toluene and naphtalene. Figures 3 and 4
show the effect of freeboard temperature on the naphtalene and phenol
concentrations of the product gas.
Set point 3/5B, with an air feed rate of only 1.4 Nm3/kg peat (maf),
is in many respects different from the other set points. Since the car
bon conversion was only 73 1>, this set point can be considered to cor
respond to conditions prevalent in partial gasification. The total con
centration of tars was high, 10 14 g/Nm3, and the tars were composed
of a wide variety of typical pyrolysis products from light oils to heavy
tars.
Table IV shows the measured vapour phase alkali metals concentra
308
Table III. Results for different set points.
3/3B
3/5B
4/5
4/1
5.01
18.5
14.8
18.7
11.5
7.07
21.2
16.2
22.5
12.8
9.55
21.4
15.5
23.4
12.2
2.4
832
862
790
5.2
831
868
795
7.5
822
856
800
4/3B
Gasification pressure, bar (abs)

Peat feed rate, g/s
Peat moisture content, % w
Primary air feed, g/s
Secondary air feed, g/s
Steam feed, g/s
Bed temperature, C
Freeboard temperature (max), C
Temperature before cyclone, C
Gas velocity in freeboard, m/s
4.97
12.6
17.5
20.2
5.09
15.8
17.2
21.8
1.0
1.3
815
806
730
1.0
0.0
817
803
700
0.48
0.50
0.73
0.65
0.50
Fuel gas output, NnH/h (wet gas)

Fuel gas composition, % vol
(wet gas)
109
117
166
198
207
10.6
13.7
13.7
10.8
12.5
10.1
11.9
13.6
13.2
9.6
9.2
13.9
12.7
13.2
12.1
CO
co
H 2
2
CHn
C 2 Hn
C2Hc
N2+Ar
H20
Tars+oils:
Benzene, mg/Nm^ (wet gas)
Toluene, mg/ (wet gas)
Naphtalene, mg/Nup (wet gas)
Tars & oils total, mg/NnP
Carbon conversion efficiency, % w
to dry product gas
to gas + tars
3.3
3.6
3.6
3.4
3.7
0.34
0.24
45.3
12.8
0.58
0.31
47.3
14.8
0.35
0.15
44.8
12.3
0.24
0.16
42.7
17.4
0.17
0.19
39.9
21.5
3600
3930
3700
3520
130
705
65
740
45
670
5500
5170
1240
1480
11200
5300
5100
4800
80.7
83.3
68.7
73.5
79.3
81.7
83.6
86.2
81.2
83.7
510
705
tions of the product gas for three set points. Due to the small number
of samples and the generally known problems in the reliability of
sampling methods, no final conclusions should be drawn from these
figures concerning the effect of operating conditions on the release of
alkali metals. However, the total concentration of alkali metals in the
product gas seems to be at least an order of magnitude higher than
allowable to a gas turbine but not quite as high as predicted by
thermodynamic equilibrium calculations.
4.
CONCLUSIONS AND FUTURE RESEARCH

The calorific value of the product gas from air gasification of peat
was more than 4 MJ/Nm^ and the gas was readily combustible without
additional support flame. The carbon conversion of gasification was,
however, too low for economic power production. Carbon conversion in
fullscale plants will be improved to certain extent by increasing the
reactor height and the residence time of the particles. However, con
versions >95 % can be achieved only by efficient recycling of all
separated particulates. The freeboard temperature should be elevated
from 870 C, which was the maximum temperature reached in these
experiments. However, the maximum temperature is limited by the
sintering and slagging properties of the peat ash.
309
CONVESWN OF PEAT CARBON T O OFFERENT PRODUCTS:

SET POINT 4 / 5
A R1.eONm3/kgpe!(mf)
STEAM 0.305 kg/kaPrt(maf)
PRODUCTQAS 83.7 I
TA RS OLS 2 . %
PARTICULATES 1.%
12%'
' ' 0.1%
CYCLONE OUST
Figure 2. Carbon conversion for a typical set point.
2400
2000
1600
1200
'. A R 1.4 Nm3/kgpeat(inaf)
< 3 mm, 5 bar
< 3 mm. 7 bar
<3mm. 9 . 5 bar
X
Peel < 3 mm
V
X
400
<5mm, 45ber
+ \
AR 1.61.8 Nma/kopMtyMf)
800
780
~~ Pert.5mm
F_
800
820
840
860
FREEBOARD TEMPERATURE ( C )
Figure 3 The effect of freeboard temperature on the naphtalene content
of the product gas (dry gas).
310
(
An 1.4 Nm3/kgpeat(maf)
600
< 3 mm, 5 bar
< 3 mm, 7 bar
< 3 mm, 9 . 5 bar
>
< 5 mm. 4 5 bar
400
(1
111
Q.
200
+
++
0
780
1
A m.e1.8Nm3/keprt<maf>
800
820
Mt<f J f-\
nil
840
860
F R E E B O A R D TEMPERATURE ( C )
Figure 4.
The effect of freeboard temperature on the phenol concentra

tion in the product gas (dry gas).
Table IV. The measured Na and concentrations in the gasifier pro

duct gas (wet gas) and the proportion of peat alkali metals
released in the vapour phase.
Set
point
4/5
4/1
4/3B
ppmw
% of Na
in vapour
phase
ppmw
% of in
vapour
phase
3.84.3
2.1
2.3
4.04.6
2.4
2.7
0.981.1
1.3
0.8
0.760.86
1.1
0.68
Pressure
Tmax
Na
bar
5
7
9.55
862
868
856
Freeboard temperatures of 830 870 C seem to be high enough to

crack the heavy tars to benzene, naphtalene and other light components,
which should not be detrimental to hightemperature gas filtration. The
results from vapour phase alkali metals sampling seem to support the
conclusions drawn from thermodynamic projections, that the concentration
of alkali vapours has to be reduced before combusting the product gas in
a gas turbine. This can be achieved by cooling the ga3 before filtration
or by using special getters like aluminosilicates.
The next phase of the gasification research will be carried out in
summer 1989. The experiments will focus on studying the effect of fines
recycling on the carbon conversion as well as the applicability of
311
ceramic candle filters to PFB gasification. A n online alkali vapour
measuring device has been constructed to enable a more accurate
measurement of the alkali metal vapours in gasification. This device,
based on atomic emission spectroscopy, will be used in the next phase
(summer 1989) of the PFB gasification experiments.
ACKNOWLEDGEMENTS
The authors wish to acknowledge the assistance of the technical and
analytical staff of the Laboratory. Special thanks are expressed to Mr.
Reino Flinkman and Mr. Jarmo Kleemola for operating the test facility.
REFERENCES
1.
Solantausta, Y. & Kurkela, E. The production of electricity from
peat by Integrated Gasification CombinedCycle Conversion. IGT Conf.
on Biomass and Wastes XII, New Orleans, Feb 15 19, 1988. 12 p.
2.
Horvath, ., Hulkkonen, S. & Jahkola, A. Emissions of a peat burning
pressurized fluidizeed bed combustor. Int. FBC Conf., Dec 12
13,.1988, London, UK. 12 p.
3.
Hulkkonen, S., Jahkola, A . & Kurkela, E.
The Otaniemi PFBC/G
research project. The 10th Int. Conf. on Fluidized Bed Combustion,
San Francisco, April 30 May 3, 1989. 8 s.
4.
Mojtahedi, W. & Backman, R. A lkali
metals volatilisation in
pressurized fluidized bed combustion and gasification of peat. 4th
Int. Fluidized Combustion Conf., Dec 1213, London, U.K. 16 p.
5.
Mojtahedi, W. & Backman, R. Release of alkali metals in pressurised
fluidisedbed combustion and gasification of peat. Espoo 1989,
Technical Research Centre of Finland, Publications 53. 48 p.
6.
Lepplahti, J., Sthlberg, P., Simell, P.
Nitrogen compounds in
peat and wood gasification and gas combustion. Conf. on Research in
Thermochemical Biomass Conversion, May 2 6 , 1988, Phoenix, A ri
zona, USA. 14 p.
7.
Simell, P. Kotimaisten polttoaineiden kaasutuksessa syntyvt terva
maiset eppuhtaudet (Tarry impurities developed in the gasification
of indigenous fuels). Espoo 1988, Technical Research Centre of Fin
land, Research Reports 631. 53 p. + app. 22 p. (in Finnish).
8.
Hulkkonen, S.
Particle Measurements of the Otaniemi PFBC/G test
rig. Espoo 1988, Technical Research Centre of Finland, Symposium
Series 83, p. 251 262.
312
RAPPORTEURS REPORT ON SESSION V

GASIFICATION CASE STUD IES
. MANIAI S
Free university of Brussels, Belgium
A.A.CM. BEENACKERS
Groningen University, The Netherlands
1. INTRODUCTION
The seven papers presented in this session indicate that extensive research has
been carried out in the field of biomass, wastes and solid fuels gasification in a
variety of reactor configurations and at practically every scale of operation varying
from the laboratory scale up to full scale demonstration plants.
However, commercialization has been hampered due to the low cost of
hydrocarbon fuels and to technical problems concerned with the use of the fuel gas in
engines, (see also rapporteur's summary of session 6).
Extensive efforts have been made by several Less Developed Countries and most
notably by Indonesia, for the implementation of gasification technologies in rural
areas (see also rapporteur's summary of session 3). In Less Developed countries, not
only techno-economic problems must be overcome but social barriers as well in order
to allow for the successful introduction, operation and maintenance of gasifiers and
their supporting systems.
2. DISCUSSION
Professor Corella commented that the performance of the ITALENERGIE dual
fluidized bed pyrolyzer/gasifier reactor was not optimal since the operating
temperature was too low and the specific throughput was only 100-300 kg/(hr. m 2
while much higher values have been reported by Battelle Columbus at 9000 kg/(hr.
m2) The low bed height to bed diameter ratio was mentioned as a possible cause. The
chairman of the section, Professor Beenackers, responded that indeed operating
problems exist but these were related mainly to the heat transfer through the wall
separating the two fluidized beds. Dr. Fonzi added that the main cause for the
operating problems was related to the new operating regime of the reactor which was
used only as a gasifier to produce a fuel gas and not synthesis gas as originally
foreseen.
In response to Dr. Shah's suggestion that local manufacturing of gasifiers in
Indonesia and more generally in the Less Developed Countries will accelerate the
transfer of technology. Prof. Beenackers reported that indeed through the Dutch
Development Cooperation project JTA 9A in Indonesia gasifiers are manufactured
locally. Dr. Maniatis added that Darmawan, a private company and Bisma Borna Indra a
state owned company, both are involved in manufacturing gasifiers in Indonesia.
Dr. Stiles commented that successful introduction of gasifiers in Less Developed
Countries strongly depends on the selection of the right materials for construction.
Too often gasifiers are badly corroded after only a few months of operation. This was
accepted by the floor but it was also suggested by Dr. Maniatis that better motivation
of the operators can improve considerably the lifetime of a gasifier by careful
controlling of the particle size of the feedstock by which usually the yield of tars can
be reduced significantly.
313
Professor Corolla asked for extra information on the pressurized fluidized bed
gasification of peat and more specifically about the type of inert bed material used and
on the reduction of tars by catalytic activity of dolomite. Dr. Kurkela responded that
although the initial bed material was sand, it was soon replaced by peat ash. Tests
with dolomite are planned, however, the emphasis will not be on the reduction of the
yield of tars since tars are no problem as the gas is burned hot in a gas turbine, but in
improving on the carbon conversion efficiency. Dr Dierven suggested that it would be
useful to have continuous in-line measurements of the concentrations of the major
gaseous components such as H2, O2 etcetera.
Professor Beenackers wondered why part of the cyclone discharge is not recycled
in the Finnish peat gasifier in order to improve on the carbon conversion efficiency.
Dr Kurkela commented that the cyclone discharge consists of very fine particles
which are difficult to handle due to their low bulk density. On the commercial aspects
of turbines fueled by gasifiers Dr. Kurkela commented that such systems can be built
soon since there is some interest from private companies on such technology but
economics play an important role on the commercial prospects.
Dr. Capart asked whether the effect of heavy metals has been evaluated at all on
gasifiers but the Chairman commented that with biomass feedstocks there are no
problems with heavy metals in the gasifier.
On the question of Professor Corella concerning experiments with dolimite, Dr.
Olsen reported that all their experiments were carried out in a thermal cracking
reactor while catalytic cracking with dolomite has been planned for future research.
Dr. Stiles reported that with dolimite tars can be converted to gas and transparent
liquid while no sintering effect has been observed. His group is working in developing
secondary catalytic reactors for the conversion and subsequent elimination of tars.
Dr Olsen commented on a question from Dr Shah, that current practice in Denmark for
straw disposal involves burning it while some heating plants also use straw as a fuel.
On a question by Dr. Dierven concerning the quality of coal used in the oxygen
enriched air updraft gasifier, Mr. Engelbergh replied that the coal had an ash content
of 25 wt % and a sulphur content of 1,5 wt %. In response to a question by Dr.
Maniatis concerning the economics of using oxygen as a gasifying medium Mr
Engelbergh stated that for the experiments in question liquid O2 from a storage tank
was used. However, he commented that with advances in pressure swing adsorption
techniques it will soon be possible to use of O2 seperation processes on site.
Prof. Beenaeckers enquired about the new aspects of this research in relation to
the Lurgi oxygen gasifier. Mr Engelbergh responded that the new aspects were in the
operation below the ash fusion temperature of coal and in applying air enriched in
oxygen up to 10% instead of 100%. The 10% limit was governed mainly by
limitations in steam addition which in used as a temperature moderator. With no
further questions from the floor the Chairman acknowledged the valuable
contributions of the participants and closed the session.
SESSION VI
UPGRADING, CLEAN OP AND UTILIZATION OF PRODUCTS
317
Gas purification: areviewof the available methods of gas cleaning

P. GUIGON and J.F. LARGE
Universit de Technologie de Compigne, France
Summary
The paper discusses the available methods to be employed for cleaning gas emitted from
Biomass gasifiers. First the extent of treatment, according to utilisation of producer gas is
presented then the different gas treatment techniques are reviewed and arrangement of
cleaning devices suggested, depending of the use of the gas. Some cost considerations are
given.
At the present time many gasification installations depend on the use of gas cleaning systems which are powerful, reliable and economic within a given context and which give all the
guarantees required for the environment. The extent and difficulty involved in the cleaning of
a gas depends on many factors: the type of installation (fixed bed updraft, downdraft, crossflow, fluidized bed or circulating bed), the size of the installation, the type of biomass used
and its water content, transportation constraints and the eventual use of the gas. At the same
time, the solution adopted must take into account the site characteristics (availability of water,
electricity supply etc.). Whatever the production system used, the gas will contain varying
quantities of dust, tar and water vapour which will give aqueous condensates when cooled.
Therefore a series of different gas cleaning systems will be required. In order to prevent the
condensation of tars and their mixture with dust to form a semi-solid mixture which could
block parts of the apparatus, the first step consists of dust removal at high temperature. This
is followed by cooling of the gas by direct or indirect contact to its dew point, causing the
formation of liquid tars and aqueous condensates. It is then often necessary to use further
techniques in order to trap water and tar mists remaining in the gas. In the particular case
where the gas is to be used in chemical synthesis, it is also necessary to remove any catalytic
poisons which could affect following processes.
The best method to obtain a clean gas at the exit of the installation is to generate the least
amount of tar possible in the first instance. Most manufactureres claim extremely low concentrations and even complete absence of tars (except for fixed bed updraft gasifiers). Practical
experience and varied research shows that the removal of tar is a serious problem and that its
total elimination is not easy (1).
In figure 1 (2) emission of different gasifiers are given and in particular the tar and solids
content of the gas produced. The main method used to obtain low tar contents is to attain very
high temperatures either in the gasifier ( in the case of downdraft, DelaCotte type recirculating
or high temperature circulating bed) or in a post combustion chamber which may be catalytic.
Catalysts have also been used in the gasifier itself to reduce tar emissions and improve the
overall energy balance.
1 - TREATMENT (PURIFICATION) ACCORDING TO UTILISATION OF GAS
1.1 Gas for direct combustion
When the gas is used to supply a furnace directly, virtually no treatment is necessary. High
temperature dust removal by cyclones is usually sufficient. However, for the heating of brick
ovens, the direct drying of seeds, or the heating of greenhouses for example, a clean gas free
of tars and dust is required. It is particularly important to control the quantity of polycyclic
hydrocarbons when drying seeds (3). These hydrocarbons, contained in the combustion gas,
are deposited on the first layer of seeds which then acts as a granular filter.
318
1.2 Gas to supply motors and turbines
Gas leaving the gasifier at a temperature of between 300 C and 800 C must have both dust
and tar plus part of its water content removed. In diesel and spark ignition engines tars must
be reduced to 1050 mg m3. For turbines it is essential to maintain the temperature of the gas
above the dew point of condensable hydrocarbons (tars). However the inlet temperature of the
gas to the motor must be as low as possible in order to maximize its volumetric efficiency.
1.3 Synthesis gas
For gas used in chemical reactions it is not only necessary to remove dust by hot filtration,
but also tar and methane. This operation is either carried out in a secondary catalytic reformer
(Mino process) or in a noncatalytic reformer (National Synfuels, Kiener, Creu sotLoire).
Figure 2 (2) gives an overall view of the extent of gas cleaning with respect to the ultimate
use of the gas.
2 GAS TREATMENT TECHNIOI JES
2.1 Introduction
The methods used for the purification of gas produced by gasifiers have not evolved greatly
since the 1930's. In publication (4) 910 references describing not only the treatment of gas
from gasifiers but also that from high temperature furnaces and coke plants are itemized for the
period from 1920 1970. Due to interest in combustion and the use of coal gasifiers linked to
gas turbines, high temperature gas removal (>700 C) has been the subject of numerous labo
ratory experiments resulting in several pilot plants over the last few years. However, opinions
are still reserved over which solution to adopt for the industrial scale removal of dust from gas
and exhaust fumes at temperatures higher than 400C (5). Particulate and tar should not be re
moved in the same cleaning step to avoid any sticky combination of tars and char.
The classification of gas purification techniques is difficult. One approach is to use the col
lection mechanism (brownian diffusion, inerial impaction or interception), but, in general,
several of these mechanisms play a part in most purification systems. The efficiency of the
mechanism depends on the size of the particles or droplets to be trapped. Those which are
most difficult to remove are approximately in diameter. The types of equipment are clas
sified as follows: mechanical, hydraulic, electrofilters, porous layers filters and finally various
devices combining several of the above. Operating principles and calculating methods will not
be given here but can be found in numerous general texts dealing with gas purification, in
particular, references (6), (7) and (8). It is intended to concentrate more on the efficiency,
implementation and potential of particular devices. In order to facilitate the presentation of de
vices available for gas treatment, the treatment process is divided into three categories:
1) The trapping at high temperature (higher than the dew point) of most solid material.
2) Condensation and elimination of condensed droplets.
3) Elimination of mists.
2.2 High temperature trapping of particles
Purification always begins by the elimination of most of the particles at a temperature above
the dew point of the gas.
2.2.1 Mechanical devices
Sedimentation chambers and inertia devices which are only suitable for large particles are
little used in the field with which this report is concerned. Centrifugal devices are, however,
very often employed as they allow the separation at high temperature (temperatures at which
tars are gaseous) of most dust particles.
Classical cyclones
By the use of appropriate refractors little difficulty is encountered in the construction of de
vices capable of operating at 500 600 C. Using ceramics, cyclones have been fabricated
which can operate at 1000 C. This technique allows dust removal to be accomplished with
ease and results in very low dust concentrations. The efficiency with which dust particles are
319
removed by the cyclone depends on the inlet gas velocity and the diameter of the entrance
window. Classical cyclones follow certain rules linked to this diameter. Theoretically, both the
efficiency of dust removal and the pressure loss increase with increased entry speed and/or re
duced diameter. The size of the cyclone and its cost may be correlated to the inlet area.. In or
der to obtain low exit concentrations (around 300 mg/m3) consisting of small particles (around
5 ) it is necessary to use small diameter cyclones which in tum leads to the use of multicy
clones. By placing several cyclones (usually 3) in series, it is possible to obtain an output
compatible with the tolerances required for gas turbines.
However, the pressure loss and cost of these small cyclones is significant
Straightthrough cyclone with reverse flow
In order to improve the efficiency of the cyclones by reducing entrainment by bouncing
small particules off the wall, a flow of clean gas is added with a descending circulatory mo
vement . These devices have a very high effeciency (95% for particles > 5 ).
Straightthrough cyclone with moving impellers
Another solution to giving gases a rotational motion is to use rotating disc devices . The
principle of these devices necessitates careful design, construction and installation.
According to reference 9 there are some devices in existance which are capable of functio
ning at flowrates of 8000 n/h and a maximum temperature of 400 C. The output dust
concentration is of the order of several mg/NirA Devices capable of handling 100,000 Nm^/h
are being studied.
2.2.2 Hydraulic dust removal
In order to function at high temperature, the cleaning fluid must remain liquid, leading to
the use of organic fluids or salts. This technique results in very high efficiencies. At the pre
sent time very little research is being carried out in this field, probably due to problems envi
saged concerning corrosion and choice of materials.
2.2.3 Electrostatic filters
These filters are mainly used to collect airborn ash in modern pulverizedfuel power plants,
and seem well adapted to the elimination of soot suspended in combustion gases. Much re
search has been carried out to increase the operating temperature of theses filters. The main
difficulty encountered is to find materials which remain insulators at high temperatures. Fur
thermore, the dust particles must be capable of being attracted. Research appears promising,
but the problems of the behaviour of electric insulators, the dimensional stability of ionisation
cells and the removal of collected dust remain to be solved.
2.2.4 Porous layer filters
Two types can be identified: flexible fibrous or rigid porous devices and granular bed de
vices.
Flexible Fibrous or rigid porous layer dust removers
A simple and efficient method for the removal of particles from a stream of gas is to pass it
through a fabric or any other porous sheet material. Progress made in the last ten years has led
to very low output concentrations (<10 mg/Nm^). The medium serves only as a support, with
the trapped particles acting as a filter. The method used to clean the filter is extremely impor
tant, as a blocked filter can cause pressure losses to exceed acceptable limits.
Fibres which can be used at high temperatures include metallic, glass, carbon or ceramic.
Metallic Fibres
These can be used at temperatures up to 650 CC and have the advantages being capable of
being woven and being available in diameters as low as 2 . It is also possible to make sin
tered filtration media of adjustable permeability. The principle drawback is cost which has
precluded their general use except where otherfibresare not suitable.
Carbon Fibres
These can be used at very high temperatures in reducing atmospheres, but in an oxidising
atmosphere temperature is limited to 350 C. Furthermore, their mechanical strength is low.
Thus, their use for high temperature filtration is limited.
320
Glass and ceramic fibres
Quartz and ceramic fibres are capable of being used at temperatures well above those used
for the inlet gas to a gas turbine. Their main problem lies in the production of woven fabrics
and needled felts. Their cost is not prohibitive.
The Acurex corporation has commercialized a filtration system (10) working at 870 C.
Normal glass fibres are limited to use at temperatures below 450 C.
Granular bed dust removal
The idea of a granular bed is not new, but is little used due to its cost, estimated at 125% of
the cost of an equivalent electrostatic precipitator (11). Such filters can be placed in three cate
gories: fixed bed, mobile bed and fluidised bed, and can be considered as efficient but costly.
One problem not yet totally resolved is behaviour in the presence of sticky particles, especially
during regeneration of the bed. Note that this problem can be avoided by the use of a
gasifiable solid so that regeneration of the bed is not necessary.
However, in general these filters cause a high pressure drop and cost more than other filters
in terms of maintenance. It is usually, therefore, cheaper to use cyclones, scrubbers and elec
trostatic filters.
2.2.5 Combined dust removers and particle preconditioning
Electrocyclones
It has been shown that the most efficient cyclones are those of small diameter. By combi
ning the corona effect and cyclone phenomena, the same efficiency can be obtained for an
electrocyclone of 3.7 m diameter as for a normal cyclone of 0.25 m diameter.
Electrically enhanced fabric filter ((8) chapter 7)
By charging particles before entry to the filter, a more permeable cake is formed which in
tum allows the use offiltrationspeeds double those normally adopted.
Acoustic agglomeration
Particles of around are very difficult to trap and a number of experiments have been
carried out to try and cause them to agglomerate before separation using conventional tech
niques. Acoustic agglomeration appears promising (6).
2.2.6 Conclusion on hot gas cleaning
It would seem that no hot dust removal technique has yet reached the stage of being capable
of reducing dust concentration to levels compatible with gas turbines (5,9). Certain devices
accomplish primary dust removal at a reasonable price: multicyclones, straight through cy
clones with reverse flow and, in the future, electrocyclones. Granular beds may be interesting
if solid regeneration is not required. With new developments in ceramics, both flexible and ri
gid porous layerfilterscould become viable in the not too distant future.
2.3 Condensation and elimination of condensate droplets
The condensation of water vapour and tars contained in gases can be accomplished by ei
ther direct or indirect heat transfer. Indirect heat transfer is avoided as much as possible due to
the possibility of fouling the exchangers. Nearly all fixed gasifiers where a water supply is
available use water scrubbers. In certain cases, o scrubbers may be used.
2.3.1 Scrubbers
These devices allow droplets and particles to be collected while cooling the gas. Generally
they are used to remove condensed tar droplets and to eliminate soluable matter. It is then ge
nerally necessary to provide for mist elimination. These spray scrubbers exist in numerous
forms. In most cases, water or aqueous condensates constitute the scrubbing agent, but occa
sionally oil, which has an absorption efficiency higher than that of water, may be used. These
scrubbers cause problems for the treatment of the liquid effluent as all soluable organic com
ponents are recovered in the aqueous phase.
Spray towers.
The spray tower is the simplest type of scrubber. It consists of an empty tower in which the
gas flows through a mist of water droplets formed by suitably placed jets. Countercurrent,
321
cocurrent or crossflow configurations may be adopted. These towers are excellent for col
lecting large particles and for cooling the gas.
Centrifugal spray scrubbers
The use of centrifugal force allows the removal efficiency of the spray scrubber to be in
creased by increasing the speed of the droplets in relation to that of the gas. Small baffles give
the gas a spiral motion. This increase in efficiency is counterbalanced by a higher pressure
drop across the system. Such devices have an efficiency of more than 97% for particles larger
than .
Self induced spray scrubbers
In this type of scrubber the gas is introduced at high speed just above or below the surface
of the liquid. The resulting high turbulence give rise to excellent gas/liquid contact. The ad
vantage of these scrubbers is their ability to cope with high solids concentrations.
Impingement plate and packed column scrubbers
The gas to be treated passes through a series of liquid layers. These scrubbers are more ef
ficient for the removal of fine particles than evaporative scrubbers, but result in high pressure
drops. The design of the columns is analogous to that of plate distillation columns or packed
absorbers. The type of packing used can be commercially available or manufactured using a
variety of materials.
Disintegrator scrubbers
If very small particles must be recovered (smaller than ), the scrubber must provide a
very finely dispersed mist. These tiny droplets result in a very high surface area over which
contact can occur. In order to obtain this fine mist, the liquid is introduced between the rotor
and stator of a special device. The gas must be prepurified (concentrations < 23 g/m3) and
have particles greater than 10 eliminated, as these would tend to erode the baffles contai
ned within. Energy requirements are high (around 5.27.0 kJ/m3 of gas treated), but effi
ciency is excellent with respect to particles below .
Venturi type scrubbers
In this type of device the speed of the gas causes atomisation of the liquid. The energy is
supplied by the pressure loss of the gas. The efficiency is improved if conditions are created
such that condensation can occur in the throat of the venturi. Venturi scrubbers can be sup
plied with one or more throats in parallel or in series. Permanent pressure drop is of the order
of 0.4 to 1.0 kPa and efficiency can reach 99% for particles smaller than 5.
Free jet washers
In this device, atomisation of the water is caused by a jet of compressible fluid and takes
place around the exit nozzle of thisfluid.Pollutants are trapped in the turbulent region directly
following the jet
2.3.2 Electrofilters
Such filters have already been used with success in coking plants to eliminate tars. Various
electrode configurations are possible: a wire placed in the centre of a vertical cyclinder, perfo
rated or corrugated electrodes, or single or double plate electrodes. Efficiency is excellent
(greater then 99%). Pressure loss in these devices is low, which suits them to the treatment of
large flows. Small electrostatic filters capable of trapping tars emitted from gasifiers are being
studied (12).
2.4 Demisters
After leaving a cooling and condensation stage, the gas still contains water and tar in the
form of mists which must be trapped in demisters. These usually consist of a porous bed. As
the liquid particles agglomerate and flow by gravity there is no need for a cleaning system, but
it is of course necessary to provide a drain for the collected liquid. Materials which can be
used vary greatly. Woven metal is often employed; fibrous waste such as wood wool may
also be used. Large particles are usually trapped by a metallic grid system. These filters re
quire frequent cleaning andreplacementand, therefore, regular and careful maintenance. In the
case where the gas is to be used in a motor, a simple paper filter which doubles as a security
322
measure is placed at the inlet. If the tar removal system is not cleaned regularly, the filter
blocks and stops the motor.
3 ARRANGEMENT OF CLEANING DEVICES.
In practice, the devices described can be arranged in very different ways in order to carry
out the cleaning of biomass gas. For each particular type of gasifier, it is necessary to set up a
chain giving an efficiency compatible with the final use of the gas. In order to ensure stable
operation, the removal of ash and tar is carried out, as much as is possible, in two different
steps. If tar removal only is required, wet scrubbers are the current system employed. Table 1
(2) gives the combination of devices necessary for particular applications and different gasi
fiers.
4 COST OF GAS TREATMENT
The cost of the gas treatment is directly linked to its extent. In general, each installation is a
particular case which makes cost prediction difficult. However, in general, the more compli
cated the installation, the more costly the investment, running and maintenance. Little infor
mation on the cleaning of gas is to be found in the literature on gasifiers. Where such
information is available, it usually concerns pilot plants, and therefore does not necessarily
represent the cost of an industrial scale system. B ridgwater (13) has established a simulation
program for the thermal conversion of biomass. The cost of gas cleaning for the simulated
installation is determined
The graph shown in figure 3 gives the relative cost of different devices with respect to the
performance required.
5 CONCLUSION
Existing technology is capable of supplying gas sufficiently clean for uses such as direct
combustion, supply to motors, or for production of synthesis gas. However, in order to be
able to dimension gas cleaning systems for various gasifiers, it is absolutely essential to have
reliable data on the content, size and composition of the particles. At the present time, wet
scrubbers are the only viable technique for removing tars. Further studies concerning their
efficiency with respect to the trapping of tars are necessary in order to allow their design.
The cost of an effective treatment remains prohibitive for most applications. For gas
turbines, the use of hot dust removal techniques remains to be proven. The methods used to
treat water before discharge into the environment have been little studied but the cost of the
treatment of water heavily contaminated with organic carbon seems high. For gasifiers
installed in developing countries, it is imperative that efficient but cheap treatment systems are
found. The most promising method seems to be to reduce tar content by the use of catalysts or
postcracking systems.
REFERENCES
(1) Rensfelt E. "Practical Achievements in Biomass Gasification " Bioenergie 84
conference Vol.1 174 ; ed. H.E. Grens et A.Ellogard; Applied Science publisher
London (1984).
(2) B rown M.D., E.G.Baker, L.K.Mudge "Environmental design considerations for
thermochemical biomass energy" Biomass 11(1986)255270.
(3) B arrett J.R., R.BJacko "Environmental aspects of biomass furnaces used in
agriculture air pollution and grain contamination " B ioenergie 84 conference Vol.4
442 ; ed. H.E. Grens et A.Ellogard; Applied Science publisher London (1984).
(4) Epuration du Gaz de bois pour la combustionSaskatchewan Power Corporation
Rapport SPC n 440019791 (nergie derechange)(1980).
(5) Emerging clean coal technologies ; Noyes data corporation (1986).
(6) Strauss W. "Industrial Gas Cleaning " Pergamon (1975).
(7) B atel WV'Dust extraction technology" Technicopy Limited (1976).
(8) Donovan R.P. "Fabricfiltrationfor combustion sources " Marcel Dekker, Inc
(1985).
323
(9)
(10)
(11)
(12)
(13)
Cahier de l'utilisation du charbon . CODETEC CERCHAR :" Dpoussirage sous

pression et haute temprature des fumes du charbon "(1984).
'Tine particlefiltrationnow possible for 600 F to 1600 F gas stream." News
release, September 12,1983, Acurex Corporation, 485 Clyde Avenue, Mountain
View, California. 94042.
Razgaitis R."An analysis of high temperature particulate collection problem"-Argonne
National Laboratory report ANL-77-14 (october 1977).
P.CORTE "Purification des gaz de gazification" Biomasse actualit ;numero special
n5 avril (1984).
Bridgwater A.V., R.E. Gowers, R.N. Shand, G.J. Walker "Simulation of complete
biomass conversion processes"-Bioenergy 84 conference Vol.3 p. 121 ; ed. H.E.
Grens et A.Ellogard; Applied Science publisher London (1984).
This work has been done under contract n86 - - 7031 - 11 - 004 - 17
mg / Normal m
100
T"
io
10.000
1.000
T"
Fixed Bed
Updraft
100.000
ESSSSSl
Fixed Bed
Downdraft
KWWWM
Fixed Bed
Cross Flow
ESS5S
Fluid Bed
tVWVv _
Entrained Bed
Tar
Particulates
Figure 1 - Emission of different types of gasifiers (from ref. 2)
324
mg/m'
Unacceptable
1000
stat
Regulation
100
NSPS
(Fadaral)
^
^
1 0
Accetable
**
c
ja
c
t
o
o
c
?
a
to
Figure 2 Allowable particulate loadings for various end uses (from ref. 2).
10
ReversedJet
"Fabric Filter
'Venturi Scrubber
Electrostatic.
Precipitator
Cost Relative
to a Medium
Efficiency
Cyclone
HighEfficiency
0,1
MediumEfficiency
I Cyclone
,' I I I I I |
Cyclone
Mil
10
100
Penetration (1 ) %
Figure 3 Relative cost of different apparatus versus efficiency (from ref. 11).
325
Performance
standards
Diesel or
Close-coupled
boiler
spark-ignition
200-1500 mg nr 3
engine
10- 50 mg m- 3
Gas turbine Syn gas or SNG

1- 80 mg m- 3
1- 80 mg m- 3
Fixed bed
updraft *
None
WS + F
WS b
WS + F
WS + ESP
ESPb
WS b
WS + F
WS + ESP
ESPb
Fixed bed
downdraft
None
C
C b'e
C + F
WS b
WS + F
Cb
2C b
C + F
C + ESP
Cb
2C b
C + F
C + ESP
Fluidized bed
2 C b,c
C + WS
C + F
C +F
C + WS b
C + ESP M
C + WS b
C + F
C + ESP d
C + WS b
C + F
C + ESP d
M
ESP M
Entrained bed
similar to
fluidized bed
C = cyclone: 2C = two cyclones in series: F= fabric filter (baghouse): WS = wet

scrubber: ESP = electrostatic precipitator.
a
C yclone not effective due to smaller particle size distribution and tar droplets - use
wet scrubber to remove tars first if any cleanup is required.
b
Lower level of contaminants is acceptable - higher level would exceed limits.
c
Assumes 50% of particulates is char and 90% burns in burner.
d
ESP is not as effective on particulates with high carbon content and may not be
applicable.
c
Cyclones are effective for this application but wet scrubbers are often used instead
because gas cooling is also required. Also cyclone efficiency is affected by large
turndown ratio required in some engine applications.
f
Pressurized operation may restrict the size or applicability of gas cleanup
equipment (particularly baghouse and ESPs).
Table 1 - Applicable gas cleaning options (from ref.2)
326
WHAT CAN WF. D O WITH PYROIYSIS OILS?
E. CHURIN and B. DELMON

Unit de Catalyse et Chimie des Matriaux D iviss
Universit Catholique de Louvain
Place Croix du Sud, 1
B-1348 Louvain-la-Neuve (Belgium)
Summary
The "liquids" obtained by pyrolysis or liquefaction of biomass present the
advantage of being easy to handle and have high energy density but
because of the high oxygen concentration the volume needed to replace
heating oils is around l.S times higher. When dried, the oils are viscous
but the water dissolved diminish greatly the viscosity; the nature of the
oil affects also the viscosity. If oxygen is removed the composition of the
oil is very similar to petroleum-derived fuels. The oxygen removal can be
carried out at almost atmospheric pressure or at high pressure. At low
pressure, in the presence of a zeolite catalyst oxygen is eliminated as CO,
CO2 and principally H2O. Hydrocarbons yields of between 5 and 10 % on a
wood basis have been reported. The coprocessing of pyrolysis vapors and
methanol allows for the obtention of higher yields. The desoxygentation
can also be effected under high hydrogen pressure and the hydrocarbon
yield is higher than for atmospheric pressure upgrading.
1- C h a r a c t e r i s t i c s
of
pvrolvsis
ails
Biomass can be converted to "liquids" by pyrolysis, by liquefaction under

high pressure or by solvolysis. The "liquids" present the advantage of being
easier to handle than biomass and present a much higher energy density. These
liquids are intended for use as fuels. In general a fuel consists of one or more
compounds containing carbon and hydrogen with or without oxygen, other
components (such as and S) have a negative influence on the quality. Biomass
"liquids" are well positioned because their and S contents are very low. From
an energy point of view, hydrocarbons without oxygen are preferable because
it do not add to the energy content of the fuel.
Table 1 shows the composition of biomass pyrolysis oils obtained by
different process as well as the composition of petroleum derived fuels. Because
of the high oxygen content, the energy density (on a weight basis) of the
pyrolysis oils is lower. The commercialization of fuels is generally done on a
volume basis and if the energy content is calculated on a volume base, the
difference with petroleum fuels diminishes because the density of the pyrolysis
oils is higher than 1.
In any case, if a given amount of heat is needed, the volume of pyrolysis
oil burned should be between 1.5 and 1.8 times greater than the volume of fuel
oil with the consequent influence of the selling price.
The fuel oils with which pyrolysis oils are compared are obtained by
mixing different residuums and distillates in order to meet the legal
327
specifications. For a N 6 fuel oil, distillates account for between 5 and 20%
while for a N 2 fuel oil they account for between 20 and 50%.
Table 1 : Composition of fuel oils and
Carbon(%)
Hydrogen(%)
Oxygen(%)
Nitrogen(%)
Sulphur(%)
H/C ratio
Density(kg/1)
pyrolysis oils.
N2 fuel oil
33 API
N6 fuel oil
15.5 API
Waterloo
pyrol. oil
87.3
12.6
0.04
84.67
11.02
0.38
0.18
3.97
1.56
52.6
6.5
40.8
0.22
1.73
Raiano
Pyrol. oil
66
7.2
26
0.8
<0.1
1.31
1.2
a
a
1.48
Due to the increasing demand for transformation fuels such as gasolines,

diesels and kerosins, a greater conversion of other fractions to these products
has been encouraged resulting in smaller volumes of residual oils.
Environmental legislation could place constraints on the use of residual fuel oils
due to the presence of sulfur, nitrogen, vanadium, nickel and iron concentrated
from crude into residue, the present commercial grades of residual fuel oils
have sulfur contents that may vary from 0.7% to 4% and the metal contents can
vary between 50 and lOOOppm. In this respect, biomass pyrolysis oils are well
placed because they contain no metals at all.
Two additional points should be considered when comparing bio-oils with
petroleum products. These are density and viscosity.
Table 1 shows the that density of bio-oils is always higher than 1 and this should
be taken into account during handling and storage since rain water or water
from leaking steam coils rises to the surface of the oil. Oil spillage is another
matter that cannot be ignored because with a density higher than 1 kg/1 the oil
settles to the bottom of the watercourse and drainage systems. Interceptors
should be adapted to cope with such oils.
As for the viscosity of the oil, it depends to a great extent on the nature of
the oil and on the water content. The latter depends on the reaction conditions
but if water is used for quenching pyrolysis vapours, the oil becomes saturated
(and it can disolve a lot of water because of its polar nature)
Table 2 shows dthe influence of the water content and the nature of the
oil on viscosity. Figure 1 is a comparison of two oils to petroleum products.
Table 2: Influence of the nature of the oil and the water content on viscosity.
Water content
et 60C (cp)
(%)
29
10
10
480
D
0.15
60
0
450
12
240
328
Maximum viscosity
tor typical storage
Maximum viscosity
for pumping and handling
Steam atomization
Mechanical atomization
Fig.l: Viscosities of petroleum products and pyrolysis oils.

Taking these considerations into account, pyrolysis oils can be burned
satisfactorily. Minor changes in atomizer design may be needed because some
deterioration of the fuel spray has been detected and which is probably due to
blockage or incrustation. This problem is apparently related to a decomposition
of the oil when heated in the atomizer by the flame or the atomizing steam (11).
For other high value utilizations, the pyrolysis oils must be upgraded and
transportation fuels or petrochemical feedstocks can be obtained.
2. Upgrading of the pvrnlvsis nil
In view of their properties, pyrolysis oils should be considered as crude
oils which need to be refined and upgraded in order to recover different
fractions of a lower viscosity, higher volatility and heat content, presenting a
good stability for use as fuels.
The heat value of a fuel can be determined easily using the elemental
composition of the material with Dulong formula:
NHV
(Kcal/kg)=81xC%+300x(H%-l/8xO%)+25xS%-53.46xH%
When the elemental composition of the pyrolysis oil is compared to the

composition of distillates or fuel oils, it can be seen that in order to increase the
heat value, oxygen should be removed. The elimination of oxygen results in a
diminution of weight and when carbon and hydrogen concentrations are
calculated on the new weight basis, composition is similar to that of petroleum
cuts. The oxygen removal can be carried out with or without a reducing gas.
2.1. Upgrading in the absence of a reducing gas
In the absence of a reducing gas, oxygen is eliminated as H2O, CO or CO2
(to form H2O) and carbon (to form CO and CO2); the yield to hydrocarbons is
rather low. Theoretical yields from calculations based on a composition of the
329
pyrolysis oil presented in Table 1 show that if all the oxygen is eliminated as
C O 2, the hydrocarbon yield is 43% with an H/C ratio of 2. If all the oxygen is
eliminated as CO the hydrocarbon yield is 27% with an H/C ration of 4 while if
the oxygen is eliminated as water, the yield is 14.0% with an H/C ratio of 1.4.
A synthetic zeolite catalyst (ZSM-5) has been particularly effective in the
conversion of oxygenated compounds, mainly methanol to hydrocarbons (1) (2).
In the case of methanol, during the early stages of the reaction, it is rapidly
converted to dimethylether and water. The first hydrocarbons produced are
mainly olefins which react to give paraffins and aromatics. Typical yields
obtained in a fixed bed are hydrocarbons, 43.7%; water, 56.2%; CO and CO2, 0.04%,
the rest being coke and oxygenates. Alcohols are good feeds for transformation
by this process because of the low tendency to produce coke which deactivates
the catalyst. One of the first researchers to study the conversion of pyrolysis
vapours over a zeolite catalyst was Frankiewicz. Vapours were produced by the
pyrolysis of solid wastes and were contacted with the catalyst in a second reactor
(3). Reaction of a model compound, furfuryl alcohol was also studied. Since then,
several groups have studied the conversion of pyrolytic vapours of biomass
over this catalyst (4)(5)(6).
Using this catalyst, most of the oxygen (between 70 and 80%) is eliminated
as water and the rest as CO and CO2. Parallel undesired reactions also take place
such as coke formation throught aromatization reactions which contribute to
the reduction of hydrocarbon yields due to the consumption of carbon atoms. As
disclosed in (6) hydroxyl and methoxy groups tend to reject oxygen in the form
of water, aryl ethers reject a nearly equal amount of oxygen as carbon
monoxide and water, carbonyl and formate groups reject oxygen as carbon
monoxide and carboxyl as carbon dioxide and water.
Since rejection of oxygen as water involves the elimation of hydrogen,
Chang et al (7) have introduced the concept of "effective hydrogen index" (EHI)
defined as :
EHI-
H-20-3N-2S
where H, C, , and S are atoms per unit weight of sample. They show that
compounds with EHI<1 cause a rapid deactivation of the catalyst and give a poor
product distribution. But they propose also that a lower catalyst deactivation a
synergistic yield improvement could be obtained by co-processing the low EHI
feed with a sufficient amount of high EHI compound, which could act as some
kind of hydrogen donor. Methanol could be used as a high EHI feed.
The yields obtained by Chen et al. (4) when pyrolysis vapour is contacted
alone with methanol (1:1 ratio) in a fluid bed with a ZSM-5 catalyst are shown in
Table 2.
Table 2: Product distribution from conversion of pyrolysis liquids over ZSM-5
catalyst.
Pyrolysis
CO%
002%
H20%
Cl-C4%
C5+ hydrocarb.%
Coke%
0.7
10.5
70.7
2.5
6.0
9.6
liquids
Pyrolysis liquids
+ methanol
82.1
2.7
11.2
4
330
The hydrocarbon yield is only around 3% on the basis of the wood
processed. The yield is rather low because the percentage of the wood carbon
retained in the liquid was only 30% (the retention of carbon in the liquids can
be as high as 60%). Researchers from the Universit de Laval (8) report yields
of between 5 and 10% on a dry wood basis without methanol. The product
obtained is a high quality gasoline consituted of mainly alky-substituted
benzene.
This process can be accomplished in a fluid bed with constant withdrawal
and addition of catalyst. The withdrawn catalyst is regenerated by combustion of
the coke and is then put back into the reactor. Another possibility would be a
moving bed such as the one used in modern catalytic reforming of naphta with
the same regeration process.
If it is proven that a very short contact time is sufficient to obtain the
desired conversion, an entrained-bed reactor such as the one used in catalytic
cracking of hydrocarbons could be used.
2.2. Upgrading in the presence of reducing gas
The upgrading effected in the presence of a reducing gas (hydrogen)
aims at removing oxygen as water and at reducing the molecular weight of the
heavy fractions. From the theoretical point of view, and based on the
composition of the pyrolysis oil presented in Table 1, it can be calculated that if
all the oxygen is rejected as water with externaly supplied hydrogen the
hydrocarbon yield could be as much as 58%.
The transformation is conducted under high pressure of hydrogen and in
the presence of a catalyst. Typical petroleum hydrotreating catalysts, namely
cobalt and molybdenum and nickel and molybdenum in the sulfided form
supported on alumina are very active. Though there are some similarities, there
are also notable differences between petroleum products and pyrolysis oil
components because the presence of the large quantities of oxygen lead to a
degradation of the oil during heating. This degradation could be interpreted in
terms of free radicals. In fact, upon heating, highly hydroxylated compounds
can generate free radicals and the nature of the products obtained depends on
the manner in which they are stabilized. The possibilities are:
- Reaction of the highly reactive free radicals with one another to give
higher molecular weight materials including coke;
- Free radicals are capable of obstracting hydrogen from
hydrogen-rich groups or molecules in the mixture.
neighbouring
The latter possibility can be exploited to stabilize the radicals and facilitate the
conversion if the concentration of hydrogen-rich compounds which are able to
donate hydrogen is high enough.
The effect of the temperature is also very important and we have found,
like Elliot (9), that a pretreatment at around 230C allows for a "stabilization" of
the oil and higher yieds are obtained in the second stage of the pretreatment.
Without the pretreatment, the polyhydroxylated compounds polymerize and
deactivate the catalyst very quickly.
In the test effected in this laboratory to upgrade pyrolysis oils, tetralin
was used as hydrogen donor.
Table 3 shows the influence of the tetralin on the nature of the product
obtained kwhen pyrolysis oils produced at the Raiano demonstration unit (Italy)
are processed in two stages.
331
Table 3: Characteristics of the hydrotreated
Oil:tetralin ratio 1
Without
tetralin
%HDO
%HDN
Volatile
fraction%
oils
70
58
50
85
85
95
Table 4 shows the results obtained at the PNL (hydrotreatment in two

stages at 274C and 353C) by Elliot and Baker on a pyrolysis oil produced at
Gergie Tech. in an entrained bed. The product obtained in the first stage is used
as feed in the second stage.
Table 4: Two-stage upgrading of Gergie Tech. Pyrolysis oils
Stage 1
Stage 2
Catalyst
Temperature (C)
Pressure (MPa)
LHSV (vol.oil/vol.cat.h)
C0M0/AI2O3
247
13.5
0.62
C0M0/AI2O3
353
13.5
0.11
Yields
Total oil (L/L feed oil)
C5-225C (L/L feed oil)
Hydrogen consumption
feed oil)
0.69
0.07
60
0.62
0.45
576
(L/L
The total oil yield obtained for the combined two-stage process is 43% and
the fraction C5-225C amounts to 31%.
The results obtained by processing different pyrolysis oils enables Elliot
(9) to estimate the following mean yields: 0.5-0.55 1 of oil could be produced per
litre of pyrolysis oil processed; the oil could contain 2-3% of oxygen and could
have a H/C ratio of 1.5 and a density of 0.9-0.92; about 50-60% vol. of the oil could
be in the gasoline boiling range; about 30% is distillable, the rest being a
residual oil.
The oxygen content of the oils obtained at different contact times show
(Fig. 2) that only an LHSV lower than 0.2 allowed for an oxygen content lower
than 2%. This is inconsistent with the facility found to remove oxygen from
model compounds (10) and cannot be attributed to the conversion of heavy
compounds because petroleum cuts with higher mean molecular weight are
processed at higher space velocities. On the contrary, such a low space velocity
can be explained by a deactivation. The use of a hydrogen donor allows for
higher conversions under the same reaction conditions. The product obtained
by hydrotreating pyrolysis oils is highly aromatic and constitutes an excellent
BTX or gasoline cut. The cetane index is too low to contribute significantly to a
diesel cut.
332
TR7
O TRI2
Pyrolysis Oils
Pyrolysis Oils
o
s
0.5
0.6
0.7
Fig. 2 : Effect of space velocities on various biomass-derived oils (F rom (9)).

The product obtained by hydrotreating pyrolysis oils is highly aromatic
and constitutes an excellent BTX or gasoline cut. The celane index is too low to
contribute significantly to a diesel cut.
Further research needs to be carried out in order to determine the cause
of the low reaction rate found when processing pyrolysis oils and to find more
active and resistant catalysts. Long duration reaction studies are needed in order
to determine the catalyst lifespan. If a severe deactivation is confirmed an
ebullating bed reactor such as the one used by Hydrocarbon Research Inc. in
the -Coal (R) process
should be considered for the industrial implementation
of the conversion. In this kind of reactors, continuous catalyst replacement
restores the activity and yields a product of a constant quality; the catalyst can
be continuously regenerated.
References
(1)
(2)
(3)
(4)
(5)
S.L. Meisel, J.P. Mc Cullogh, CH. Lechthaier and P.B. Weiz, "Gasoline from
methanol in one step", Chemtech, Vol. 6, 1976, p. 86.
C D . Chang and A.J. Silvestri, "The conversion of methanol and other
oxygenated compounds to hydrocarbons over zeolithe catalysts", J. Calai.,
Vol. 47, 1977, p. 249.
T.C. F rankiewicz, The conversion of biomass derived pyrolytic vapors to
hydrocarbons, p. 123 in Proceedings Specialists' Workshop on F ast
Pyrolysis of Biomass, ed. J.P. Diebold, Copper Mountain, Colorado, USA,
October, 19-22,1980.
N.Y. Chen, D.E. Walsh and L.R. Kocnig, "F luidized bed upgrading of wood
pyrolysis liquids and related compounds", Am. Chem. Soc. Div. F uel. Chem.,
Preprints, Vol. 32, n 2, p. 264, April 5-10, 1957, Denver, Colorado, USA.
P.D. Chantal, S. Kaliaguine and J.L. Grandmaison, "Reactions of Phenolic
compounds over H-ZSM 5", Appi. Cat., 18, 133-145 (1985).
333
(7)
(8)
(9)
(10)
(11)
CD. Chang, W.H. Lang and A.J. Silvestri, U.S Patent 3.998.898 (1976).
M. Renaud, J.L. Grandmaison, Ch. Roy and S. Kaliaguine, "Conversion of
vacuum pyrolytic oils from populus deltoides over H-ZSM 5", Am. Chem.
Soc. Div. Fuel. Chem., Preprints, Vol. 32, n 2, p. 276, April 5-10, 1957,
Denver, Colorado, USA.
D. Elliot and E. Baker, "Hydrotreating biomass liquids to produce
hydrocarbon fuels", in Energy from Biomass and Wastes-X, Ed. D. Klass,
Elsevier Applied Science Publishers, London, 1987, p. 765.
M. Callara , MSc. Thesis, September 1988, University Catholique de
Louvain.
Finney CS. and Sottier J.G., AICHE Symposium Series N 164, Vol. 71, p. 51.
334
COMPOSITION, PURIFICATION AND USE OF PRODUCER GAS
J . VAN DER WEIDE and J . J . SEPPEN
TNO R o a d - V e h i c l e s Research I n s t i t u t e
SUMMARY
The paper discusses the strong variation in the composition of producer gas. This variation is generally caused by insufficient control on
the process and quality of the feed stock. The amount of impurities
(tar and particles) also tend to increase when the process is not
under optimal control. In conventional systems these problems are the
cause of a substantial power variation and often too much engine maintenance. The latter can be overcome reasonably by proper purification.
Producer gas is generally used in spark ignition engines and diesel
engines. In spark ignition engines sometimes petrol is used for start
up. Diesel engines are generally started on 100% diesel. The producer
gas is used by gradually feeding it into the combustion air and reducing the amount of diesel used simultaneously. These system lay-outs
are discussed. The paper concludes that by additional hardware a better process control of the whole system is necessary. Proposed thereby
is to use low cost automotive micro-electronic componentry. Good low
cost sensors are available for measuring oxygen content, temperatures
and pressures. As an output of such an automotive micro-processor the
process can be controlled by air injection or grate activation and
automatic engine adjustment.
1. INTRODUCTION
In the Netherlands the concern for the greenhouse effect is strongly
increasing beside many other environmental concerns. Using biomass materials for energy generation has compared to the conventional fuels the great
advantage of no C02-contribution to the atmosphere, because of the closed
cycle in which it is used. It will become probable that political pressure
with regard to the use of biomass materials for energy generation will
arise. Until sofar quite a lot of producer gas projects have failed. Many
problems still have to be solved. For the developed world, in particular,
an extra problem is that generally rather a lot of manpower attention is
necessary to operate a producer gas engine system. This is than an important cost factor. This paper emphasizes on the enumeration of the different
problems in gasifier engine systems. Furtheron new technologies to overcome
these problems are discussed. The paper ends up by making recommendations
for the future research.
2. SUMMARIZATION OF CONSTRAINTS
2.1 PROBLEMS IN GASIFIERS
Generally there is an interaction between problems in the gasifier and the
engines. For this reason these problems are summed up in general terms.
The most important problem, with the application of gasifiers, is the
fact that the gas quality (calorific value and the amount of dirt) is dependent on the fuel parameters. In particularly in respect to water content, ash content and chop size.
335
Water content of the fuel: Tar formation is the most general problem,
due to lower temperatures in the reactor. Tar formation leads to rapid
engine failure when it is not filtered out. This means that the possibility
to control the gasifier is strongly reduced with increasing water content
of the fuel.
Ash content of the fuel: In case the ash content of the fuel exceeds a
certain value there is a possibility of slagging in the reactor. Generally
this problem is solved (at least in smaller gasifiers) by manual operation
of the grate. This needs a lot of attention from the operator.
Chop size: Generally the chop size has to be adapted to the reactor
design. Sometimes it is necessary to reduce the chop size. This is labour
and mechanical power consuming.
2 . 2 GENERAL PROBLEMS IN ENGINES
The most common problem with the application of producergas in combustion

engines is the lifetime of the engine. This is quite a general complain although documented cases are known of very good lifetime combined with good
gas cleaning.
Engine wear is a result of unwanted components such as dust, tar and
corrosive components in the gas. This is strongly dependent on the proper
operation of the gas cleaning system.
Dust: Soot, carbon and ash particles are produced in the reactor and
carried with the gas. In case the gas cleaning operates insufficient, this
material comes into the engine cylinders and creates wear of the cylinder
wall and piston rings. Due to the resulting "blow by" these particles can
also come into the lubricating oil. These particles, in particular when
they are larger than the thickness of the oil film, can also damage the
bearings. The information avalaible is insufficient with regard to maximum
allowable concentrations and size. Noticed is that the wear is also dependent on the type of engine.
Tar: Tar is formed during the gasifying process. Although some manufacturers of gasifiers claim that no tar is formed it is noticed that tar
is always present sometimes as small droplets. Tar as such does not create
abrasive wear but can settle down on valves, piston rings, etc. and thereby
obstruct the operation. Sometimes tar becomes bitumenous, which can create
problems at particularly at starting of a cold engine.
Corrosive components: The corrosive components in the gas (carbon
acids, ammonia) do not create problems when the engine is on its working
temperature. But during cooling down of the engine condensates can be formed resulting in fast corrosive wear of cylinder and piston rings. Furtheron
there is the suspect that small amounts of sodium in the lubricating oil
(from the producergas fuel) can create valve corrosion.
A specific problem with the application of producergas in engines is
the fluctuating caloric value of the gas. This leads to changing engine power.
The chemical composition of producergas is such that in particularly
due to the large carbon monoxide content a relative slow combustion speed
occurs. In particularly with fast running engines this results in reduced
power and efficiency. Generally power and efficiency start to reduce at engine speeds above 2300 rpm. This means that for obtaining a certain power
relative slow running and thus large and expensive engines are necessary.
Good mixing of the gas with the combustion air is necessary to obtain
a homogeneous mixture and to avoid wrong fuel distribution over the different cylinders. This can substantially reduce engine power and efficiency.
2.3 PROBLEMS MORE TYPICAL TO OTTO ENGINES
The most common problem with the application of producergas in otto engines
is the power loss in comparison with the operation on petrol or natural
336
g a s . T h i s i s d u e t o t h e r e l a t i v e l o w c a l o r i f i c v a l u e of t h e g a s , r e s u l t i n g
g e n e r a l l y i n r e d u c i n g e n g i n e power by some 4 0 - 5 0 % . T h i s makes a much more
expensive engine n e c e s s a r y t o r e a l i z e a c e r t a i n power.
C a s e s a r e known ( i n p a r t i c u l a r l y w i t h o n e o r two c y l i n d e r s ) t h a t o s c i l l a t i o n i n t h e i n l e t m a n i f o l d , a g a s s t r e a m o c c u r s , r e s u l t i n g i n power
l o s s e s up t o 70%.
I n p a r t i c u l a r l y i n o t t o e n g i n e s due t o hot p a r t s b a c k f i r e can o c c u r .
T h i s c a n r e s u l t i n damaged e n g i n e p a r t s a n d i n some c a s e s e v e n t o e x p l o s i o n
in the gasifier.
2 . 4 PROBLEMS MORE TYPICAL TO DIESEL ENGINES
D i e s e l e n g i n e s c a n be o p e r a t e d p a r t l y on p r o d u c e r g a s i n s o c a l l e d d u a l - f u e l
o p e r a t i o n . Due t o t h e f a c t t h a t a d i e s e l e n g i n e h a s r e l a t i v e e x c e s s a i r
a v a i l a b l e , t h e power l o s s i s r e d u c e d t o some 10%. I n j e c t i o n o v e r s m a l l
q u a n t i t y o f d i e s e l o i l (some 10-15% of t h e amount on maximum power) i s a l ways n e c e s s a r y t o i g n i t e t h e g a s / a i r m i x t u r e . E n g i n e s w i t h d i r e c t i n j e c t i o n
a r e more f a v o u r a b l e f o r t h i s o p e r a t i o n t h a n e n g i n e s w i t h a p r e - c h a m b e r
( p r e - c h a m b e r t e n d s t o c r e a t e p r e - i g n i t o n ) . I t w i l l be c l e a r t h a t a t low
e n g i n e power t h e r e l a t i v e amount of d i e s e l o i l r e p l a c e d t e n d s t o become
s m a l l e r . T h e r e f o r e t h i s type of o p e r a t i o n i s f a v o u r a b l e for engines running
under c o n s t a n t high l o a d .
Sometimes t h e d i e s e l f u e l i n j e c t o r s i n d u a l - f u e l o p e r a t i o n become
o v e r h e a t e d . Due t o t h e f a c t t h a t t h e s m a l l e r amount of d i e s e l o i l g i v e s a
s m a l l e r amount of c o o l i n g on t h e i n j e c t o r .
In d u a l - f u e l o p e r a t i o n sometimes knocking o c c u r s . This engine knocking
can r e s u l t i n s e v e r e e n g i n e d a m a g e . T h e c a u s e i s p r o b a b l y o v e r f u e l l i n g o r a
r e l a t i v e high hydrogen content i n t h e g a s .
3.
DISCUSSION WITH REGARD TO NEW TECHNOLOGIES

The f o r e m e n t i o n e d p r o b l e m s w i l l be d i s c u s s e d w i t h a n e m p h a s i s on t h e
a p p l i c a t i o n of new t e c h n o l g i e s .
M i c r o - e l e c t r o n i c s : The s t r o n g e s t e x h a u s t e m i s s i o n r e g u l a t i o n s f o r c a r s
a r e a p p l i e d i n t h e USA and J a p a n . More r e c e n t l y a l s o s t r i n g e n t r e g u l a t i o n s
w i l l be a p p l i e d i n E u r o p e . T h e c a r i n d u s t r y h a s d e v e l o p p e d m i c r o - e l e c t r o n i c
s y s t e m s t o meet t h e s e r e g u l a t i o n s . The most i m p o r t a n t q u a l i f i c a t i o n s of
these m i c r o - e l e c t r o n i c systems a r e :
- low c o s t due t o t h e f a c t t h a t they a r e mass produced
- v e r y r e l i a b l e . Most of t h e componentry i s designed for use under t h e bonn e t of t h e c a r s . This means t h a t i t i s r e s i s t e n t a g a i n s t s t r o n g temperat u r e changes, humidity and v i b r a t i o n . The emission r e g u l a t i o n s a l s o r e q u i r e long l i f e t i m e of t h e componentry
- a v a i l a b l e a r e s e n s o r s for t e m p e r a t u r e s , p r e s s u r e s and oxygen c o n t e n t i n
gases
- a v a i l a b l e are actuators to adjust v a l v e s , e t c .
- a v a i l a b l e a r e improved i g n i t i o n systems w i t h timing c o n t r o l over t h e
software
- a v a i l a b l e i s a l a r g e amount of software for many kinds of c o n t r o l s a l s o
under t r a n s i e n t c o n d i t i o n s
- a v a i l a b l e i s v e r y users f r i e n d l y a p p l i c a t i o n equipment. I f t h e proper
software i s a v a i l a b l e , c a l i b r a t i o n s can even be made i n t h e f i e l d
- a v a i l a b l e i s t h e software for very simple d i a g n o s t i c s .
This kind of equipment i s a l r e a d y i n use for s t a t i o n a r y , n a t u r a l gas
engines and v e h i c l e s running on LPG or n a t u r a l g a s . See F i g u r e s 1 and 2 .
I t i s q u i t e c l e a r t h a t t h e s e m i c r o - e l e c t r o n i c systems can be a p p l i e d
on producergas e n g i n e s . Problems such as v a r y i n g power, low e f f i c i e n c y a t
high engine speeds can be solved t o a v e r y l a r g e e x t e n t . With t h i s compon e n t r y and software and p a r t l y new to be developed software d i f f e r e n t p r o -
337
MICROPROCESSOR-CONTROLLED AIR/FUEL RATIO SYSTEM

inputs
EitE^-
outputs
O.
heck engine light
Lambda sensor
steppermoior position
speed
pickup
microprocessor
control
unit
Fig. 1: Schematicei design of a closed loop control based on measurement

of the oxygen content in the engine exhaust
.. .
Fig. 2: Example of the hardware,
at the left the microprocessor, in the middle
the oxygen sensor and at
the right the carburettor
for gaseous fuels with a
steppermotor for the final
control.
blems in the gasifier itself can be controlled more accurately with much
less attention from an operator. Think e.g. of measurement of the oxygen
content in the producergas. That is an important parameter regarding the
proper functioning. Furtheron temperatures can be measured in the gasifier
in the bed and automatic actions such as some air injection or operation of
the grate can be done automatically. By such an accurate control tar and
soot formation will be reduced. It will be clear that with such system a
very good interaction between the engine and the gasifier becomes possible.
This also can be of great advantage for start-up and turn down.
New sensors: When a system is operating under micro-electronic control, new sensors could be added. These new sensors than could influence
the process or give a warning. Examples:
- sensor for water content in the fuel. Generally a gasifier is designed
for a fuel with a limited amount of water content. If, however, water
content would be different and this would be known continuously, the process could probably be influenced to a certain extent. This influencing
could be e.g. slowing down the process
- sensor for tar in the gas. Tar is quite dangerous for the engine. If tar
is formed, although not expected, a warning would be very useful. Also to
338
a certain extent the process can be automatically controlled to optimise
on tar content
- sensor for dust. For dust the same applies as for tar. Such a sensor
would give a warning
- sensor for other components in the gas. Also hydrogen sulfide, ammonia
and halogen hydrocarbons tend to be wrong for the engine. A warning that
such components enter the engine in a large amount, would be very useful.
Scrubbing e.g. could be increased to reduce such components
- sensor for lubricating oil condition. A lot of expensive engine damage
occurs due to operation on engine oil in a bad condition. This can be due
to acids or dust. A sensor which could give global information on this
would be very useful
- sensor for filter pollution. Automatic sensing of pollution of filters is
quite good possible by measuring the pressure drop over the filter. The
micro-electronic system knows engine speed and load and thereby the gas
flow. It can compare the measured pressure drop with known normal values
and thereby give an alarm in time. This pressure drop can be measured
with existing automotive sensors. The incoming signal can also be differentiated against time and thereby give an early warning that the process
is not running well.
General remark on sensors: Development of new sensors is generally
rather expensive. It is however useful to study what is available on the
market for industrial applications. Known are e.g. non-automatic operating
equipment for measuring the water content in grains.
Oxygen enrichment: In the Netherlands (and some other countries) development work is done for oxygen enrichment of the air. This is generally
for industrial applications. There is a development whereby socalled hollow
fiber membrane technic is applied. These are thin hollow fibers, whereby in
a limited volume a large surface is created. The material is such that with
some overpressure oxygen passes easier through the surface than nitrogen
and by that a different oxygen content is obtained. Oxygen enriched air
would be very attractive for the gasifier. This is because of the fact that
such air makes products more "combustible". Higher temperatures would be
created and by that the amount of tar w uld be reduced. Also a fuel with a
higher water content could be applied. A system could be such that independence of e.g. water content of the fuel (new sensor) or tar in the gas (new
sensor) the amount of oxygen enrichment would be controlled. Of course,
mechanical power is needed to drive the compressor for the air.
Engine design: Lifetime: The most important problem in engines is the
lifetime. Beside filtering and scrubbing and adaption of the oil (see further), adaption'of engine design is a possibility. However, because of the
fact that the amount of engines used is generally small, it means that special manufactured components tend to become expensive. Copper e.g., used in
the bearings and oil coolers and nickel in camshafts, tend to be sensitive
for in particular sul far corrosion. Application of other materials is quite
difficult. It could be manufactured but other disadvantages such as less
good heat transfer or sensitivity for abrasive wear would occur. Generally
it is concluded that such developments are too expensive, mainly because of
small amounts. Quite a different approach to avoid in particularly acids by
condensation, is to increase the engine temperature and to keep engine on
temperature also when this is stopped. Keeping engine on temperature is already longtime applied in large ship engines. In such system it would also
be attractive to blow air through the engine crankcase before stopping.
Abrasive wear is of course not reduced by such system. This could be improved by applying a more frequent oil filter change or by applying a larger
filter.
339
Power Improvement: Due to the low calorific value of the gas the high
power loss generally occurs, which results therein that a more expensive
engine has to be applied to obtain a certain power. The following actions
can improve engine power:
- ignition. Stronger ignition can keep engine longer on good power. Such
electronic ignitions with also more improved timing characteristics and
correct spark plugs for this are available on the market
- spark plug engines tend to have a compression ratio which is not optimal
for producergas. For producergas engines a compression ratio of about
12.5 is possible and this gives some 10% power increase and some 8% reduction in fuel consumption. Manufacturing of modified pistons is often
possible without extreme cost
- oxygen enrichment. When oxygen enrichment would be applied for the gasifier, it can also be considered to apply it for the engine. Each volume
percent increased oxygen can generate some 5% more power. This enrichment
can probably only be done up to some 26 volume percent in air because
otherwise probably engine knocking will occur
- more air supply to the engine. Power of the engine will be increased leanier with more air for the combustion. For this the following possibilities can be considered:
. turbocharging. Turbocharging is widely applied on diesel engines and
more recently on spark ignition engines as well. The componentry is
available for most of the engines. This method increases engine power
easily by some 30%. Until sofar it is nearly not applied with producergas, because of insufficient filtering. The speed in the turbo is so
high that small particles rapidly create corrosive wear. This means
that filtering on in particularly dust has to be nearly total, which
makes it neccesary to apply larger and more expensive filters. The application of roots blowers looks to be more attractive for the time
being.
. roots blowers. Roots blowers are mechanically driven, so called positive displacement pumps. These blowers are less sensitive to dust and
tar. Herewith also the power can be increased by some 30%. However,
compression ratio of the engine generally has to be reduced to some 7
t avoid engine knocking, thus for that other pistons have to be applied as well.
. tuning. The suction of the air for combustion is of a pulsating nature
due to the opening and closing of the air intake valve. Due to this waves occur in the intake system. Generally these waves reduce the amount
of air sucked in. It is however possible to give the intake system such
dimensions that these waves increase the amount of air sucked in. Quite
often a power increase of 10-15% is possible. The modification of the
engine manifold is such that part of the intake manifold consists of
tubes for each cylinder. The method is not sensitive for dust and is as
a construction rather simple. The disadvantage of the method is that is
generally works in a small engine speed range (which for stationary engines is generally not problematic) and quite specific knowledge is necesary for the designing.
. less air resistance. Sometimes producergas systems are built with a lot
of tubing with sharp edges, etc. In such tubing sometimes negative working waves occur. Optimizing on this design is generally quite useful
and relative simple.
- micro-electronic control. Maintaining an optimal adjustment will increase
the average power output.
Adapted engine oils: Special lubricating oils for engines which run on
acid containing gases have been developed. These oils generally have a high
340
Total Base Number (TBN). A high TBN means that the oil has a high acid nutralizing capacity. These oils generally nutralize a sul far well, but not
always chlorine and fluorine. With an optimal engine jail protection against
an hydrogen sulfide concentration of some 2000 mg/m is possible. In that
case oil change time has to be reduced by half. Concentrations larger than
5000 mg/m cannot be dealt with by adapted engine oils and reasonable oil
change times.
Back-up gas: When gas quality and gas amount changes drasticly and
when a rather continuous power is required, the application of a socalled
back-up gas can be considered. This could be natural gas or LPG when available. Some engine manufacturters have developed a system whereby can be
switched from one gas to another. It is however possible to operate the
back-up gas on a continuous base and not just be switching. Such a system
operating on a continuous base basicly uses all the producer gas available
but takes additional backup gas until the required power is obtained. This
system operates by a pressure controller which has some difference to the
setting of the producergas pressure. Also the application of micro-electronics simplify the application of such a back-up gas.
4. CONCLUSIONS/RECOMMENDATION FOR FUTURE RESEARCH
It is recommended to initiate research and development whereby the
producergas engine is controlled by micro-electronics. The use of low-cost
automotive hardware and adapted software is recommended.
It is recommended to initiate research and development whereby the gasifier will be controlled with additional micro-electronics. In the first
phase low-cost automotive hardware and adapted software shall be applied.
It is recommended to initiate a paper study to investigate the possibility of existing industrial sensors for dust, tar, hydrogen sulfide and
halogen hydrocarbons.
It is recommended to initiate a demonstration project whereby the engine power in increased by tuning of the inlet manifold and by the application of a roots blower.
It is recommended to initiate a paper study regarding the cost effectiviness on the application of oxygen enrichment of the air via hollow
fiber membrane technics.
It is recommended to advise users of producergas engines to use special lubricating oils with a high Total Base Number.
It is recommended to initiate a demonstration in a country where backup gas is available to use this in combination with difficult fuel that generally creates strong fluctuation in the gas quality and gas amount.
If forementioned research has been carried out partly, it is recommended to organize a full-scale demonstration whereby most of the developped
new technologies are applied.
REFERENCES
(1) DEKKER, H.J., Pilotinjektie DAF 575, Delft, IW-TNO, 1982.
(2) HEYNIS, G. and RAMACKERS, M., Application of Producergas in Otto and
Diesel engines, Delft, IW-TNO, 1983.
(3) LYON, D.; HOWLAND, A.H.; LOM, W.L., Controlling exhaust emissions from
a Diesel engine by LPG dual fuelling. Instn. Mech Engrs. C126/71.
(4) RELE, R.R.J, ter, Ontwikkeling en toetsing van biogasmotoren op veehouderijen. Utrecht, Projectenbeheerbureau Energieonderzoek, 1984.
(5) WEIDE, J. van der, STASSEN, H.E.M., GEURTS, M.J.G., Diversificatie gasvormige brandstoffen voor gasmotoren, TNO nr. 7700360698, Delft.
341
(6) WEIDE, J. van der and SEPPEN, J.J. Avanced hardware and combustion
technology for gaseous fuels at TNO, Conference Gaseous Fuels for
Transportation, Vancouver 1986
(7) Weide, J. van der, et.al. Experiences with CNG and LPG operated heav
duty vehicles with emphasis on US HD diesel emission standards, SAE
paper 881657.
342
RAPPORTEURS REPORT ON SESSION VI
UPGRADING, CLEAN UP AND UTILIZATION OF PRODUCTS
J. DIEBOLD
SERI, Colorado, USA
1. GAS PURIFICA TION

Techniques exist for the clean up of gasifier gases for engine usage,
but they are expensive. They do require periodic filter maintenance or else
they fail on a system. It was mentioned that at the Loma Plata plant in
Paraguay there are three engines with 40 000 to 60 000 hours of successful
operation.
In response to van der Weide suggesting research to couple state-ofthe-art computer for engine control to a gasifier, Dr Esnouf commented that
such a system, both hardware and software, had been used to control a
charcoal gasifier at CEMAGRAF with an engine.
Dr Luengo commented that on-board computer control of engines burning
gasahol had not been very successful in Brazil. Dr van der Weide replied
that they had to add a fuel analyser before they could successfully control
gasahol combustion; a feature which Ford Motor Co will incorporate in a
flexible fuel vehicle.
2. PYROLYSIS OIL UPGRADING
Dr Beenackers expressed doubt that a plant as small as 1000 TPD could
be economically viable. Dr Luengo commented that for many site specific
applications, e.g. remote areas, it is the avoided cost of fuel that will
determine the value of a locally produced fuel. Thus, although the cost at
the gate of the refinery may be low, the price of fuel delivered to a remote
user may be very high. Mr Diebold replied that a US DOE sponsored technoeconomic study showed that after successful R&D, both the high pressure
hydrognation and the low pressure zeolite cracking of pyrolysis oils to
gasoline are projected to result in fuel at about US 1.00 per gallon with a
1000 TPD plant. However, the plant needs to be as simple as possible to
achieve this goal. Both Dr Churin and Mr Diebold agreed that more research
needs to be completed in the process to convert pyrolysis oil to gasoline.
Dr Meyer commented that pyrolysis oils are rich in phenolics, but lean
in actual phenol. Catalysts which dealkylate phenolics to phenol would be
very useful to produce a pure chemical (or for use to form methyl aryl
ethers, as being researched by Dr Kiokos from Greece).
It was mentioned that the "Mann Oil" process was to be scaled up to
50 TPD. Currently the smaller scale system produces a product which is high
in asphaltenes (propane insolubles).
3. RECOMMENDATIONS FOR RESEARCH
The following areas were suggested or were implied from the floor
during the discussion, and may well be worth consideration:
A.
Gas Clean Up Processes.

1.
Lower cost emphasis.
2.
Low maintenance emphasis.
343
3.
B.
Computer control development.

a. Biomass gasifier-engine combination.
b. A spin off of automotive engine control.
Pyrolysis Oil Upgrading.

1.
Think in terms of costs avoided by the user when making economic
conclusions and plant siting.
2.
Develop small modular, package plants to avoid the high cost of
field erection. This could help to reduce the typically adverse
effects of the "economy of scale", which would be helpful to the
biomass industry.
3.
More research is needed in the catalytic upgrading of pyrolysis
oil
a. High pressure hydrognation.
b. Low pressure zeolite cracking
(Both processes 3a and 3b are using catalysts developed for
other processes, so catalyst, as well as process development,
would seem promising.)
c. Specialty catalysts : phenolics to phenol.
SESSION VII
347
ECONOMIC AND MARKET OPPORTUNITIES FOR

BIOMASS DERIVED FUELS
A V Bridgwater

Chemical Engineering and Applied Chemistry Department
Aston University
Aston Triangle
Birmingham B4 7ET
UK
ABSTRACT
The economic and market opportunities for thermochemical biomass conversion
through gasification, pyrolysis or liquefaction are concerned with costs of production
and values of products. An analysis of capital and operating costs is presented for fuels
that may be produced by either gasification processes (Part 1) or pyrolysis processes
(Part 2), from which production costs have been estimated for fuel gas and power. The
results suggest that the current lack of interest is not just due to adverse economic
viability, since a wide range of attractive opportunities appears to exist for wastes and
residues to be utilised in the short term, and energy crops in the longer term. The
current low price of conventional energy products contributes to this disinterest, as well
as the status of the technology. Lack of long term operation, operating experience and
perceived reliability problems all contribute to the relatively poor image of the
technology. There seems litde doubt that there will be considerable opportunities for
thermochemical conversion of biomass and solid wastes in the future particularly if
there is pressure from increasing conventional energy prices and also from
environmental concerns over waste management practices. There is need for
technology assessment and, if appropriate, support for long term demonstration. This
will help ensure that the technologies are sufficiently developed and mature to provide
reliable service when the occasion demands.
PART 1 : GASD7ICATION
INTRODUCTION
The economics of gasification and pyrolysis is concerned with costs of production,
values of products, and markets. There are a variety of roles in the implementation of a novel
idea to a commercial installation: the technology developer, the technology licensee, the
equipment manufacturer, the equipment user, and the energy product user. Some of these
functions may be combined.
Implementation
It is important to distinguish between the different expectations of these different
groups:
The technology developer invests on a relatively speculative basis that he will make a profit
on sales of the equipment and/or the licence in the medium to long term. He will commit
resources at relatively high risk, possibly as part of an R&D strategy, or possibly as an
opportunistic response to a funding resource.
The technology licensee acts as an interface or broker between developer and equipment
manufacturer. His role can be significant for non-commercial developers of technology
such as Universities. The equipment manufacturer will often adopt this role as part of the
normal process of commercialisation of new ideas.
348
The equipment manufacturer may have developed his own technology, or be the
technology licensee. He will manufacture and usually market the complete system to the
equipment user to produce his own energy product. Alternatively he may set up an
operation to use his own process to produce energy which he directly sells into the energy
market, in which case he is also the equipment user. He will have conventional industrial
profitability targets to meet in terms of overall company profitability, and in terms of
venture profitability.
The equipment user will either buy the equipment for production of an energy product
(such as fuel gas or power) for his own use, or to export it These two situations will have
different economic criteria to meet If the energy product is generated for internal use, such
as to replace a more expensive fossil fuel, the financial target is quite stringent, typically
requiring a payback time of less than 2 years as it will have to be funded out of revenue
costs. In the case of exporting energy as a utility, the operation would often be viewed as a
more conventional investment, and judged against a much longer time horizon according to
the orthodox practice of the industrial sector concerned - for example for power production
a 20 year equipment lifetime is not unreasonable.
The energy product user may be the purchaser of the equipment, or he may be the customer
of a renewable energy utility. In either case his financial objective is clear: to buy energy as
cheaply as possible, and if investment is required, to minimise the payback time, which
might be not more than one or two years.
There are two main roles in this development chain - the equipment manufacturer, and
the energy product user. Their viewpoints are summarised in Table 1.
Table 1
Requirements and Interactions of Equipment Seller and Energy

Product User
Plant Manufacturer
or Supplier
Product User
or Buyer
Technology
Gas product quality

Alternatives
Performance guarantee needed
Gas product quality

Alternatives
Is performance guarantee available?
Reliability
Technology status
Economics
Cost of plant to make

Economies of scale to make
Profitability
Capital cost of plant to buy (ie price)

Economies of scale in use
Profitability
Variable costs of operation
Feed cost
Product cost
Availability
Reliability
Competition
Feed availability
Minimum size of plant
Product value
Market size
Market growth rate
Time scale
Profitability
Uncertainty
Alternatives
Feed availability
Market
349
Costs, Incomes and Profitability
In all the situations described above, there are a variety of costs to be to be considered:
Research and development cost,
Capital cost of the gasification or pyrolysis plant,
Variable or operating costs of running the plant, such as feedstock, labour,
utilities, maintenance, overheads, etc.,
Production cost of the energy product,
Value of the energy product, which is realised as an income or a saving,
Profitability of the investment required.
Justification for implementation of a new fuel or fuel production system is invariably on
the economic grounds of profitability - is the investment justified according to current company
financial targets, and/or in comparison with alternative investment opportunities? The
techniques usually employed depend on the situation amongst those described above, and can
include payback time, return on investment, net present value and discounted cash flow rate of
return. Sensitivity analysis is often performed to assess the effect of uncertainty on the
economic case. All these aspects are discussed later.
It is important to distinguish between cost and price. It is rare for an investment to be
sanctioned without adequate financial justification in terms of profitability. This means that
there has to be an adequate margin between cost of production and the price that is charged to
justify the investment The expectations for profitability will vary according to sector and role
as explained above, and this is also considered in the cost analyses below.
CAPITAL COST
Scope
The total plant cost of a gasification or pyrolysis system is the sum of all the equipment
costs for the steps required, together with costs of design, installation and commissioning.
The complete system starts with delivery of feed material, which will require some handling,
possibly storage, and may require pretreatment according to the characteristics of the material
and of the gasifier or pyrolyser. Pretreatment is discussed later. After gasification or pyrolysis,
the fuel gas will usually require some clean-up, the nature and extent of which depends on the
feed characteristics and pretreatment afforded, type of reactor, and application.
If the user is some distance away, a high level of gas clean-up is necessary to avoid
deposits in the pipeline, together with a blower or compressor and a pipeline. For power
generation, a high degree of clean-up is essential, and there are efficiency advantages from fuel
gas cooling. Extensive gas clean-up is usually effected by water scrubbing which gives rise to
a waste water problem, the extent of which depends on the feed characteristics and pretreatment
afforded, type of gasifier or pyrolyser, and application. The full scope of a biomass
gasification system is summarised in Table 2, with comments on system requirements and
interactions.
Table 2
Scope and Requirements of Gasification or Pyrolysis Systems
Operation
Need and Dependency
Reception of feed
Storage
Handung
Size reduction
Screening
Drying
Gasification or pyrolysis
Gas cleaning
Wastewater treatment
Gas compression
Pipeline to user
Power generation
Essential - depends on material

Optional - depends on material and reactor
Not always essential - depends on application
Optional - depends on application and gas cleaning
Optional - depends on application and location
Optional - depends on location of application
Optional - depends on application
350
There are, therefore, complex interactions between feed, reactor, and application,
which cannot be generalised and defined by a standard system. The more sophisticated
systems can cost several times more than a basic system where the feed may be in a form that
may be fed directly to a gasifier or pyrolyser, and the application requires minimal gas cleanup. An indication of the relative capital costs of various components of a complete system is
summarised in Table 3 - this is only a very approximate guide to illustrate relative magnitudes
rather than absolute relationships.
Table 3
Typical Relative Capital Costs of Gasification or Pyrolysis

System Components
Operation
Reception of feed
Storage
Handling
Size reduction
Screening
Drying
Gasification or pyrolysis reactor #
Gas cleaning - dry
Gas cleaning - wet
Heat recovery
Wastewater treatment
Gas compression for local use
Gas compression for pipeline
Pipe to user (50 m )
Pipeline to user (1000 m )
Pipeline to user (5000 m )
Power generation (engine)
Approx. cost
relative to
reactor
5
5
10
20
15
40
100
5
20
30
30
20
50
5
30
80
120
Battelle
Columbus
(1)
} 54
John
Brown
(2)
}
}
}
100
100
0
28
14
20
32
0
Notes # This is defined as the reactor system from feed on the ground to hot raw gas from
the reactor, and includes feeder, reactor, ash discharge, piping and conveying, and
instrumentation.
Analysis of Capital Cost and Relationships

Capital cost data broken down by items of equipment or process step is not often
available. As a rule of thumb, the cost of the gasifier/pyrolyser reactor and associated feeder is
about 60% of the equipment cost (3). This is supported by analysis of other studies where the
gasifier costs between 51 and 63% of the total system equipment cost (4).
There is more data available on the relationship between equipment cost and total
installed plant cost of reactor systems. The ratio of total plant cost to equipment cost varies
depending on the type of gasifier construction. This can be estimated with a fair degree of
confidence by orthodox factor estimating methods and ranges from 2.0 to 4.0 (5)
For packaged and skid-mounted units of typically up to 1 t/h capacity, the gasification
or pyrolysis plant is complete except for a concrete area to stand on, and piping up to utilities.
A light shed or cover may also be required. Figures quoted by various manufacturers indicate
that the total installed cost for such a system would be about 1.2 to 1.4 times the equipment
cost (6).
For larger field erected units, over about 1 t/h capacity, much civil and fabrication work
is usually required on site, and available data indicates that the total plant cost is about 2.25
351
times the equipment cost. In the paper industry (with similar types of processing equipment),
the accepted ratio of total plant cost to equipment cost is about 2.25, confirming this
conclusion.
For smaller units which are not skidmounted, less onsite fabrication would be
required than for the large units, and the ratio of total plant cost to equipment cost will be
smaller than that for large units. Afigureof 1.75 has been used for calculating total plant costs
from equipment costs where no installed cost data is available.
Cost data
In order to provide a consistent basis for analysis and estimation of gasification and
pyrolysis system capital costs, information has been collated from a variety of sources for 48
systems in respect of a basic gasifier/pyrolyser from prepared feed on the ground to a clean,
cold fuel gas (3, 7). Included is the feeding system, gasifier or pyrolyser, ash discharge,
cyclone, wet scrubber and water recycle. Excluded are all operations prior to the reactor (such
as drying, chipping etc), wastewater treatment, gas distribution, and utilisation.
Data are usually available as a single figure representing the equipment cost of a
gasifier/pyrolyser system from the feeding equipment to clean gas ie it includes equipment for
the feeding, gasification/pyrolysis and gas cleanup steps of the process. In some cases total
plant costs are available in addition to or instead of the delivered equipment cost. Where
necessary adjustments have been made to exclude or include relevant equipment and/or costs
according to the defined scope. All throughputs are based on dry ash free (daf) basis
feedstocks.
The capital cost considered is a total plant cost including equipment, installation,
design, project management and commissioning, but excluding land costs. Where data have
been collected on a delivered equipment cost basis, this has been converted to a total plant cost
by multiplying by suitable factors. In all cases it has been adjusted to a 1989 time basis with a
process plant cost index, and to a West European location with a location factor. The data is
correlated in Figure 1, shown in Figure 2 by type of reactor, and by process in Figure 3. (8)
Capital cost,
1988
10 :
High cost level
* >
10
10'
Low cost level
'
J
^r%
*l^
10: :
f"y
104
10"1
Figure 1
10"
101
10
Capacity,
daft/h
Biomass Gasifier and Pyrolyser Capital Costs and Correlations
352
10
Q
Capital cost,
1988
Fixed beds
Fluid beds
10'
"
10
11
10
**
"
10*
10"
101
10
102
Capacity,
daf t/h
Figure 2 B iomass Gasifier and Pyrolyser Capital Costs by Type of

Reactor
10"
Capital cost,
1988
107i
106f
Pyrolysers
Gasifiers
CtfU
"
10a
a i
10"
10"
I I I Ill4
10u
I I MIN)
10'
l i l i
Ulf |
10
Capacity,
daf t/h
Figure 3 B iomass Gasifier and Pyrolyser Capital Costs by Type of

Process
Capital Cost Relationships
The data points generally lie on or close to two parallel lines as shown in Figure 1. The
lower line represents the lower limit of gasifier or pyrolyser capital costs, typically achieved by
technically relatively simple gasifier systems and/or systems supplied by small companies, who
do not have the resources to provide extensive backup facilities for example for
353
troubleshooting and performance guarantee This probably also represents the target or lowest
achievable cost for gasification systems. The upper line represents the cost of high technology
systems eg twin fluid bed systems and stirred bed systems and/or systems supplied by major
companies who can provide extensive technical support, and performance guarantees. The
data is correlated in cost models summarised in Table 4.
In the longer term, learning and development will tend to reduce capital costs towards
the lower end and a "target" capital cost has therefore been employed in the economic analysis
to represent a short to medium term realistic goal. This target figure has been used for
estimation of fuel gas production costs.
Table 4
Capital Cost Correlations for Gasifiers and Pyrolysers (8)
Developed or industrialised country locations:

Lower
i988
= 213 000 (capacity, daft/h)0.72

Systems that are more basic technically, or those
marketed by less established companies who are not able
to provide the same level of performance guarantees and
backup
Highen
i988
= 735 000 (capacity, daf t/h)0.72

High technology systems such as twin fluid bed
systems, or systems offered by substantial companies
with backup and guarantees.
Average:
$1988
370 00
Target:
^1988
292 00
(capacity, daf t/h)0.72

Average of all data
(capacity, daf t/h)0.72

This reperesent a reasonable and achievable cost of a
system that is developed and attracts multiple sales, and
thus benefits from the learning effects of an emerging
commercial process. It is the mean of the average and
lower capital costs
Developing countries locations:

l988
= 115 000 (capacity, daf t/h)0.72

Gasifiers that are built in developing countries for local
use (not included in Figure.2). This is very location
sensitive and therefore approximate.
Power Generation
An add-on cost based on a gas engine system is given in the equation below based on
reported data from about 10 sources and discussions with experts. The rule of thumb
relationship that 1 t/h daf biomass will generate 1MW power is reasonable at large plant sizes
of more than 1MW, but as the plant size decreases the biomass requirement increases due to
lower system efficiencies at lower capacities. A relationship between biomass consumption
and power generation has been derived and is given in Table 5, together with capital cost
correlations for power generation and system costs (9). It should be noted that power costs are
354
conventionally expressed as a cost per installed kW which gives no economy of scale.
Table 5
Capital Cost Correlations for Power Generation (9)
Power generation from clean fuel gas in an engine

l988
=
315 000 (capacity, MW electrical )0.72
Turbine system costs would be higher, and additional gas
cleaning plant would be required.
A reasonably efficient biomass to power plant is usually assumed to generate 1 MW for
each 1 t/h daf feed. A more realistic relationship is given by the following equation for the
number of tonnes of biomass required to generate 1 MWh:
=
1.1-O.llogioC
where = tonnes of biomass to generate 1 MWh
and C = capacity of system in MW
Combining these equations gives:

=
^1988
294 000 (capacity, biomass daf t/h)0.75
Total System of Biomass to Power
685
1988
=
O00 (capacity, MW electrical ) 0 7 2
Cost-benefit analysis and trade-offs

The design of a complete system has to consider all equipment necessary to handle and
process feed delivered to the plant to a marketable product - a product manufactured to the
specifications of the application. As feeds will vary in composition and quality, the process
will perform differently according to design and specification, and the quality demands on the
product are dependent on the application, there can be a wide range of process configurations.
Pretreatment operations such as drying, are expensive in capital and operating cost, and can
only be justified by comparing the benefits from a higher quality product or more efficient
process, with the higher costs of installing and operating a dryer.
This would be carried out by comparing production costs, or performing an incremental
profitability assessment on the marginal capital cost (see later). Generally drying cannot be
economically justified for relatively small scale fuel gas production systems, but would be
considered for large scale liquid fuel production systems. Similarly feed storage and handling
requirements will be assessed according to type of feed material, regularity of arisings,
facilities available locally, contractual arrangements for feed delivery and price etc. F eed
storage and handling facilities are thus also site and situation specific. There are few known
guidelines as to what can be justified, and some suggestions are summarised in Table 6. A
discussion of the interactions is given in (10).
VARIABLE OR OPERATING COSTS
The variable or operating costs for a system from prepared feed on the ground to cold clean gas
are considered in this section. The variable costs considered here are feedstocks, utilities,
maintenance, overheads and labour.
355
Table 6
Suggested Guidelines for Economic Justification of Peripherals in

a Gasification System
Operation
Requirements and Limitations
Weighbridge
Daybin
for feed control and management

for levelling out feed deliveries before handling, storage or
processing. Desirable for larger scale processes
for size sensitive reactors; rejects require utilisation. Also
important for removal of non-biomass inclusions such as
concrete and metal for hazard reduction and equipment
protection.
Usually specified as protection in early stages of handling and
storage operations, as part of screening operation.
Some storage is usually required with retrieval facilities. Extent
depends on supply chain and reliability, usually not less than
one week.
for water sensitive materials such as refuse derived fuel pellets.
for poorly prepared feedstock and/or for upper size sensitive
reactors; rejects require utilisation.
usually only justified for large scale operations; and/or where
low cost energy is available such as waste heat.
can only be justified where biomass is very scarce, and product
value is very high. Circumstances are difficult to identify for all
feeds except RDF, when improved performance and reliability
may outweigh higher cost.
is necessary for some highly specific reactors Due to high cost,
this can only be justified for production of high value products
such as chemicals.
to provide intermediate storage in processing chain, typically just
before reactor, and particulary is feed material has been
extensively pretreated such as drying or grinding
Screening
Magnet
Bulk storage in open
Bulk covered storage
Rechipping
Drying
Densification
Grinding
Silo for holding
Feedstock
Three feedstocks are considered: straw as representative of agricultural waste; refuse or
MSW as domestic, commercial and industrial solid waste; wood as representative of energy
crops and forestry products.
Considerable data on arisings in terms of quantity and quality and cost of feedstock
have been collated in recent years by the EEC and national bodies, and this section summarises
the essential features of available feedstocks in order to relate these to gasification and pyrolysis
technology and economics. Costs of feeds relating to UK situations and practice, with some
European data, are summarised in Table 7 (8,11). Wastes are likely to attract higher credits in
Europe due to higher disposal costs, while energy crops and similar materials are likely to have
similar costs. This data, therefore, can be viewed as conservative.
Straw
About 7 million t/y of surplus straw arise each year in the UK for which no ready
market is available, out of a total arising of about 14 million t/y (12). Comparable figures
pertain to Europe. Prices vary by location from 5 to 50/t, but costs have been estimated at
about 17/t or 22/t delivered (12).
356
Table 7
Costs of Feedstock
Characteristics (8)
Materials
and
Effects
of
Feedstock
All costs are in per dry ash free tonne

All costs are currently achievable. Optimisation would be expected to significantly reduce
these figures
Straw
With bam storage at farm, cost at source
Delivered (80 km)
17
22
Refuse/MSW
Domestic
Disposal credit
/raw tonne
5
10
15
20
5
10
15
20
5
10
15
20
Wet "fluff RDF
Dry "fluff RDF
Pelleted RDF
Commercial
as Domestic
Industrial
as Domestic
Cost per daft product

/tonne product
13.50
-1.00
-15.50
-30.00
25.50
11.00
-3.50
-18.00
37.50
23.00
8.50
-6.00
Wood
Forestry Residues, all grades
Ranee. /daf t
Oto 100
Secondary saw mill Residues

Wet wastes (eg bark), 50% moisture
Dry waste, 25% moisture
Energy crops.
Conventional forestry: UK, green chips, daf basis
Short rotation forestry: UK, green chips, daf basis5
Sewage sludge
Dry solid basis
0-30
0-30
Mean. / daf t
30
20
20
30
45
50
Refuse
Domestic About 13 million t/y of domestic refuse are produced with a heating value
of about 9 GJ/t , and containing about 8 million t/y of combustibles.(12), ie about 250
kg/head/y. The average cost of disposal in the UK is claimed to be about 6/t but these are
believed to be very conservative with average costs of disposal nearer 12/t, over a range of
5/t to as high as 40/t. (2) .In Europe, disposal costs are much higher by a factor of up to 5,
with typical figures at around 30/t. This will have a significant effect on conversion
economics below if these costs are translated into credits.
357
Commercial: Arisings of commercial solid waste have been estimated as 7.4 million
t/y (dry basis) with a heating value of around 16 GJ/t ie about 130 kg/head/y. The material is
generally cleaner and drier than domestic refuse with a higher proportion of packaging ie paper,
plastics, wood, etc.
Industrial: Combustible waste arisings from the UK industrial sector have been
estimated at 8.4 million t/y (dry basis) with a heating value of 16 GJ/t, ie about 150 kg/head/y.
Wood and wood waste
Wood and wastes are available in a variety of forms:
Forest residues These have to be removed from existing plantations
for silvicultural reasons.
Wood processing residues - These are wastes that arise in the timber production
industry, usually adjacent to the forest resource.
Waste from the wood manufacturing industry
Fuel wood
Energy crops
Typically the forest products industry generate about 50% waste in the production
process. A considerable proportion of this is utilised in a variety of industries for combustion
and specialist products such as cat litter, horse show ground cover, poultry bedding, etc. There
is still a considerable potential resource available.
Other Wastes
Sewage sludge is another resource that is being investigated for thermochemical
processing. Sludge is generated at the rate of about 25 kg dry solids/head/y. A disposal credit
of up to 50/dry t is potentially available.
Costs
The types of feedstock and costs are summarised in Table 8A, with the effect on feed
cost and gasifier performance summarised in Table 8B.
Utilities
Utilities include:
electricity, for driving pumps, blowers and feeding systems,
wash water for product gas scrubbers,

and
fuel gas for drying,

fines for drying, and/or separate gasification to produce fuel gas,
steam for steam gasification, or moderation of oxygen gasification. If required, steam

would probably be raised on site within plant battery limits, and probably from a waste
heat boiler.
oxygen for oxygen gasification. If required, oxygen would probably be purchased and
charged to feedstock.
waste water treatment.

None of the systems examined require fuel gas, fines, steam or oxygen services.
Noneof the systems allowed for waste water treatment in process or cost terms. It is assumed
that all other energy requirements are met in-house without requiring conventional fuels except
for start-up.
Power costs of gasifiers and pyrolysers have been collated and analysed for which the
mean value is 0.114/GJ (2). However, this does not include any other utilities costs such as
water purchase and waste water treatment, where very little data is available. A utilities cost of
0.25/GJ was used for the base case in the production cost calculations which includes a
contribution for water purchase and treatment.
Maintenance
Yearly maintenance cost is usually estimated as a proportion of the system capital cost,
for which an average value of 2.5% of total plant cost has been found (2).
358
Table 8
Feedstock Characteristics: Effect on Cost and Efficiency
A - Effect on Cost
Moisture
Effect on gasifier
efficiencv
Cost, raw
basis. /t
Cost, daf basis after

processing. /daf t
Straw, on farm
Straw, delivered
17%
17%
78%
78%
17
22
20
26
Refuse,
Refuse,
Refuse,
Refuse,
35%
35%
35%
35%
71%
71%
71%
71%
0
-5
-10
-15
25
15
5
-5
Refuse, dried
17%
78%
-10
15
Wood, on site
Wood, delivered
50%
50%
62%
62%
13
17
26
34
Material
undried
undried
undried
undried
- Effect on Gasifier Efficiency

Moisture content
%. wet basis
(%. drv basis')
0
10
20
30
40
50
(0)
(11)
(25)
(43)
(67)
(100)
Eficiencv to
cold clean gas. %
82
80
77
73
68
62
Eficiencv to
hot raw gas. %
95
92
89
85
80
74
Overheads
Annual overheads cost is usually expressed as a proportion of the capital cost, similar
to maintenance cost. The economic model uses a fraction of the total plant cost to calculate
annual overheads which include rates (local tax), insurance and all head office expenses.
Payroll overheads have been included in the labour costs.
No relevant published data has been found which can be used to estimate overheads for
any one location. The only data available estimated the overheads for a commercial fluid bed
system to be 8% of the total plant cost (2). The local rates and insurance for a gasifier or
pyrolyser would typically be 4% of the capital cost. Multiplying this figure by 2 to cover head
office expenses, gives 8%, which matches the earlier estimate. This figure of 8% of total plant
cost was therefore used in the economic analysis.
Labour
The cost per shift used for the base case is 25 000/year. This includes the cost of one
operator per shift, plus the costs of supervision and payroll overheads. It has been assumed
that the costs of supervision are shared with other plants on a site. F our shifts are required for
continuous operation, three shifts per day, plus an extra shift to cover rest days. If operation is
restricted to weekdays only, then three shifts will be sufficient. There can be significant
variation in labour costs by location and in overheads according to local practice, so each case
has to be assessed on its own merits. Labour costs, however, are usually a relatively small
part of the total product cost. F or less than full time utilisation of the equipment
correspondingly less labour is required, for example 4 or 5 shifts may be required for 8000 h/y
359
or 330 d/y operation, and only thre required for 5 or 4.5 d/week operation.
Power Generation
It is assumed that no additional raw materials, utilities, or labour are required for power
generation. Maintenance and overheads are allowed for in the relationships to total capital cost.
Plant Availability
Plant availability is a measure of the proportion of time that a plant operates compared
to the time that it should be available. Gasification is continuous process that is not conducive
to stopping and starting, and it would therefore be usual to expect a gasification system to
operate continuously. There are many reasons why this does not happen in practice such as
equipment failure, feed problems, planned maintenance requirements, disputes, unfavourable
costs, and lack of demand for products. Plant availability can thus be considered to have two
components: planned and unplanned shutdown. A fluid bed gasifier, for example, may readily
be shut down overnight and restarted from hot within minutes, whereas a fixed bed gasifier can
perhaps be turned down significantly, but cannot be turned off, so different systems will have
different capabilities.
A full year contains 8760 hours, and it is usual in the process industries to allow about
10% of this time for routine or planned maintenance, leaving typically 8000 hours for
operation. Utilisation of equipment for less than 8000 hours per year is thus affecting costs in
an adverse way by increasing the capital element of the production cost. Relatively small scale
gasifiers, however, will often not need to operate all year round, for example at weekends
when the factory may be closed, which would reduce operating hours to around 5000 h/y. For
power production, demand may only be for hours of darkness or aound 4000 h/y. These
effects can be readily incorporated into economic analyses.
There is also unplanned maintenance that is caused, for example, by equipment
breakdown, lack of training, feed blockage, or ash sintering. All are associated with emerging
technologies that are not yet fully developed, and which are responsible for many of the
unfavourable reports associated with biomass gasification. There are many reasons and always
good solutions to these problems, but they do not provide sufficient reassurance to the potential
user or purchaser. These effects are more difficult to include in economic assessments due to
their unpredictability and lack of data for evalution. It is therefore only possible to account for
this aspect of availability by a blanket approximate figure. Subsequent analyses combine all
these effects into one overall figure.
One of the largest biomass gasifiers currently operating in the world is achieving an
availability of 85% on a scheduled 8000 h/y, from operation for over a year, in Quincy,
Florida. It is, therefore, possible to design and operate a gasifier with high reliability and
availability, and there is a need to support such iniatives to overcome the uncertainties still
associated with this technology.
GASIFICATION FOR FUEL GAS PRODUCTION
Methods of Fuel Gas Production Cost Estimation
There are two approaches to the evaluation of a proposed project - calculation of a
product cost with comparison of this cost to the alternatives, or conventional measurement of
profitability using criteria such as payback time, return on investment (ROI), net present value
(NPV) and discounted cash flow rate of return (DCFRR).
Product cost is conventionally calculated by totalling the feedstock cost and operating
costs and adding to them a capital amortisation charge, which covers recovery of the capital and
interest payments on the capital employed.. The product cost may then be compared with the
product selling price to assess profitability of the initial investment. Product cost can either be
an actual cost of production as described above, or a return on the investment can be added to
give a notional selling price, which is again compared to the current market price to establish if
there is a surplus. This latter approach is less common as two measures are required - setting a
target return for the venture, and comparison of calculated product selling price with market
place prices.
360
In contrast, conventional profitability measures include all cash flows, both income and
expenditure, but do not include charges for interest or capital recovery. This is because they
are designed as a method of comparing investment in a project with the investment of a similar
sum in a bank for example or similar investment medium. DCFrr and ROI are expressed as a
percentage rate of return, which can be compared with the bank interest rate, or more usually
with a target rate of return that the company sets for any new investment and which considers
cost of capital and risk. NPV is expressed as the value of a project in current money values, at
a fixed rate of return which is usually taken as the companies target rate of return. All these
measures are usually expressed in real terms. Payback time is the time taken for the capital to
be recovered, ignoring interest payments, and is usually expressed in nominal terms.
Information Requirements
A considerable amount of information has to be collated or estimated in order to derive
a production cost estimate. This is summarised in Table 9 for a "base case", which is used to
estimate production costs of fuel gas and power, and to carry out a sensitivity analysis. The
various operating cost estimates have been derived from procedures or estimates set out above
and key aspects are amplified below. The effect of small changes in financial data, such as
interest rates and escalation rates, can be significant over the long lifetimes anticipated for
process plant such as this, (lives of 15 years are commonly quoted), due to the compounding
effect of small annual changes. These effects have not been explored here but can be examined
through sensitivity analyses. Supplementary data is included in Table 10.
Table 9
Economic and Technical Parameters for Production Cost Estimates
Gasifier technology
Gasifier efficiency (see text)
Feedstock
Feedstock heating value
Number of shifts (for 8000 h/y operation)
Project life
Scheduled operating hours per year
Availablility (Actual operating hours / Scheduled operating hours)
Actual operating hours (see Table 10)
Throughput
Capital cost (including working capital)
Feedstock cost after processing (see Tables 7 & 10)
Utilities cost
Yearly maintenance cost, fraction of capital cost
Yearly overheads, fraction of capital cost
Total cost of labour per shift
Nominal cost of capital
Inflation rate
Air blown fluid bed

58 to 93%
Refuse, straw and wood
20.00 GJ/t daf
4
10 y
8000
80%
6400
5 te/h, daf basis
928 700
as stated
0.24/GJ produced
0.025
0.080
25 000/y
10 %
5%
Gasifier technology: An air blown fluid bed is assumed to be employed although the choice
will have little effect on costs.
Gasifier efficiency: Gasifier efficiencies of 58% to 93% have been used dependant on moisture
content of feed and product. Appropriate data has been used in the calculations and cost
estimates (8)
Feedstock: Three feedstocks are considered - straw, refuse and wood. In each case several
variations are included to represent the most likely alternatives. This is one of the major cost
sensitivities that is explored in detail below for each energy product Other variationsd are
included in the sensitivity analyses later.
Feedstock heating value: This is assumed to be 20.00 GJ/t on a dry ash free basis (daf).
Number of shifts (for 8000 h/v operationl: This is taken as 4 for continuous operation as it is
361
common practice in the process industries. Lower levels of operation are assumed to require
less shifts as summarised in Table 10 below. Hours of planned operation must not be
confused with hours of achieved operation - the former requires manning for the hours
planned, while the latter is a consequence of unplanned shutdown which reduces output
without a concommittant saving in fixed costs suchn as labour.
Pertinent Data for Estimation of
Performance of Sensitivity Analyses
Table 10
A
Production
lt/h
2.5 t/h
Cold clean fuel gas - target cost

291 500
563 800
(target cost = mean of average and lower cost - see text)
Hot raw fuel gas
247 800
479 300
(target less 15% for omission of gas cleaning equipment)
Power generation (from Table 5)
606 500 1 173 100
(1 t/MWh, target cost + generating costs)
Capital cost to cold clean gas (from Table 4)
Lower
213 000
Average
370 000
Higher
735 000
412 000
715 700
1 421 700
5t/h
10 t/h
928 700
1 529 800
789 500
1 300 500
1 932 400
3 183 000
678 600
1 178 900
2 341 800
1 117 800
1 941 800
3 857 300
Operation, hours per year
Basic h/v
No of Shifts
50%
2
3
4
4
4
4 500
5000
6000
7000
8000
C
and
Capital costs (see Table 4)
Case
Costs
2 250
2 500
3000
3 500
4000
Actual h/v at Availabilities

70%
80%
60%
90%
3 150
3 500
4 200
4900
5600
4 050
4 500
5400
6 300
7 200
2 700
3000
3600
4 200
4 800
3600
4000
4 800
5600
6 400
Refuse feedstock cost for different cases (from Table 7)
Product
Disposal
credit. /te
Cost raw
refuse. /te
Cost product:.
Ms.
Cost d.a.f.
product. /te
Wet "fluff' RDF
5
10
15
20
3.38
-0.25
-3.88
-7.50
8.45
-0.60
-9.63
-18.70
13.50
-1.00
-15.50
-30.00
Dry "fluff' RDF
5
10
15
20
6.38
2.75
-0.88
-4.50
18.75
8.10
-2.55
-13.20
25.50
11.00
-3.50
-18.00
Pelleted RDF
5
10
15
20
9.38
5.75
2.13
-1.50
27.55
16.90
6.25
-4.40
37.50
23.00
8.50
-6.00
362
Project life: This taken to be 10 years in common with process plant in the process industries.
Scheduled operating hours per year: An 8000 h year is assumed (the availability of 80% gives
6400 h/y). Lower levels of plant utilisation can be considered in a sensitivity analysis.
Availablility (Actual operating hours / Scheduled operating hours): 80% is a reasonable and
achievable target for well run biomass gasification plants.
Actual operating hours (see Table 10): This is the planned operating hours of 8000 h multiplied
by the anticipated availability of 80% giving an actual operation of 6400 h/y.
Throughput: This is taken as 5 te/h on a daf basis, as being able to exploit the economies of
scale at a reasonable and achievable size for short term implementation. This is one of the
major cost sensitivities that is explored in detail below for each energy product
Capital cost (including working capital): This is taken as the mean of the lower and average
capital costs derived in the cost analysis above, and is refered to as the "target" capital cosd.
For the 5t/h plant the cost adopted is 928 700, and details of the data employed for the range
of plant sizes considered is summarised in Table 10. This approach was taken as there are
substantial learning effects to be enjoyed from replication, and the cost figures used will
therefore provide a production cost that is representative of short term achievable costs, without
adopting an unduly optimistic viewpoint of minimum cost, or an unnecessarily pessimistic
view of average or high costs with no further developments possible.
Feedstock cost after processing as stated (see Table 7).
Utilities cost is taken as 0.24/GJ produced (8).
Yearly maintenance cost, is expressed as a fraction of the capital cost at 0.025 which is taken
from Table 9.3.5.
Yearly overheads is taken as a fraction of the capital cost at 8.0% (2)
Total cost of labour per shift of 25 000/y from Table 9
Nominal cost of capital. An average long term view of the cost of money is taken as 10 % in
real terms, which is that usually attributed to a low risk investment Sensitivity analyses can be
carried out on both on cost of capital and plant life, but previous experience shows that these
are not significant
Inflation rate is assumed to average 5%/y.
Production Cost Estimates
Production cost estimates have ben derived for a range of typical feedstocks for Europe
at different scales of operation. These are summarised in tabular form thus:
Fuel Gas Production Costs by Feed Type - Cold Clean Gas
This situation is often considered to the most likely short term opportunity for fuel gas low heating value clean and cold fuel gas for retrofitting. The system has been described
earlier as an erected plant which processes feed on the ground to a clean fuel gas. All capital
costs and direct operating costs are included except:
wastewater treatment - there is wide range of contamination possible depending on
gasification technology and feed, and a wide range of treatment costs depending on
extent of contamination, technology, and local requirements,
a return on the investment - expectations of a commercial return depend on several
factors such as the role of the investor, the perceived risk, and short and long term
views of the energy market.
The estimated production costs are shown in Table 11.
Fuel Gas Production Costs by Feed Type - Hot Raw Gas
Production of hot raw gas instead of cold clean gas as shown in the above analysis,
has been derived by subtracting 15% from the capital cost for loss of water washing
facilities, and an increase in gasifier efficiency due to utilisation of the sensible heat in the
hot gas which amounts to an increase in gasifier efficiency of about 12% (see Table 11).
The results are summarised in Table 12. There is less confidence in the production costs
for hot raw gas due to less reliable data on costs and performance of such systems, and
definition of realisable sensible heat.
363
Table 11
Fuel Gas Production Costs by Feed Type - Cold Clean Gas
Scope: As in Table 9
The current maximum published interruptible natural gas price is 2.9/GJ. 80%
gives a fuel gas price of 2.32/GJ. Costs underlined are those below this current
market value of 2.32/GJ
Feedstock
1 t/h
STRAW
Conversion at 75% efficiency
22/t delivered (26/t daf)
17/t on-farm (20/t daf)
3.72
3.32
REFUSE
Wet fluff -0.60/t product (-l/t daf)
2.01
Includes disposal credit 10/t raw refuse
Conversion at 71% efficiency with moisture at 25%
Dry fluff 8.10/t product (11/t daf)
2.68
WOOD
30/tdaf
5.08
20/tdaf
4.22
Table 12
Production cost. /GJ

2.5 t/h
5i/h
10 t/h
2.93
2.52
2.63
2.45
1.18
0.86
0.67
L21
1.61
4.07
3.20
3.67
2.81
3.44
2.57
Fuel Gas Production Costs by Feed Type - Hot Raw Gas
Scope: As in Table 9
Current published interruptible natural gas price is 2.9/GJ. 80% gives a fuel gas
price of 2.32/GJ. Costs underlined are those below this current market value of
2.32/GJ
10 t/h
2.5 t/h
5t/h
1 t/h
STRAW
17 on-farm (20/t daf)
3.04
2.72
REFUSE
L52
7o
2.19
Dry fluff 8.10/t product (11/t daf)
WOOD
30/tdaf
3.98
20/tdaf
3.29
2.48
2.08
2,17
2.03
0.94
0,69
0.54
1.57
1.33
12
3.19
2.51
2.90
2.21
2.72
2.04
364
Electricity Production Costs
Production costs of electricity have been estimated from the capital and operating
cost models above, and are summarised in Table 13. It is assumed that 1 daf t biomass will
generate 1 MWh in a state of the art system. This relationship has been widely verified
with practical experience. Theoretically, 3.6 GJ = 1 MWh. 11 daf biomass has an energy
content of 20 GJ, which is converted at say 70% efficiency to gas, and from there to
electricity at say 30% efficiency. This gives an overall conversion of 1 t daf biomass to
1.16 MWh. The 1 t to lMWh (or 1 t/h to 1 MW) relationship has been taken as a
conservative estimate.
Table 13
Electricity Production Costs
Scope: As for Table 9

Current bulk supply electricity cost tarif for industry is about 3.0p/kWh
(0.03/kWh), although many smaller users who are more likely to be customers of
power from systems considered here will be paying much more. Arecentlyquoted
figure is 4.21 p/kWh. A figure of 4.0p/kWh (0.04/kWh) is therefore used as the
cut-off price. Costs underlined are those below this latter figure.
Feedstock
STRAW
Production cost pence/kWh

lt/h
2.5t/h
5t/h
lOt/h
1MW 2.5 MW
5MW
10 MW
6.71
6.11
REFUSE
3.99
Dry fluff 8.10/t product (11/t dafi
5.21
WOOD
30/tdaf
7.03
20/tdaf
6.03
5.28
4.68
4.67
4.26
2.56
1.95
1.54
3.78
3.17
2.77
5.59
4.59
4.98
3.98
4.58
3.58
Production Cost Analysis: Cold Clean Gas

A detailed analysis of production costs of cold clean fuel gas for a range of cases is
given in Table 14. This shows the significance of feed cost in most situations.
365
Table 14
Production Cost Analysis: Cold Clean Gas
Scope: 5 t/h feed daf; conditions as base case, Table 9.
FREDSTOCK
Total Capital
cost
cost
/G.T /CiJ
STRAW
17 onfarm (20/t daf)
2.63
2.22
0.24
0.24
2.39
1.98
1.73
1.33
0.21
0.21
0.24
0.24
0.20
0.20
REFUSE
Wet fluff l/t daf
Dry fluff ll/t daf
0.86
1.61
0.26
0.24
0.60
1.37
0.07
0.72
0.22
0.21
0.24
0.24
0.21
0.20
WOOD
30/tdaf
20/tdaf
3.67
2.81
0.31
0.31
3.36
2.50
2.59
1.72
0.27
0.27
0.24
0.24
0.26
0.26
Variable cost
Subtotal Feed Labour Utilities O/H&M
/GJ /GJ /GJ g/Ql
PART 2 : PYROLYSIS
PYROLYSIS TECHNOLOGIES AND PRODUCTS
Pyrolysis produces gas, liquid and char: the relative proportions of which depend very
much on the pyrolysis method and reaction parameters. Much of the present interest in
pyrolysis currently centres on the liquid products due to their high energy density and potential
for premium liquid fuel substitution. Several liquid fuels can be produced directly or indirectly
oil or biooil and slurries of charcoal with water or oil. In order to carry out the cost analysis
it is helpful to briefly review the technology and products (13).
The main products of pyrolysis are:
Liquid. "Oil" or biooil has been produced in yields of up to 70% wt on feed (dry basis)
from flash pyrolysis on laboratory experiments. Commercial operation may not give such
high yields and a more conservative figure of 50% wt is used in the calculations below. It
has an elemental analysis similar to source biomass and an HHV of 2025 MJ/kg. The
product can be used directly as liquid fuel oil or upgraded to a hydrocarbon fuel. Cost
analyses for both products are included.
Solid char can be produced at yields of up to 30% wt on a volatilefree basis (up to 50%
with high volatiles) depending on the process. Low char yields accompany high liquid
yields. The char has an HHV of 30 MJ/kg and the product can be used as solid fuel
directly, or briquetted, or slurried with water or oil to give a liquid fuel. Cost analyses for
both slurry fuels are included.
A fuel gas is also produced:
EITHER an MHV fuel gas from indirectly heated processes at yields of up to 80% wt on
feed from flash pyrolysis at high temperatures; or up to 20% wt from low temperature flash
pyrolysis. It has an HHV of 1520 MJ/Nm3 and the product can be exported or used in
plant for process heat, feed drying or power generation. This is not considered further as
the process is assumed to be energetically self sufficient by using this byproduct gas.
OR an LHV fuel gas is produced from partial gasification processes at yields of 80140%
wt on feed. It has an HHV of 48 MJ/Nm3 and again the product can be exported or used
inplant for process heat, feed drying or power generation. This is not considered further
366
as the process is assumed to be energetically self sufficient by using this byproduct gas.
LIQUID PRODUCTS
Yields of liquids from pyrolysis can be influenced by the rate of reaction, with fast or
flash pyrolysis at lower maximum temperatures giving the highest liquid yields, with up to
75% wt being reported. This liquid product may be readily bumed and has been employed for
this purpose. Problems have, however, been reported in its use, and special precautions may
have to be taken in handling, storage and combustion. For these reasons, pyrolysis liquids
cannot be readily assimilated into a conventional fuel marketing infrastructure, although there is
adequate evidence that they can substitute for fuel oils in several applications. The discount
necessary for these lower quality fuels to be adopted in place of conventional fuels could be up
to 20%, but this is insignificant compared to the current range of oil prices in the market place
as shown later. Upgrading is necessary to give a product that is compatible with conventional
fuels, but this is expensive. The products that are considered in the economic analysis are
listed in Table 1 with explanations for selection, and significant parameters and properties.
Table 1
Liquid Products from Flash Pyrolysis

Composition
Crude pyrolysis liquid (oil or bio-oil)

Char-water slurry
Char-oil slurry
Notes
60% wt char (a)

20%wtchar(d)
HHV
MJ/kg
22.5
18.0(b)
24.0
Yield, wt %
ondaffeed
50
50(c)
60(e)
a this is a probable upper limit for a pumpable slurry

b based on a char heating value of 30 MJ/kg
c based on 30% wt char yield (volatile free) on daf feed and 60% wt solids in the
slurry
d this is a probable upper limit for a pumpable slurry
e based on 50% wt oil yield andl0% wt char yield on daf feed and 20% wt solids
in the slurry
COSTS OF PYROLYSIS DERIVED LIQUID FUELS

Of major importance in implementation of pyrolysis technologies, as with gasification
technologies, is the economics of production. The costs of production are made up in a very
similar way as for gasification (see Part 1), and the relevant parameters are summarised in
Table 2. Significant differences do, however, arise in capital cost which are shown in Table 3,
and in process yield which is summarised in Table 1.
Production costs for each product have been derived in analogous ways as for
gasification and results are summarised in Tables 4 to 6. These are based on directly
attributable costs with no allowances for environmental benefits such as low sulphur, or fiscal
benefits suchreplacement/reductionof imports.
367
Table 2
Typical Economic and Financial Parameters for Pyrolysis Base

Cases
Pyrolysis technology
Entrained flow or fluid bed
Pyrolyser efficiency (see text)
58 to 93%
Feedstocks
Refuse, straw and wood
Feedstock heating value
20.00 GJ/t daf
Number of shifts (for 8000 h/y operation)
4
Project life
10 y
Scheduled operating hours per year
8000
Availablility (Actual operating hours / Scheduled operating hours)
80%
Actual operating hours (see Part 1)
6400
Throughput
5 te/h, daf basis
Capital cost (including working capital)
See Table 3
Feedstock cost after processing (see Part 1)
as stated
Utilities cost
0.24/GJ produced
Yearly maintenance cost, fraction of capital cost
0.025
Yearly overheads, fraction of capital cost
0.080
Total cost of labour per shift
25 000/y
Nominal cost of capital
10 %
Inflation rate
5%
Table 3
Capital Costs of Pyrolysis Processes for Bio-oil, Char-water

slurry and Char-oil slurry Production
Capital cost of pyrolysis processes
1 t/h
2.5 t/h
5 t/h
Basic pyrolysis process

Lower (from Part 1)
213 000
412 000
678 600
Average (from Part 1)
370 000
715 700 1178 900
Higher (from Part 1)
735 000 1 421 700 2 341 800
Target capital cost (from Part 1) 291 500
563 800
928 700
(target capital cost = mean of average and lower cost - see Part 1)
lOt/h
1117 800
1941800
3 857 300
1 529 800
Pyrolysis for Bio-oil

437 250
845 700 1393 000
Target plus 50% for feed preparation, feed drying and oil recovery
2 294 700
Pyrolysis for Char-water slurry

320 650
Target plus 10% for slurry preparation
1 682 800
620 200
1 021 600
Pyrolysis for Char-oil slurry

466 400
902100 1485 900 2 447 700
Target plus 60% for feed preparation, feed drying, oil recovery and slurry preparation
368
Table 4
Scope:
Pyrolysis Liquid (Biooil) Production Costs by Feed Type and

Scale
As in Table 2
Costs include drying and using surplus process gas
The current average (scheduled and typical) medium fuel oil price is 2.26/GJ,
and cover a range from 1.53 to 3.02/GJ. Costs in bold underlined are those
below this current market value. This is probably the nearest product to biooil in
terms of ease of handling.
The current average (scheduled and typical) light fuel oil price is 2.84/GJ, and
cover a range from 2.08 to 3.63/GJ. Costs underlined are those below this
current market value
The current average (scheduled and typical) heavy fuel oil price is 1.95/GJ, and
cover a range from 1.41 to 2.52/GJ.
1 t/h 2.5 t/h
5t/h
10 t/h
STRAW
17/t onfarm (20/t daf)
REFUSE
Wet fluff 0.60/t product (l/t daf)
Includes disposal credit of 10/t raw refuse
WOOD
30/tdaf
20/tdaf
Table 5
Scope:
5.34
4.81
4.19
3.66
3.72
3.19
3.43
2.89
2.94
1.79
1.32
1.03
5.70
4.81
4.55
3.66
4.08
3.19
3.78
2.89
CharWater Slurry Production Costs by Feed Type and Scale

As in Table 2
and cover a range from 1.53 to 3.02/GJ. Costs in bold underlined are those
below this current market value. This is probably the nearest product to biooil in
cover a range from 2.08 to 3.63/GJ. Costs underlined are those below this
1 t/h
2.5 t/h
5 t/h
10 t/h
STRAW
17 onfarm (20/t daf)
REFUSE
Wet fluff 0.60/t product (l/t daf)
WOOD
30/tdaf
20/tdaf
6.15
5.48
4.82
4.15
4.29
3.63
3.98
3.31
3.15
L2
L23.
fL2&
6.59
5.48
5.26
4.15
4.74
3.63
4.42
3.31
369
Table 6
Scope;
Char-Oil S lurry Production Costs by Feed Type and S cale

As in Table 2
and cover a range from 1.53 to 3.02/GJ . Costs in bold underlined are those
below this current market value. This is probably the nearest product to bio-oil in
cover a range from 2.08 to 3.63/GJ . Costs underlined are those below this
lt/h
lOt/h
5t/h
2.5 t/h
STRAW
REFUSE
Wet fluff -0.60 product (- 1/t daf)
WOOD
30/tdaf
20/tdaf
3.99
3.60
3.14
2.76
2.79
2.41
2.57
2.19
2.26
1.41
1.06
0.42
4.24
3.60
3.40
2.76
3.05
2.41
2.83
2.19
DISCUSSION
Liquid fuel production from waste with its high disposal credit clearly offers the more
attractive opportunities for commercial implementation, with oil and char-water slurries giving
similar production costs. Char-oil slurries offer a significant advantages due to the higher
yields of products, but there are more uncertainties in their production and use which require
resolution. Both feed cost and product yield are major economic factor in minimising product
cost. Both wood and agricultural wastes offer opportunities for oil and char-oil products at
higher capacity plants and if the feed cost is sufficiently low. Char-water slurries are less
interesting in these situations.
A major uncertainty is the value to be attached to the product It might be compared to a
light fuel oil with a scheduled price in the UK as high as 3.63/GJ which opens up wider
opportunities for wood, agricultural wastyes such as straw, and energy crops. Alternatively if
the product is compared to heavy fuel on the open market, and also requires a discount for
successful sales, then only larger capacity high disposal credit waste fed processes have a
chance of success. On the market side, therefore, conventional liquid fuel product prices and
their movements are a dominant influence on the rate of implementation and degree of success
of these technologies.
UPGRADING OIL TO HYDROCARBONS
Upgrading technology is not well developed with most attention being paid to either
hydrognation or zeolite processing to give synthetic gasoline and other hydrocarbons. The
third alternative is slurrying with water or oil to give a liquid fuel substitute. This is only at an
early stage of development, with few details available on technology complexity, additives or
costs.
Some preliminary estimates of production costs of upgraded liquids as hydrocarbons
are indicated in Table 7, to give some idea of the performance of the two main technologies for
producing gasoline, diesel and fuel oil from biomass by flash pyrolysis and liquefaction.
These technologies are at a much less advanced stage of development. The data is taken fom
370
the recently completed IEA DBL (Direct Biomass Liquefaction) study (14), which will be
continued as ALPS (Assessment of Liquefaction and Pyrolysis Systems).
Table 7
Liquid Hydrocarbons Production Cost by Flash Pyrolysis and

Direct Liquefaction (14)
Scale
1000 daf t/d wood
Rash Pvrolvsis
/GJ
Direct Liquefaction
4
ZIQI
Primary liquid
Product cost
Primary product
Product value *
94.3
5.3
Pyrolysis liquids
48.0
2.1
266.1
7.7
Liquefaction liquid
66.0
2.2
Final product
Product cost
Final product
Product value *
423.6
9.3
Gasoline, high octane
225/t
512.3
11.2
Gasoline, low octane; + Diesel
Product costs
it
200/t
Note * Current approximate UK figures
CONCLUSIONS
The production cost analyses presented above show the short term potential for energy
production from wastes, particularly where there is a substantial credit associated with disposal
of the waste, as feedstock contribution is particularly significant. Why, then, has so little been
done to gasify these wastes, or any attractively priced biomass resource?
The answers are firstly that considerable attention has been paid to waste conversion
throughout the world, and secondly the lack of success is due to many factors, including
technology, economics, environment, politics, and social attitudes. A comprehensive
assessment of these factors and their interactions cannot be considered here, but some of the
salient points are identified.
There arg still technical problems to be resolved in reliability and performance, but these are
not insurmountable and there is evidence in several operating examples in Europe and
North America where problems have been satisfactorily resolved.
The economic attractiveness has been reduced by low conventional energy prices which has
removed the pressure to resolve technical problems and develop better systems. This is
compounded by the perceived uncertainty of these newer methods of energy production,
with a preference by industry and government to invest in low risk ventures in the absence
of any significant economic advantage.
A further factor in the perception of gasification arises from comparisons with conventional
fuels i.e. natural gas. This is widely available, totally reliable, and with zero contaminants,
none of which applies to biomass or waste derived low or medium heating value fuel gas.
There is considered indifference to examination of alternative fuel specifications by many
users who take a conservative viewpoint. There is a similar perception of pyrolysis
products arising from comparisons with conventional fuels i.e. fuel oils. The lack of
understanding of the nature and utilisation constraints of these new fuels is likely to inhibit
their use in the short term.
In a more unstable environment, the incentives to find alternative energy sources will cause
more serious attention to be placed on these technologies. The pressures will come from
the environmental lobby who expect cleaner and safer waste disposal methods, and the
energy lobby who will react to an unstable energy supply situation when it arises.
There seems little doubt that there will be considerable opportunities for thermochemical
371
conversion of biomass and solid wastes in the future particularly if there is pressure from
increasing conventional energy prices and also from environmental concerns over waste
management practices. There is need for technology assessment and, if appropriate, support
for long term demonstration. This will help ensure that the technologies are sufficiently
developed and mature to provide reliable service when the occasion demands.
ACKNOWLEDGEMENTS
Much of the data reported in this paper were generated for the Energy Technology
Support Unit at the UKAEA, Harwell, UK, as an update of earlier work (4). They are
intended to be published in due course in a strategic review of thermochemical conversion
technologies for biomass and wastes (8). All opinions and statements are the views of the
author and in no way reflect any views of the UKAEA or the UK Department of Energy.
REFERENCES
1
2
3
4
5
6
7
8
9.
10
11
12
13
14
Feldman, H, et al., US DoE Thermochemical Contractors Meetings, Portland 1984,

and Minneapolis 1985
Smith, D, John Brown Engineers and Constructors Ltd, Private communication
H Levelton & Associates Ltd, Enfor project C-258, "A Comparative Assessment of
Forest Biomass Conversion to Energy Forms." Volume V, D ata Book of Unit
Processes for Primary Conversion by Thermal, Chemical and Biological Methods.
Bridgwater, A V, Double, J M, and Earp, D M, "Technical and market assessment of
biomass gasification in the UK", report to ETSU, UK Dept Energy, 1986
"Revised Guide to Capital Cost Estimation", Institution of Chemical Engineers, UK,
1988
Watt Committee: Working Party on Gasification; "The Cost and Competitiveness of
Low Calorific Value Fuel Gas from Coal".
"Energy from Biomass: A Process Manual for 90 Conversion Routes:. Technical
Insights Inc, Fort Lee, New Jersey, USA, October 1983.
Bridgwater, A V and Stronach, J, "A Review of Thermochemical Conversion
Technologies", Report to ETSU, Department of Energy, 1989
Bridgwater, A V and Double, J M, Institute of Energy, May, 1988
Bridgwater, A V and Double, J M, 4th EC Conference on Biomass for Industry and
Energy, Orlans, (Elsevier Applied Science, 1987)
Mitchell, C and Bridgwater, A V, These proceedings
ETSU personal communications
Bridgwater, A V, Beenackers, A A C M and van Swaaij W M, "Biomass Pyrolysis
and Liquefaction: Status and Opportunities in the European Community", Proceedings
of Euroforum New Energies, EEC Conference, Saarbrcken, October 1988
Elliott, D C, et al "A Technical and Economie Analysis of D irect Biomass
Liquefaction", in Energy from Biomass and Wastes XJU, IGT, February 1989.
372
ENVIRONMENTAL PROBLEMS IN THE USE OF BIOMASS FUELS

GLOBAL AND LOCAL ASPECTS
Philippe GIRARD, CENTRE TECHNIQUE FORESTIER TROPICAL
DEPARTEMENT DU CENTRE DE COOPERATION INTERNATIONALE EN
RECHERCHE AGRONOMIQUE POUR LE DEVELOPPEMENT
45 bis, Avenue de la Belle Gabrielle
94736 NOGENT SUR MARNE CEDEX
FRANCE
Tel : (1) 48 73 32 95
Telex : CETEFO 211085F
Sumnary
In Europe and especially in France, biomass energy use has increased
over the last few years. The various issues, concerning biomass energy use seriously dealt with so far are such as : trade balances, market positioning according to sector, fuel supply problems and distribution. On the other hand, related environmental problems are more often ignored.
The emission levels depend upon the transformation process utilized
viz combustion, gazification, carbonisation. Industrial units deal
reasonably well with the pollution problems. It is not the case for
residential heating and small scale charcoal making.
In term of quantity, non condensable vapours represents the major
tant. Hydrocarbons and pyroligenous oils contain many species of chemical compounds and some of them are known to be carcinogenic. Whereas, the particulates could cause different lung infections.
The emissions represent not only the environmental problem but mean
also the economic loss due to unburnt combustible. Therefore reducing pollution from unburnt combustibles could also improve the financial gains as a result of efficient performance.
Therefore, it is necessary to compare this form of pollution to pollution levels from different fuels.
In Europe, and especially in France, biomass-derived energy production by thermochemical means has increased considerably over the last few
years, particularly in the field of residential heating. In France, public bodies have been instrumental in promoting development in this area.
Official commitment has encouraged the development of a new sector of
economic activity and has contributed to a proportional reduction in oil
imports. Until now, reviews of this sector have always kept to the analysis of trade balances, market positioning according to sector, fuel supply problems and distribution. However, a detailed study of problems related to the use of biomass as fuel reveals a number of environmental aspects which are a cause for grave concern but are more often than not
ignored.
373
Woodfuels may be characterized by a generally high and variable moisture content and by high levels of volatile matter (80 % in weight). Levels of emission can only be controlled through the control of heat propagation. Thermal regulation requires great care, which present techniques
do not always permit. This results in :
- over-estimation of energy yields
- difficult and sometimes hampering operating procedure
- unacceptable levels of atmospheric pollution.
Awareness of an concern for these problems vary with the different sectors involved in thermochemical biomass transformation. Pollution problems are dealt with reasonably well in the case of high-output
industrial units, either directly as such or indirectly through optimization of equipment performance, but in the case of residential heating and
small-scale charcoal-making equipment there is considerable room for improvement .
- Combustion : with the recent crisis in oil supplies, many people in industrialized countries have turned to firewood for individual
heating needs, primarily for financial reasons. The impact on the environment can be considerable, as certain American studies have down <1> <2>
<3>. Pollution in this case is essentially atmospheric (dust and hydrocarbons ). Emission levels can be very high and vary according to the nature
of the equipment and fuel used.
- Gasification : the nature of pollutants from gas producers (dust
and hydrocarbons) is an obstacle to development in this sector. This is
true for heat production in agro-industry where tolerance to certain compounds is very low <4>, as well as for energy production for motors supplying driving power or electricity <5>. In the latter case, the need for
reliable and low-cost gas-scrubbing systems is the final obstacle in the
development of gas-producing equipment, especially for developing countries where potential demands is very high. At the present stage in technical development, activities in this area are purely exploratory and
woodfuel consumption is correspondingly low.
- Charcoal production : this sector has until now been considered
of marginal importance, but recent studies by the CTFT, the Laboratoire
National d'Essais - LNE and the CITEPA (*) <6> have shown that local atmospheric pollution resulting from charcoal-making activity can be considerable. As a result of these studies, the French Ministry of the Environment has introduced legislation aiming to implement controls on listed
units.
We aim here to set out results acquired to date in order to give
an overall view of environmental problems resulting from biomass transformation, with particular regard for woodfuels used in residential and
small-scale industrial combustion and pyrolyser installations, these sectors being by far the most polluting and the heaviest consumers of wood.
NATURE OF THE PRINCIPAL POLLUTANTS EMITTED THROUGH THERMOCHEMICAL BIOMASS TRANSFORMATION
Pollutants are generally placed under three different headings :
- Particles in suspension in gas emissions.
- Hydrocarbons and condensable or pyroligneous organic compounds present
in vapour or aerosol form.
(*) CITEPA : Centre Interprofessionnel Technique de la Pollution Atmosphrique .
374
- Noxious gases as 00, NO, SO*. Wood and biomass rarely contain sulphur,
which means that fuels derived from them have significant advantages
over the conventional fuels.
The mechanisms of the pyrolysis process determine the nature and concentration of pollutants, which vary according to a wide range of parameters. Among these, reaction temperature and the kinetics of thermal transfer are the most significant.
Where industrial combustion units are concerned, pollution is limited thanks to the optimisation of techniques or to the installation of
effluent reprocessing systems. The same is true for industrial charcoal
production units where emissions are infrequent and very brief when techniques are well mastered, the main polluters are small-scale units using
partial-combustion techniques where all smoke is discharged into the air.
Production units with clean kilns are uncommon in Europe and almost unknown in developing countries.
The table 1 gives data from different studies in the matter. The figures given are not necessarily directly comparable as the objectives
and methods used in the studies were not identical.
These studies show fairly high levels of pollution and wide variation in results, the latter being mostly due to the differing conditions
of equipment operation as the table makes clear. For example, the particle emission factor varies from 0.5 to 22 g/kg of wood according to furnace temperature and to the size of wood pieces. Under poor operating conditions, domestic heating appliances become "faulty pyrolysers".
Work by DUSSERRE <15> on wood-fired boilers confirms these results
and clearly indicates the prospects that can be opened up by improving
equipment.
IMPACT ON THE ENVIRONMENT
Where particle emission is concerned, studies carried out in the US
have shown that almost all dust particles can be inhaled. Although they
are not a direct cause of illness, these particles can be a contributing
factor in the development of lung infections <7>.
There a large numbers of hydrocarbons and condensable organic compounds, over 300 compounds having been identified <7> <10> <11>. Scientists are particularly concerned with the polycyclic hydrocarbons, some
of which have been clearly shown to be carcinogenic (see Annexe). A significant proportion of these substances are emitted together with dust particles, thus increasing the risk of propagation and contamination.
Incondensable substances make up the larger part of effluent. The
use of wood as fuel or for charcoal production produces large amounts of
carbon monoxide whose insidious toxicity has long been proved. The presence of nitrous oxides in woodsmoke is noted in <7>.
According to a CERN study carried out in France <12>, 5 million homes were using wood for fuel in 1984, with wood being the primary fuel in
50 % of cases. Average unit consumption, measured during a field survey
and weighted according to local woodland structure, was found to be 16
stacked m 3 in a nomai heating season where wood was the primary fuel,
and 3 stacked m 3 where it was used as an auxiliary fuel. This brings total fuelwood consumption in this sector to 45.5 million stacked m 3 (i.e.
17 million tonnes or 6.7 million TPE*).
*TPE : Tonne Petroleum Equivalent.
375
In 1985 wood consumption for French charcoal production amounted to
only 400 000 tonnes according to our estimate. When communal wood or biomass fuelled heating installations are added to these figures, the national total for biomass-derived fuels is equivalent to 8 million TPE or 4 X
of French energy consumption in 1986 <13>.
According to our sources, consumption in some European countries is
in all probability higher than this, but it must be noted that we do not
at present have any European figures on this.
ECONOMIC IMPACT
In addition to environmental problems, high emission levels of unburnt effluent have the following consequences :
- Corresponding reduction in conversion yields. Energy yields are of less
than 50 X for charcoal production by means of partial combustion techniques without heat recovery systems.
- Reduced efficiency and reliability of equipment. Flues in residential
heating units require more frequent maintenance and fire hazards are increased with poor performance.
- Wood becomes less competitive in relation to conventional fuels such as
coal.
This gives all the more cause for concern for the following reasons :
- Wood is superior to other biomass fuels and is the most convenient to
use in all the sectors concerned and especially for residential heating purposes. It must also be noted that wood and charcoal meet as
much as 90 X of energy needs in some developing countries, where the improvement in energy yields from charcoal production is essential and
must be given priority. Any action taken in this area must include measures to reduce pollution.
- Wood has a very good public image, which provides a firm basis for all
action taken in view of developing its use for energy production. This
is particularly true in the present context of increasing public awareness of environmental and ecological problems.
- Pollution could be significantly reduced if techniques which have now
been perfected were applied under appropriate conditions. Manufacturers should be aware of these and provide instructions as to the size
of wood pieces to be used, maximum moisture content, loading frequency,
etc ...
Besides reducing pollution, lowering emission levels through optimisation, better definition of equipment and effluent recovery during the
carbonization process will lead to financial gains as a result of improvements in yields and performance. Prospects are therefore promising in
this respect as reducing pollution does not necessarily involve additional expense to the user.
Although pollution resulting from the use of wood for energy production should not be underestimated, woodfuel use must be considered within a wider context.
The table 2 <14> <15> makes a comparison between the different fuels
used for heating purposes in units of different sizes :
As for the previous table, care should be taken in comparing these results. These clearly indicate that residential heating is a source of pollution, with coal being the worst offender.
It should also be noted that motorway transport causes the following forms of pollution <16> :
376
For guidance, it should be noted that 25 million cars with a pay
load under 3.5 are on the road in Prance, travelling 12 000 km per year
on average with an average fuel consumption of 9 litres per 100 km for pe
trol and 7.2 litres per 100 km for diesel oil. (Studies are now under way
on a proposal for European norms aiming to reduce pollution).
CONCLUSIONS
lhe observations given here and the numerous research programmes now
in progress indicate that there are prospects for significant improve
ments in equipment performance. Unfortunately, as can be seen from the bi
bliography, few coordinated programmes have been implemented at Euro
pean level, in comparison with studies carried out in the US over the
last 10 years. It is therefore necessary to :
Develope methods and equipment for standard!zed sampling and analysis
which are specific to each situation. The methods used by DUSSERRE, for
instance, were not applicable to carbonization processes.
Such methods must be recognized and accepted by all laboratories and
should be flexible enough to allow for the following :
. application by all laboratories (cost of implementation)
. ease of implementation
. permanent review of cycles allowing sequential sampling of suffi
cient duration.
Carry out fundamental research on pyrolysis with particular regard for
yield improvement and a corresponding reduction in unburnt emission
through a better understanding of phenomena and the redefining of appa
ratus and their implementation.
Carry out a large number of equipment performance tests by working on
the parameters affecting thermochemical reactions in the conversion pro
cess. The aim is to acquire data needed for further development and fi
nalizing of new techniques. Quantification of effects on the environ
ment must be undertaken at the same time.
Supply training and information to users.
Develope new and more efficient techniques and equipment. In the case
of charcoal production, this will necessarily require the elaboration
of effective smokerecovery systems. The prospects of smokeincinera
ting systems appear to be promising as these would not only reduce pol
lution but also supply considerable quantities of heat which can be ma
de use of during the process (drying out of wood before carbonization).
Significant reductions in emission levels and the corresponding im
provements in energy yields, together with optimization of equipment per
formance should make woodfuels more competitive in relation to conventio
nal fuels such as coal or domestic fueloil. Pollution levels generated
by residential heating should drop with a switch to such alternative
fuels.
A more specific approach to European fuelwood consumption would be
of benefit and would certainly clarify the issue at stake.
In this context, an increase in wood and bicmass use for energy pro
duction can provide a tenable answer to the problems of sustaining Euro
pean agriculture, bearing in mind that at the beginning of 1988 it was de
cided to lay fallow one million hectares of land, and that several thou
sand hectares more are left fallow each year. If costeffectiveness thres
holds can be overcome, progress in genetic engineering can open up pros
pects for the development of coppice plantations in Europe for energy pro
duction purposes.
377
BIBLIOGRAPHY
(1) ROBERT E., MANNING I &. J., COOK W., HAYES T. Preliminary report on a
study of the ambient impact of residential wood combustion in Petersville, Alabama. Residential solid fuels conference, Portland, Oregon,
USA, 1981.
(2) CARLSON J., Residential wood combustion in Missoula, Montana.
An overview of its air pollution contributions, health effects, and
proposed regulatory solutions. Residential solid fuels conference,
Portland, Oregon, USA. 1981.
(3) DECESAR R. The quantitative impact of residential wood combustion and
other vegetative burning sources of the air quality in Medfrd, Oregon. Residential solid fuels conference, Portland, Oregon, USA, 1981.
(4) S.C. BHATTACHARYA, N. SHAH. Utilization of producer gas for drying
agricultural crops. Regional seminar on alternative energy application in agriculture. THAILAND, 1986.
(5) M. STASSEN. Baseline monitoring need. Chevet gazifier station in Sechelle. UNDP European Bank. Biomass technology group. TWENTE. Juillet 86.
(6) GIRARD P., MEYER C , BOILOT M., FONTELLE. Caractrisation des missions de carbonisation en four combustion partielle. Mise au point
de systmes de traitement des fumes de carbonisation. 4me Confrence europenne. Biomass for energy and industry. 1987.
(7) HUBBLE B.R., STETTER J.R., GEBERT E., HARKNESS J.B.L., FLOTARD R.D.
Experimental measurement of missions from residential wood burning
stoves. Residential solid fuels conference, Portland, Oregon, USA.
1981.
(8) CITEPA. Monographie. Carbonisation du bois et pollution atmosphrique. 1986.
(9) MEYER C. Dtermination des rejets atmosphriques lors de la carbonisation par combustion partielle. Mmoire de fin d'tudes ENITA-CTFT.
1986.
(10) RUDLING L., AHLING B., LFROTH G. Chemical and biological characterization of emissions from combustion of wood and woodchips in small
furnaces ans stoves in Sweden. Residential solid fuels conference,
Portland, Oregon, USA. 1981.
(11) BEAUMONT 0., Pyrolyse extractive du bois. Ecole des Mines de Paris.
1981.
(12) CERN. Etude de la consommation de bois de chauffage en maisons individuelles (rsidences principales). Saison de chauffe. 1984-1985.
(13) P. CORTE., T. DURAND., T. GONARD., B. MOREL DE LA COLOMBE. Thermochemical use of biomass in France. Evaluation and trends in AFME strategies. 4me Confrence europnne. Biomass for energy and industry.
1987.
(14) COOPER. Evironnemental impact of residential wood combustion emission and its application. Air pollution control. Vol. 30. pp. 855
861. 1980.
(15) DUSSERE P., Etude des chaudires bois : contribution la mesure
des missions des composs imbrls, l'valuation des rendements
nergtiques et la modlisation de la combustion. INSA. 1986.
(16) DELSEY M., La pollution due aux moyens de transport. INRETS Laboratoire nergie nuisances. Note d'information n' 13. 1979.
378
Table 1.
POLLUTANTS EMISSIONS FROM RESIDENTIAL WOOD

COMBUSTION AND CARBONIZATION
Combustion
(7)
Residential Heating
Combustion
(7)
Res. Heating
Carbonization
(8)(9)
Partial Combustion
Red Oak
(large pieces)
Ditto
(small pieces)
0.82 2.58
3.9 7.7
Furnace Temperature "C
250 360
500 800
400450
CO (g/kg wood)
138 196
92 148
0.8 22.2
0.5 2.3
3.0 8.4
0.8 2.1
Wood
Consumption (kg/h)
Particles
(g/kg wood)
Condensable organic
compound (g/kg wood)
P.A.H. (g/kg wood)
0.004 0.04
Pinus
sylvestris
80110
5.110.2**
14.525.3
0.100.432
0.008 0.03
* Cycle l a s t i n g approx. 20 h f o r a t o t a l load of 600 kg anhydrous wood.

** Measures made i n conformity with French standard NF 44051 and
NF 43003. S t u d i e s now i n p r o g r e s s a t the CTFT and LNE appear t o c a s t
doubts on the use of measuring apparatus under c o n d i t i o n s imposed by c a r
b o n i z a t i o n t e c h n i q u e s and s u g g e s t t h e implementation of a more appropria
t e sampling method.
T a b l e 2 . POLLUTANTS EMISSIONS FROM DIFFERENT

FUELS USED FOR HEATING PURPOSES
CO g/th
NO, g/th SO g/th
Particle
g/th
B(a)P
Mg/th
(*)
Gaz
0.036
0.144
0.001
0.036
0.32
Fueloil
0.072
0.162
0.5412.6
0.126
3.6
Coal
6.3
0.18
0.9 13.6
1.08
10 000
Wood (open hearth)
5.4
0.45
2.34
180
0.126
0.054
2.16
535
39.6
Wood (stoves)
(*) Benzo (a) pyrne.
Table 3.
POLLUTANTS EMISSION FROM MOTORWAY TRANSPORT
NO
Total hydrocarbons..
4star petroKNCV*: 12300 th/t) Diesel (NCV : 10900 th/t)

g/th
g/kg fuel
g/th
g/kg
0.73 0.91
200 250
16.26 20.32
810
0.91 1.37
10 30
0.81 2.44 10 15
0.46 0.73
>> 1
5 8
0.18 0.27
20 50
1.63 4.06
2 3
379
WASTE MANAGEMENT AND PYROLYSIS:
CURRENT SITUATION, TRENDS AND PROSPECTS
C H . NELS
Federal Office for the Environment, Berlin
Summary
For the past 15 years researchers from both the scientific world and
industry have been attempting to develop new waste treatment processes
which might prove more effective than the conventional methods of
landfill, composting and incineration in meeting current demands for
the exploitation of waste by the recovery of raw materials and energy.
One such process is pyrolysis. High hopes were initially vested in
this process,
so high in fact that the judicious . use of known
technology was occasionally prevented. Only a very small number of the
waste treatment processes which have proved successful in the Federal
Republic of Germany have been, or are yet to be, tested on a large
scale. Materials recovery or waste disposal is given main priority
depending on the type of waste used as feedstock. Ultimately, the
overall criterion by which such processes are judged is their impact
on the environment. Although pyrolysis is not expected to revolutionize the treatment of waste in the future, it should, in individual
instances, be able to complement existing processes, or offer a
practical alternative.
1. INTRODUCTION
In the early seventies, two main methods were used to treat household
waste in the Federal Republic of Germany: landfill and incineration. Under
the landfill programme, a total of more than 50 000 refuse tips were in the
process of being reduced to approximately 500 controlled landfill sites.
Waste incineration technology had reached a relatively advanced level, after
being given a particularly important boost in 1974 by changes to the
technical specifications for air pollution control : these introduced limit
values for the emission of noxious gases such as HCL and HF for the first
time, and made the use of waste gas scrubbers obligatory in incineration
plants.
It was then that the first energy crisis struck. An artificially
induced fall in the supply of crude oil, the main source of energy, prompted
various countries in the West to step up their search, not just for new
reserves of oil and natural gas, but also for alternative organic materials
which, after suitable treatment (pyrolysis, degasification, gasification),
might yield oil and gas. Consideration was given to anything with a high
organic content: household refuse, sewage sludge, special category waste,
scrap tyres, the organic component of material from breakers' yards, waste
from the plastics industry, etc. Research was carried out into processes for
treating this waste, such as the rotary kiln, the vertical reactor and the
fluidized bed (direct and indirect heating).
380
Very few of these processes were in fact new. The practice of heating
wood to produce charcoal, a clean fuel which gives off very little smoke,
was widespread even in the Middle Ages.
The degasif ication of coal to
produce town gas became popular in the 19th century, though it was rendered
largely redundant by the advent of natural gas, and is now confined to the
production of coke for the iron industry. The coal and gas industries also
produced most of the raw materials for the chemical industry before the
development of petrochemistry.
On the basis of past experience,
it ought therefore to have been
fairly obvious that pyrolysis and gasification would not solve the energy
problem in one fell swoop, and that such processes might even lead to new
pollution problems. In certain circles, however, euphoria reached such a
pitch that experts who were anything but wholly enthusiastic were branded
"anti-environmentalist". The words of one inventor summed it all up: "If we
pyrolysed all household waste using my process, and then did the same with
all plastic waste, scrap tyres, dead wood from the forests and all old
asphalt road surfaces, we would have so much oil that we wouldn't have to
import any. Plans for new nuclear power stations could be scrapped, and
power stations which are already operational could be shut down. So why
won't the state promote research into this form of energy?".
That is precisely what the state has done. In the Federal Republic of
Germany,
approximately DM 400 million was spent on research into waste
disposal between 1976 and 1989, of which 10% (DM 40 million) was devoted to
pyrolysis and gasification. What exactly has been achieved, and where do we
stand today?
2. AIMS OF PYROLYSIS AND GASIFICATION

Pyrolysis and gasification aimed to achieve
essentially three
different goals. The primary objective as regards the treatment of household
and related wastes was that of disposal. The main concern was to reduce the
volume of waste and convert it into a residue that could be disposed of as
landfill without damage to the environment. The raw materials and energy
created in the process were welcome by-products which were sold commercially
to reduce running costs.
The pyrolysis and gasification of special category waste with a high
calorific value (e.g. plastic wastes, used tyres, organic residues from
breakers' yards) was essentially aimed at the recovery of raw materials such
as oil, metals and, where possible, coke and carbon black. Unlike processes
used for treating household refuse, processes such as these were to be
employed only if overall costs could be offset by the sale of the raw
materials produced.
Finally, there were pyrolysis processes which involved the careful
separation of different types of materials. These types of process, which
were generally discontinuous, were used for separating composite organic
materials from metal components, or removing organic impurities from metal
(e.g.
conveyors used in paint shops).
This last category will not be
discussed in further detail here.
The following four hopes played an important role in generating
support for the initial and subsequent development of pyrolysis and
gasification processes, particularly as a means of treating household waste:
1.
The new processes would make it possible to build

plants for the thermal treatment of waste. These would
even when throughput was low (perhaps down to 250 t/d)
used to dispose of waste in the smaller administrative
easy-to-operate
be cheap to run
and so could be
regions.
381
2.
3.
4.
These new processes would make it possible to recover not only energy,
but also large quantities of valuable materials contained in waste,
such as synthesis gas, oil, coke and metals.
These new processes would be able to cope with varying quantities of
non-homogenous waste, so that all types of waste (including special
category waste and sewage sludge) produced within a given collection
area could be disposed of together.
These new processes, besides achieving all the above, would have
minimal impact on the environment.
Since any material that can be incinerated (household waste, plastic

waste, used tyres and other organic materials, etc.) can also be either
degasified or gasified, supporters of these new processes initially saw
themselves as being in direct competition with the waste incineration
industry. This occasionally led them to point out in no uncertain terms the
inherent weaknesses of the rival process. Incineration,
they stressed,
produces excessive volumes of waste gas which require scrubbing, as well as
a solid residue which has not fully burned out. Furthermore, incineration
furnaces often have difficulty coping with wastes having a high calorific
value (e.g. scrap tyres) and certain other types of waste such as glass and
plastics,
the resultant energy cannot be stored,
valuable scrap iron
separated out of the slag is lost through oxydization, and finally, large
quantities of noxious emissions are produced. Sometimes, the disadvantages
of the rival process were taken as automatic proof of the advantages of
pyrolysis and gasification. This disregarded three points:
1.
2.
3.
Waste incineration was an easy target for the critics: the process had
been in use for more than 30 years and had thus been subject to
rigorous scrutiny. Small wonder, then, that its disadvantages were so
well known. By contrast, no pyrolysis or gasification process had yet
undergone such a gruelling test.
Incineration as a process cannot be dismissed out of hand simply
because some plants are badly designed or poorly run. The incineration
of waste is itself primarily an environmental protection measure. The
fact that it, like any conversion process, has its disadvantages,
should and does encourage efforts to improve it. The great potential
in this field has not yet been exhausted by any means, as can be seen
from the latest developments in waste incineration as a way of
reducing harmful substances.
The debate tended to become unduly restricted when incineration and
pyrolysis/gasification were being considered as alternatives. The new
processes also have their advantages and disadvantages, so decisions
as to which of these processes to adopt should be made on a case-bycase basis - and other possibilities should also be considered.
Whatever truth there may be in the saying that the better is the enemy
of the good,
the fact remains that the debate on incineration versus
pyrolysis has occasionally produced quite unsatisfactory solutions. Suppose,
for example, that all the waste disposal sites in one particular area were
full, and that the required reduction in the volume of waste could not be
achieved by recycling, then incineration might well be the only solution
left. However, it proved impossible to persuade the politicians of this
fact: the technology employed in the incineration industry may well be
state-of-the-art, but pyrolysis was considered to be better. The upshot was
that tips which were already full to capacity continued to be used (perhaps
without proper foundation work being carried out and without due attention
being given to the problem of water seepage) , or waste was moved to other
382
areas (thereby causing traffic congestion) , or perhaps even exported
altogether, which is highly unsatisfactory from a political point of view.
The current crisis in waste disposal, much bemoaned by the Minister for the
Environment, can be blamed at least partly on the fact that badly needed
waste incineration plants were not constructed because people thought they
should wait for pyrolysis, which was supposed to be "better".
3. CURRENT STAGE OF DEVELOPMENT

Even more
significant
than the technical
differences
between
incineration and pyrolysis as alternative means of treating municipal waste
is the fact that waste incineration plants have been operating commercially
for more than 25 years, and thus have a proven track record. The first waste
incineration plant was built in Hamburg at the end of the last century.
The large-scale industrial exploitation of pyrolysis is, by contrast,
still very much in its infancy despite approximately 15 years of development. The first full-scale pyrolysis plant for waste disposal, which is
situated in Burgau and has a low annual throughput (35 000 t) has been in
operation for just two years now (1) .
The processes developed over the past few years have given rise to
four different types of household waste treatment plants, all of them based
on pyrolysis. The following is a description of the various component parts
of pilot and industrial installations (1):
KWU plant (Goldshfe): scrap reduction; pyrolysis drum heated indirectly via
internal off-gas pipe; gas converter (cracking achieved by substoichiometric
partial combustion in coke bed at approximately 1 000C);
two-stage
scrubber; gas engine with generator; deposition of pyrolysis residues.
Alternatively,
it has been suggested that the cracked pyrolysis gas be
cleaned in a spray dryer producing no waste water, and burned off directly
in a waste heat boiler.
DBA plant (Burgau): scrap reduction; pyrolysis drum heated indirectly via
outside wall; cyclone for partial dust removal; secondary combustion chamber
at around 1200C; boiler with turbine and generator; deposition of pyrolysis
residues (further reprocessing of residues in planned).
PKA plant (Aalen/Unterkochen): waste sorting plant; reprocessing plant for
the "light fraction" (compressed pellets); pyrolysis drum heated indirectly
via gas burner; cyclone for partial dust removal; gas convertor (cracking in
coke bed); single-stage wet scrubbing; rotary burner; boiler with turbine
and generator; burning off of pyrolysis gas together with biogas from a
waste composting plant (alternatively, gases can be used in a gas engine);
calcination plant for the processing of pyrolysis residues ; ozonation plant
for cleaning continuously discharged waste water.
KWU low temperature carbonaization plant (Ulm/Wiblingen): waste treatment;
pyrolysis drum; sorting of pyrolysis residues; cylinder crushers or swing
pipes for pulverizing fine fraction;
smelting furnace for pulverized
pyrolysis residue and low-temperature carbonization gas (at between 1200
and 1300C); waste heat boiler with turbine and generator. There are plans
to use the smelt granulate as building material or landfill.
Two other
pyrolysis processes are being developed, mainly for plastic and special
category wastes. These are the fluidized bed process (Ebenhausen) and the
rotary drum process (Salzgitter) (2).
BBC plant (Ebenhausen): special category waste fed in small pieces into a
fluidized bed reactor via rotary feeder and worm conveyor; fluidized medium
heated to between 500 and 850C depending on final product desired; removal
of dusts and carbon black from pyrolysis gas; cooling of gas and, where
383
possible, distillation of high- and low-boiling pyrolysis products; removal
of sand and metal waste from bottom of reactor.
Salzgitter pyrolysis (Salzgitter): special category industrial wastes (solid
and fluid) fed into rotary tube in the absence of oxygen; degasification of
between 650 and 700C;
outward transfer of solid pyrolysis products;
separation into pyrolysed coke and metal fractions
(where possible);
two-stage cooling and scrubbing of pyrolysis gases ; burning off of waste gas
in combustion chamber with waste heat boiler; multi-stage treatment of waste
water.
The pyrolysis of sewage sludge is not yet sufficiently advanced to
enable large-scale industrial plants to be constructed.
Further research
will thus be carried out into the following two general concepts, each of
them involving a pilot plant with a capacity of approximately 0.5 t/h:
medium-temperature pyrolysis (approximately 500C), with the option of
materials recovery and industrial use of products;
low-temperature pyrolysis (approximately 300C) with the option of use
of products for heat generation and industrial use of products (e.g.
fatty acids) where appropriate.
These plants will generate large quantities of products. Investigations are to be carried out into the exploitability of such products and the
possible effects of such plants on the environment, particularly as regards
secondary emissions. When the pilot phase comes to an end, both concepts are
to be the subject of a detailed scientific and technical evaluation by an
independent body.
The above descriptions of initial research in this field show quite
clearly that the main priority when the development of pyrolysis first began
was the recovery of raw materials such as gas, oil, coke and carbon black.
Today, by contrast, the emphasis is on waste disposal. There are three main
reasons for this change in direction: firstly, there is a shortage of space
for tipping household refuse and waste from breakers' yards;
secondly,
plastic wastes are not ideally suited to processing, as they yield only a
limited amount of new products; and thirdly, the amount of sewage sludge
being used in agriculture is decreasing whilst the total volume of sludge
produced is on the increase.
It is, of course, better to exploit raw materials and energy produced
during the treatment of waste, rather than simply discharging such products
into the environment. But there is no prospect of waste being pyrolysed on a
regular basis inorder to recover energy and raw materials. Rather, pyrolysis
must be regarded as an alternative or complementary way of treating
materials which would otherwise have to be disposed of as waste. What role,
then, can pyrolysis play in the future?
4. WASTE MANAGEMENT: THE CHALLENGE (3)
The objectives of waste management have been an integral part of the
Federal Republic's environmental policy since about 1970. The 1971 programme
on the environment contains a report by the waste disposal project group
giving a detailed analysis of the situation at the beginning of the decade.
This report was critical, but it also pointed to the legal and technical
measures which could help solve the problem, as well as the likely cost of
such measures. The main requirements were : systematic arrangement for the
removal of all waste from households
and industrial plants ;
the
discontinuation of indiscriminate dumping of mixed waste at small tips and
the establishment of central plants where waste could be disposed of
384
according to category, or exploited for other purposes. The 1971 environment
programme constituted the first large-scale survey of waste management
objectives since 1945.
A comprehensive catalogue of objectives was drawn up in a document
entitled "The Federal Government's waste management programme '75". Adopted
in 1975 and published the following year, this policy programme is as
relevant to waste management today as it was when it first appeared.
A 1978 report by the committee of experts on environmental matters
gave the first detailed account of the environmental and economic ramifications of waste management problems. The waste management objectives of the
various environment policy programmes can be represented in a schematic
diagram (cf. Figure 1 ) .
RAW MATERIALS EXTRACTION
PRODUCTION/CONSUMPTION
MINIMIZATION OF RESIDUES
RE-USE
UNAVOIDABLE RESIDUES
INTERMEDIATE PRODUCTION LEVEL

SUITABILITY CHECKS FOR RE-USE
PRIMARY
UNAVOIDABLE WASTE
PRIMARY WASTE TREATMENT

SECONDARY
RECYCLING
SEPARATION OF VALUABLE MATERIAL
WASTE WHICH CANNOT BE SEPARATED
SECONDARY WASTE TREATMENT

CONVERSION INTO MATERIAL
WHTrH rhN f^v. FYPT.nTTEn
MATERIAL WHICH CANNOT BE EXPLOITED
TERTIARY WASTE TREATMENT

DUMPING OF RESIDUE
WASTE WATER/AIR
NUISANCE EFFECT 0 F RESIDUE
Fig. 1. Waste Management Action Model

This model is linked to the natural ecosystem via input (supply of raw
materials) and output (amount of residue).
Waste management activities
impose a system of internal and external cycles on this flow chart, dividing
385
it up into five separate levels of action. The top two levels correspond to
production and consumption,
whilst the bottom three represent waste
treatment and the various technical processes available.
If a high percentage of targets is met on one level, the amount of
materials passed down to the next level will be smaller relative to the
quantity of material passed into the recycling chain. The further down this
model a type of material moves,
the more specialized the technology
required. The meeting of waste management targets becomes more elaborate and
expensive with every step. Put another way, action taken at production and
consumption level is much more effective as a means of conserving resources
and protecting the environment than are attempts to treat the waste
produced.
The waste management targets for each action level can equally be
regarded as the "five principles" of waste management, as follows:
1.
2.
3.
4.
5.
The amount of residues and waste of all kinds generated by production,

services and consumption should be kept to a minimum, or preferably
avoided altogether. This first principle covers activities such as the
following:
- the development and application of production processes which use a
minimum of raw materials and generate little waste;
- the development and production of consumer goods which are more
durable;
- the development and production of goods which do not create disposal
problems once their service life is exhausted;
- the introduction and further development of repurchase systems.
This first law impinges on the freedom of both producers and
consumers.
It is first and foremost a political principle which
requires a change of thinking in a number of areas and the abandonment
of a number of convenient consumer habits.
Unavoidable waste should be returned to the production or consumption
cycle as soon as possible. This is the principle of primary recycling,
which requires responsible decisions to be taken, on the basis of
careful checks, as to the suitability of waste for the production of
secondary raw materials. It also calls for the separate collection of
certain types of waste in households and industry. Primary recycling
involves collecting certain materials and residues before they become
mixed up with other materials to form rubbish.
Maximum quantities of usable materials should be obtained from
collected waste.
This principle is based on the assumption that,
generally speaking, waste cannot be avoided. Those responsible for
waste disposal must make every effort to remove valuable substances
from the waste collected (secondary recycling).
Waste which remains after the removal of valuable substances should be
further exploited. This fourth principle requires the use of treatment
processes (e.g. composting, incineration, pyrolysis) in order to
convert waste into usable substances or energy. Activities such as
these not only serve to recover valuable products, but help reduce the
general volume and thus ease pressure on the ecosystem, and the high
degree of mineralization means that only substances which are fairly
compatible with the natural background of a particular site need be
dumped.
Any substances still remaining after having passed through all the
stages described above should be carefully deposited in a way that
will not harm the environment. This last means of waste disposal
should be resorted to only when the particular conditions or
386
characteristics of a certain type of waste do not permit treatment at
a higher level.
5. CONCLUSIONS
It is clear from this action programme that pyrolysis and gasification
can be used for the following purposes :
as a means of complementing conventional processes for the exploit
ation of waste (e.g. production of oil from plastic waste);
as an alternative to incineration for the purposes of treating waste
before dumping (mineralization) .
In the latter case, pyrolysis will gain acceptance only if fractions
which are not exploited (pyrolysis residues) are suitable as landfill
material. A
pyrolysis process in which gases or oils produced after
condensation are simply burned off (possibly with pulverized residue
containing carbon) is basically no different from incineration: the only
real difference is that the individual stages in the process are separate
and can thus be better controlled.
Largescale testing of such a process will ensure that realistic
comparisons can be drawn with incineration processes, and will also mean
that persistent discussion of pyrolysis will not stand in the way of
alternative solutions. However, it must be admitted that perhaps one of the
greatest virtues of pyrolysis is the fact that the theoretical debate has
also made a major contribution towards the further development of
incineration.
REFERENCES
(1)
(2)
(3)
SCHOEMPS, H.,
"Verbrennung
oder
Pyrolyse?"
(Incineration
or
pyrolysis?) in LWA Materialen No.2/89.
Contains a discussion of the
current role of pyrolysis in the treatment of municipal waste.
A
G BRIEL, H.
et a l , "Umweltschutztechnik, laufende F+E Vorhaben 1998"
(Environmental protection, current R+D projects, 1 9 8 8 ) , published by
the Project group for environmental protection at the German Institute
for A erospace Research and Testing,
for the Federal Minister of
Research and Technology, p.309 et seq.
A
J EGER, .
"A bfallverwertung in der Bundesrepublik" (Waste exploit
ation in the Federal R e p u b l i c ) ,
published by the Project group for
waste management and landfill redevelopment at the Federal Office for
the Environment, for the Federal Minister of Research and Technology,
p.l et seq. (in p r e s s ) .
387
RAPPORTEURS REPORT ON SESSION VII
ECONOMIC, E N V I R O N M E N T A L A N D LEGAL ASPECTS
R.
FBRY
Commission of the European Communities, Brussels, Belgium
Session 8, together with Session 1 dealing with a general introduction

and with country overviews, was the only session which was not focussed on
the technical aspects, but covered other aspects which are also vital for
the future of pyrolysis and gasification, i.e. economic, environmental and
waste policy aspects.
Dr A.V. BRIDGWATER presented an estimation of the economic viability
of gasification and pyrolysis operations which was based on a very detailed
and well constructed study.
Firstly, a lot of economic and technical assumptions are needed to
define a basic operation configuration, on which the economic calculations
are based. Different types of feedstocks and products are envisaged.
The economics are globally more favourable for refuse than for biomass
(wooden material, straw) treatment because of the refuse disposal credit.
The economic estimation shows that some opportunities exist (based on
the UK situation) for economic operation, even in the short term and at
small scale (about 1 t/h).
However, the present low energy prices have tempered the enthusiasm
for adopting new technologies which often still need to confirm their long
term reliability.
There is a clear need for long-term demonstration operations under the
most favourable circumstances in order to prove the reliability and verify
the economic viability anticipated by calculation.
Mr P. GIRARD gave a lecture concerning the environmental problems
related to the thermal conversion of wood.
Wood is basically a low pollutant fuel and wood conversion has
positive effects on the environment : no SO emissions, CO remaining in
principle in a closed cycle.
However,
a substantial increase in wood consumption for thermal
conversion (f.i.
8 Mio toe of wood was consumed in France in 1986,
equivalent to 4% of the country's energy consumption) could lead to a
non-negligible impact on the environment.
Small scale plants for carbonization and residential heating, whose
operational control is not as good as industrial units,
may lead to
significant pollutant emissions and effluents: small size particulates which
increase lung infections, hydrocarbons and pyroligneous oils of which some
components are carcinogenic, non-condensable vapours such as CO and NOx.
It is important in the case of the small scale plants to train and
inform the users in a better way, while at the same time improving the
thermal conversion control and efficiency.
Dr C. NELS presented the evolution of refuse management in West
Germany.
In the early seventies, the initial trend was drastically to reduce
the number of landfill sites from 5 000 to less than 500. Then came the oil
crisis and the subsequent search for alternative energy feedstocks. Refuse
pyrolysis was enthusiastically embraced as an alternative technology to
municipal waste incineration, whose disadvantages were known from long term
operations. It was hoped that refuse pyrolysis would be a simple technology
388
for smaller throughputs at low costs and with low environmental impacts.
Important RSD funds were allocated for that purpose and some pyrolysis
plants were put into operation.
It appeared however that urban waste
pyrolysis showed specific disadvantages and still required improvement in
order to be competitive.
Anyway,
all the technologies are to be considered with their
respective advantages and disadvantages on a case by case basis, without
leaning too much towards one single technology in particular.
ORKSHOPS
391
WORKSHOP 1 - PRETREATMENT AND CHARACTERIZATION
Chairman: J. BARTON
Rapporteur: J.PISKORZ
Given the limited time available it was agreed that the scope of the
discussions should be directed to identifying aspects of pretreatment and
characterization where further RSD or coordination activity was required.
Based on the conference presentations and experiences of the group members,
it was clear that pretreatment requirements for differing feedstocks varied
widely and there would be little benefit in detailing the design performance
and cost criteria associated with any particular system or equipments.
However, differentiation between waste feedstocks and biomass was considered
to be an important factor in terms of the approach adopted and scope or
degree of pretreatment required.
Generally waste feedstocks attracted a disposal credit, they required
and could support (using the disposal credits) a higher degree of feed
preparation.
Treatment option would be influenced not only by the
requirements of the thermal treatment step but also by disposal or recovery
option for the residues from pretreatment. In addition, the distribution and
fate of toxic or hazardous components in the waste would play a more
important role in determining pretreatment requirements.
For biomass,
whether specifically 'farmed' or the residues from
cropping activities, alternative disposal costs tended to be low and hence
the collection and pretreatment costs had to be fully justified by product
revenues from the thermal treatment stage. However, biomass was usually less
complex in terms of physical and chemical characteristics and thus simpler,
less costly feed preparation methods could usually be developed.
In terms of specific processes used in pretreatment, a few general
comments were made on the following :
1.
Sizing
Although good experiences were reported with rotary

(trommel) screens, flat bed and disc screens for sizing
various feedstocks, the machine selected and screendeck
design had to match the feedstock characteristics and
process requirements. Trommel and disc screens tended to
be more appropriate designs for 'difficult' materials such
as refuse.
2.
Shredding
Although
effective
size
reduction
equipments
were
available for most feedstocks, most group members felt
this was an area where improved design could lead to
reduced operating
costs.
For wood,
chippers were
considered particularly effective in providing suitable
feedstocks for pyrolysis/gasification reactors.
3.
Drying
Whilst
problems have
been experienced
with dust,
explosions and poor drying efficiencies, again the group
reported that suitable designs were available. Cascade
dryers, conveyor 'fluid bed' dryers, flash and pneumatic
dryers, had all proved effective in different applications . Attention was drawn to the effect of drying on the
392
physico-chemical
proparties
of
the
feedstock.
At
relatively
low
temperature
(+110C)
changes
in
crystallinity
of cellulose,
lignin degradation
and
volatile losses would affect yield and composition of the
products from thermal treatment.
4.
Densification
The group reported that a range of different designs is

available and most have been shown to work despite initial
problems. As with shredding equipment the group considered
design improvements were achievable for the densification
process and it was reported that few machines achieved the
reliability and throughputs originally anticipated when
processing
waste feedstocks.
Generally
all
systems
required
feed
moisture
content
levels
below
15%,
preferably below 10%, to achieve a stable, dense product.
It was concluded that whilst many mistakes had been made in selecting
pretreatment equipments, there were enough good examples available and
reported of the above processes to avoid major problems in the future
provided designers and manufacturers took on board past experience. For
novel feedstocks prior testing would always be recommended and this should
be closely linked with an assessment of the response of the downstream
thermal treatment stage.
Whilst the selection of equipments was inevitably feedstock and
process specific, a common factor for all systems was the need for effective
handling, feeding and storage systems. A catalogue of problems was reported
by group members for this aspect with many processes failing due to an
inability to maintain and control material flow.
Three main factors were considered to require further study.
1.
Development of standard test protocols for assessing the flow and
handling characteristics of these feedstocks.
Conventional materials
handling test methods such as those used in the minerals and chemical
industries for hopper design,
conveying systems etc.
rarely provided
satisfactory information for the design and scale-up of equipment for
biomass and waste feedstocks.
2.
Development of standard test protocols to assess biodegradation of
feedstock in storage and its effect on feed composition,
handling
characteristics and health and safety aspects
(e.g.
fire,
airborne
emissions).
3.
Development of automatic control systems for feed handling and
storage. This was considered a particular problem for the developed nations
where labour costs were high. As well as improved system design, development
of robust sensing equipment to assess levels, bulk density, volumetric flow
etc. were needed.
As a general point regarding the problems experienced in handling
these materials, the group agreed that knowledge of the problems and
potential solutions generally resided with plant operators rather than
equipment suppliers. This knowledge should be gathered together, reviewed
and more widely disseminated.
Where similar feed materials can be
identified, the study should include experience from established industries
such as food processing, agriculture and forestry.
In terms of feedstock characterization for thermal treatment the group
considered that thermo-chemical characteristics
were generally
given
attention and well reported by researchers in pyrolysis and gasification.
However, the physical specification of the feed was frequently overlooked
393
when reporting test work and experience. The size, shape, particle and bulk
densities and permeability of feedstocks used affect the thermal process and
such information was needed for developing suitable pretreatment options.
This was an area where an expert group could develop a checklist of
specification requirements, how they should be measured and how they should
be reported.
On specific techniques, mention was made that when assessing slagging
characteristics, the conventional determination of the deformation and flow
temperatures of ash could give misleading results. Initial preparation of
the test sample from the feed material using low temperature,
plasma
techniques, as opposed to using a conventional ashing furnace or ash from
the process,
could avoid physico-chemical
reactions
which prevent
identification of the presence of low melting temperature components.
Based on the discussions, the priority areas for further study which
could be supported by the EC in future programmes were as follows :
1.
A consultancy study of full scale handling and storage systems for
biomass and waste feedstocks. The study should be directed to obtaining
information primarily from the experiences at operating and 'failed' plants
rather than equipment suppliers.
2.
Development of test protocols to assess the handling and storage
properties of biomass and waste feedstocks.
3.
Development of automatic storage and feed systems and associated
sensing instruments for biomass and waste feedstocks.
4.
Development of a common approach to the measurement and reporting of
the characteristics
of feedstocks
for thermal
treatment processes,
particularly physical properties.
394
WORKSHOP 2 - PYROLYSIS
A V Bridgwater
C Roy
Universit Laval
Chemical Engineering D epartment D partement de gnie chimique
Aston University
Ste-Foy
Aston Triangle
Quebec
Birmingham B4 7ET
G1 7P4
UK
Canada
INTRODUCTION
The chairman opened the session by showing a series of transparencies
which summarised the main characteristics of the pyrolysis technologies available.
The advanced pyrolysis technologies are: fast pyrolysis, flash pyrolysis, ultra
pyrolysis, vacuum pyrolysis and hydropyrolysis. These were compared with the
more conventional carbonisation technologies. As opposed to conventional
pyrolysis where the main objective is to produce charcoal, the advanced pyrolysis
route leads to a high yield of organic liquids in the first instance.
The general characteristics of pyrolysis oils were described together with the
properties of the solid product (charcoal). The oil can be used as a fuel and also
contains hundreds of valuable chemicals which can potentially be recovered.
There is also a consensus on how slurries of char-oil and char-water can be
prepared for power generation. The chairman concluded his brief introduction by
showing the different prospective combinations of primary and secondary products
from biomass pyrolysis.
SHOULD PYROLYSIS OF MSW BE CONSIDERED?
This very simple question kept the workshop participants involved in
animated discussion for a substantial amount of time at the beginning of the
workshop. On the one hand there is a growing interest for a better quality of life
and a safer environment. On the other hand, there is also a growing concern about
the traditional methods of Municipal Solid Waste disposal, i.e. incineration
including ash disposal, cost of gaseous emission control etc, and the landfill
approach with problems of leachates, land availability, etc. Can pyrolysis
significantly contribute to the recycling of MSW? It is reported that the Japanese
have already achieved large scale pyrolysis of MSW to gases for power
generation. There is no commercial experience at this stage, however, in the world
for the conversion of MSW to liquid fuels which are easier to burn than solid fuels in
terms of control of emissions.
One problem which was mentioned is the inconsistency of the inlet materials
which will also reflect on the varying quality of the char and the pyrolysis oil
products. The char is loaded with metal and other inorganic substances. What can
be done with it? Should it be burned, gasified or simply dispose of by orthodox
methods? Sorting out the inorganic material as a pretreatment step prior to
pyrolysis might be a more advisable way to go, although not necessarily
economical at the present time. Another problem is what to do with the
halogenated hydrocarbon by-products which will possibly find their way into the
liquid fuels?
An opinion was expressed that most effort should be spent in primarily
mastering feedstocks such as biomass, instead of treating difficult feedstocks such
395
as MSW, in order to give pyrolysis as many chances as possible to emerge as a
leading technology. Nevertheless, there appeared to be a consensus that the
scientific community should immediately afford time and effort at working on MSW
because there is an urgent need for better recycling technologies to get rid of solid
wastes.
One additional remark that an attendee expressed is that something should
also be done with the enormous surplus of straw which is available in some
European countries.
IMPORTANT R&D TOPICS
Some of the problems which ought to be addressed by the scientific
community for the further development of pyrolysis technology include the
following:
improve heat transfer during pyrolysis,
assess the quality of the pyrolysis oil in terms of corrosive properties,
chemical stability, mutagenicity and toxicity, and its fuel properties,
especially if it is derived from MSW,
mention was made about the upgrading of oils. Apart from the
deoxygenation of these oils in gasoline, one further possibility is the
recovery of valuable fine chemicals such as food aromas and perfumes from
these oils, using new separation methods that are more efficient than the
simple distillation method which is commercially used elsewhere.
CONCLUSIONS
There was a consensus about the fact that finding a market for the pyrolysis
products is vital for the feasibility of the process. However, getting rid of wastes is
another goal which is not always compatible with this primary objective of finding a
market for the products. As a consequence, it is imperative that the governments
contribute to the development of recycling technologies together with the private
sector. In fact, there is a growing interest nowadays from large firms for pyrolysis,
due to the positive image such an involvement can stir in the public.
Pyrolysis has many applications, both in the lage variety of feedstocks that
can be treated and in terms of the many types of products it is possible to obtain
during the different processes in development. This development requires time,
financial assistance and collaboration between all participants.
This International Congress and the Workshop are examples of
collaboration which should be mainyained on a regular basis, perhaps in North
America and in Europe.
396
WORKSHOP 3 - GASIFICATION TECHNOLOGY AND ECONOMICS
Y. SOLANTAUSTA
Technical Research Centre of Finland
A.A.C.M. BEENACKERS
Dept. of Chemical Engineering
University of Groningen, Netherlands
INTRODUCTION
A total of about 60 persons participated in the workshop
gasification. The aim of the workshop was to emphasise the aspects
research that should be addressed in future work. An effort was made
define the technologies that should be implemented.
The economics
gasification systems were reviewed.
on
of
to
of
RESEARCH
The following areas of gasification research should be addressed in
future CEC biomass programs.
1.
Catalytic Gasification
Both gasification rate and product gas composition can be affected by

adding catalyst in the gasifier.
Gas impurities can be reduced by
introducing a second catalytic reactor after the gasifier. Both approaches
should be investigated further. Initial results obtained at the University
of Zaragossa are encouraging.
2.
Gas Cleaning for Turbine Applications
One of the most promising areas, where gasification can be utilized,

is power production by combined cycles. However, gas turbines are very
sensitive to impurities in the fuel gas (particles, alkali metal vapours).
Future gasification combined cycles should be equipped with hot gas cleaning
devices to realize the potentially very high efficiency of power production.
Research in this area is therefore of great importance.
3.
Environmental Effects of Gasification
All the environmental aspects of gasification should be studied.

Possible emissions to atmosphere, the nature of the ash, and the quality of
possible washwater should be measured, and the effects of these should be
evaluated.
Gasification combined cycles for coal are assessed as being
environmentally superior to conventional power plants. It should be studied
whether this is also the case with biomass systems.
397
4.
Gasification of Municipal Solid Waste (MSW)
Some participants wanted to promote also research on gasification of

MSW, whereas some were reluctant to do this because of the preceding
unfavourable experiences.
Gasification offers a potentially improved
prospect for removal of impurities from the fuel gas compared to mass
burning. It is particularly noteworthy to monitor the experience in MSW
gasification to be gained from the Sarbrcken plant.
LESS DEVELOPED COUNTRIES (LDC)
Gasification has been applied in numerous cases in LDCs for supplying
fuel for engines pumping water etc. Most of the operations have been plagued
with considerable technical and financial difficulties. More research is
needed to bring about :
reduction of investment cost,
improved reliability of the system,
improved user friendliness, and
gasification of difficult feedstocks.
IMPLEMENTATION
Both low and medium joule gasification should be implemented.
1.
Low joule gasification should be implemented

heat, and in power production 1 to 5 MW scale.
in the production of
2.
Medium joule gasification should be implemented in the production of

power in combined cycles, in which case the gasification has to be
pressurized.
It would be of interest if this application could be
explored in the Clamecy plant. An additional promising technology is
steam gasification in double fluid bed, which enables the production
of medium joule gas without purified oxygen.
ECONOMICS
Gasification of biomass has been applied only in a relatively small
number of cases in Europe. This is mainly due to the low price of oil and
natural gas, which are the main competitors of fuel gas.
Below are presented some economic indicators for different gasification methods. Numbers are only indicative for a superficial comparison,
and they are based on Finnish conditions as of 1986. It should be noted that
the oil prices were considerably higher than now.
POWER PRODUCTION
Atmospheric gasification, conventional power cycle
- competitive in the power range 20-50 MW
Pressurized air gasification, combined cycle
- competitive above 150 MW
e
Pressurized oxygen gasification, combined cycle
398
HEAT PRODUCTION
Fixed bed gasification
Fluid bed gasification
CONCLUSIONS
The largest workshop of the conference wishes to make a call not to
neglect gasification in either research or implementation. The opportunities
of the technology are signficant while considerable expertise has been
developed already during the past years.
ACKNOWLEDGEMENTS
The chairman wishes to thank all who participated to the workshop. The
input of E. Kurkela and M.S. Mendis is especially acknowledged.
399
WORKSHOP 4 - PYROLYSIS AND UTILIZATION
E. Churin
Unit de Chimie et Catalyse des Matriaux Diviss
Place Croix du Sud, 1
134 Louvain-la-Neuve, Belgium
The workshop was organised to discuss the possibilities for the upgrading of
biomass-derived oils to transportation fuels or high-value chemicals and other potential
uses other than just as a heavy fuel.
A typical characteristic of biomass-derived oils is their very high oxygen content
which supposes that they can only be used replace heavy fuel oils.
To obtain high quality fuels or chemicals the oils must be upgradfed in order to
reduce the oxygen content, increase volatility and reduce molecular weight.
This transformation can only be obtained in the presence of a catalyst. At
present, two major catalytic processes are being investigated to this end.
Hydroprocessing of biomass-derived oils is based on the technology applied in the
petroleum refining industry. Typical reaction conditions are temperatures of between
250C and 400C and pressures of between 7.0 MPa and 20.0 MPa (pressures as high
as 35 MP are being tested). Low space velocities are necessary and the best results are
obtained between 0.1 and 0.3 volumes of oil per hour per volume of catalyst. During
this treatment, hydrodeoxygenation takes place through the elimination of the oxygen
constituting the molecules in the form of water, the high hydrogen pressure allows for a
hydrocracking of the heavy molecules but, depending on the reaction conditions, side
reactions lead to the formation of more or less substantial amounts of gaseous
hydrocarbons. High pressure liquefaction oils constitute the best feed for the
hydroprocessing because of the lower oxygen contents but pyrolysis oils can be
processed provided that a pretreatment is effected at lower temperatures as
demonstrated by Elliot at PNL.
400
The catalysts used in this process are CoMo and NiMo supported on alumina,
the liftime of which needs to be established. It was stressed that it could be very
interesting to conduct a study that would lead to the understanding of the degradation of
the oils or hydrotreated oils containing some phenols which could act as antioxydants.
The low pressure upgrading process (almost atmospheric pressure) is based on
the ZSM-5 zeolite catalyst. This zeolite exhibited very high yields to gasoline
compounds when oxygenated compounds, mainly methanol, were transformed.
Pyrolysis vapours from a votex reactor and pyrolysis oils were reacted over this
catalyst but pyrolyis vapours were preferred because the pores of the zeolite are narrow
and the big molecules produced during the condensation of the vapours would be
unable to enter the pores.
It was estimated that about 75% of the primary pyrolytic vapours could enter the
pores (as studied by molecular beam mass spectrometry at SERI) which means that the
time lapse between pyrolysis vapour production and zeolite contact should be very
short. Phenolic compounds exhibit a low reactivity on this catalyst and contribute to
coke formation. For this process, research should be oriented towards the modified
zeolites in order to diminish coke formation and increase the reactivity of some
compounds.
Both processes produce gasoline boiling range compounds constituted of alkylsubstituted benzenes but BTX contents in gasoline is going to be limited by a new
legislation because of their toxicity. This will constitute a serious drawback for the
commercialisation of the upgraded products as transportation fuel.
A method of upgrading the phenolic fraction of the biomass-derived oi without
deoxygenating is the production of aromatic ethers. They can be mixed up to 15% in
the gasoline thus improving the octane number.
Concerning the use of the pyrolysis oils without any chemical transformations,
the only utilization discussed was the replacement of pure phenol in resin production.
The phenolic and neutral fraction extracted after elimination of acidic compounds could
replace half of the puie phenol used in phenol-formaldehyde resin. This research is
sponsored by the industry and industrial implementation is well advanced.
POSTERS PRESENTED
SECTION 1
PRE-TREATMENT, PRODUCTS AND OTHER ASPECTS
405
FULL-SCALE DEMONSTRA TION PROJECTS OF THF, EUROPEAN COMMUNITY
IN THE FIELD OF PYROLYSIS, GASIFICATION A ND CA RBONISA TION OF
BIOMASS AND WA STE
By R.Fabry and G.L.Ferrer
Directorate General for Energy
Commision of the European Communities, Brussels and
K. Maniatis
Vrije Universiteit Brussel
ABSTRACT
The first part of this article is concerned with a
statistical analysis of the proposals for demonstration
projects which have been submitted and selected (or
not) since 1983 in the framework of the annual calls
for offers for the Energy Demonstration Programme of
the European Communities in the field of pyrolysis,
gasification and carbonization of biomass and waste.
The evolution with time of the number of proposals in
function of the technology, the country of origin and
the type of waste used is discussed.
The
second part
reviews
the
selected
projects
(terminated,
in progress or cancelled) and evaluates
the
results
obtained
until
now,
the
problems
encountered and the reasons for the cancellation of
some of the projects.
1 STATISTICAL A N
A LYSIS QE THE DEMONSTRA TION
PROPOSALS SUBMITTED A ND SELECTED
PROJECT
The Energy Demonstration Programme launched in 1978 by

the Directorate General for Energy of the Commission of the
European
Communities
provides
financial
support
for
demonstration projects of an innovatory nature at industrial
scale in respect to energy saving, renewable energy sources
and substitutes for hydrocarbons.
In the period 1978 to 1988, 1631 demonstration projects
have been selected from the 5176 proposals submitted;
resulting in a total
financial support of 841 million ECU,
which makes this programme the largest of its type in the
whole world. A t the beginning of the programme the projects
concerning "Biomass and Energy from Waste" were included in
the sectors "Energy Savings" and "Solar Energy" of the
406
Programme. However since 1983 due to its increasing
importance the sector "Biomass and Energy from waste" became
a completely independent one. In this sector 191
demonstration projects have been selected since the
initiation of the programme for a total financial support of
87.4 million ECU.
The sector "Biomass and Energy from waste" is divided
into 11 subsectors with 1 subsector devoted to pyrolysis,
gasification and carbonisation of biomass and waste. Since
1983, 140 proposals for demonstration projects from the
annual calls for offers of the Commission have been submitted
in the sector "Pyrolysis gasification and carbonization".
Figure 1 presents the evolution in function of time of
the number of the proposals submitted and selected since
1983, when the subsector Biomass and Energy form waste was
implemented. A distinction has been made between the
proposals on carbonisation where the emphasis is on the
production of charcoal (or possibly on the production of
roasted wood or activated carbon) on one hand, and on the
other hand the proposals on pyrolysis and gasification where
the aim is the production of pyrolytic oils and/or the
production of a fuel gas. It is clear that the number of
proposals on pyrolysis/ gasification has been steadily
declining until 198 8 when there was however notably a sudden
increase in the number of the proposals concerning municipal
refuse (4 prop.) and especially various industrial wastes (6
prop.) . It should also be noted that in 1987 the thermal
conversion of wastes in general was excluded from the call
for offers and the 5 proposals
shown in Figure 1 were
submitted by error.
It can be noticed that the selection rate of
pyrolysis/gasification proposals has been very severe : 15%
selected proposals on average (with a zero selection in 1986
and, being normal, in 1987) which is
5% less than the
average approval rate for the complete sector "Biomass and
Energy from Waste". This very severe selection on
pyrolysis/gasification as well as the decline in the number
of proposals submitted between 1984 and 1987 is related to
the technico-economic difficulties that this branch still has
to overcome.
The innovative aspects of the submitted proposals were
often related either to the utilization of the fluidized bed
technology and/or to the nature of the wastes to be treated,
in particular for indutrial wastes.
In the field of carbonization the number of submitted
proposals has been inferior but relatively constant. The
selection rate of the proposals in this field corresponds to
the average selection rate of the entire sector being 20%.
The proposals on carbonization which were not approved either
had no innovative character or did not offer satisfactory
perspectives for economical viability. Generally seen, the
innovative aspects of the selected proposals fell in one of
407
the following categories :

a ) u t i l i z i n g new t y p e s and wider range of dimensions
of
a g r i c u l t u r a l and forestry r e s i d u e s ;
b)improving t h e thermal e f f i c i e n c y and p r o t e c t i o n of t h e
environment by recycling and/or seperate use of the p y r o l y s i s
gases;
c)new products, such as roasted wood.
The classification of the proposals according to the
type of waste utilized is shown in Figure 2. The category of
wood waste comprises logs, chips, waste from the wood
industry and forestry residues. In the group of industrial
waste, wastes of very different origin can be found:
textiles, plastics, used oil, tyres, rubber, shredder and
various PME wastes . In this group the few proposals (5)
concerning commercial wastes, such as carton and packaging
waste is also included. As expected, the group of wood waste
is the most important in particular for carbonization since
it is essential for the production of charcoal and roasted
wood.
However, the other types of wastes and more particularly
industrial wastes are well represented
in the pyrolysis/
gasification proposals. For the industrial wastes, the
selection of pyrolysis/gasification proposals has been a
little bit more favorable than the average. This is partly
often linked either to the fact that materials of high added
value are recuperated from specific wastes (such as carbon
black from tyres) or to the fact that difficult to be treated
wastes (such as wastes with high concentration of plastics,
textile waste, shredder waste) can be eliminated with a more
accurate process control than by combustion, with a
simultaneous fuel gas production. The product gas can either
be used in an engine to produce electricity or in a
boiler/furnace with little modifications to produce steam. On
the other hand, from the 21 submitted proposals on municipal
waste only one project has been selected. This reflects the
severe techno-economic problems associated with this field.
The classification per country of the submitted
proposals is represented in Figure 3. It is clear that 3/4
of the proposals are originating form 3 countries: France,
Italy and Federal Republic of Germany.
Each of them
submitted about 25 % of the proposals. However, for Spain
and Portugal, the proposals could only be submitted as from
1986. It
should also be mentioned that in certain cases a
proposal, not selected one year, has been resubmitted the
following years, (such as for straw gasification or municipal
waste pyrolysis) . Sometimes also the same basic technology
has been used in proposals concerning different wastes and
context, (eg. fluidized bed pyrolysis of wood waste).
However, the impact of such proposals which can not really be
considered as totally distinct, remains-limited.
408
2. THE SELECTED PROJECTS
Before 1983, only 3 projects had been selected; 1 for
each category of : wood, agricultural and industrial wastes.
Nevertheless between 1983 and 1988, 21 projects were selected
in the subsector pyrolysis, gasification & carbonisation.
From the 24 selected proposals, 6 have been completed (the
average duration for the realization of a project starting
from the selection of the proposal till the complete
execution of the programme is about 4 years).
6 projects
were cancelled before or shortly after the signature of the
contract between the beneficiary and the European Commission
and 12 are in progress. The reasons for cancellation of the
projects are essentially economic and/or financial:
bankrupties, restructuring (3 projects), reduced economic
rentability due to increased value of waste (2 projects),
financial plus technical problems (1 project). The number of
selected projects per country is more or less proportional
to the number of the submitted proposals illustrated in
Figure 3.
3. RESULTS AND TRENDS
From the 6 completed projects only one can be considered
successful.
This concerns the production of roasted wood
(Project BM/333/84) which can be used as a reducive agent in
electro-metallurgy or as fuel for barbecues. The technical
reliability of the process has been demonstrated at
industrial scale. However, serious technical problems had to
be overcome during the optimisation phase with increased
investment costs, resulting in lack of rentability of the
demonstration plant. This rentability would be secured for
further replications.
The
other completed projects resulted in different
degrees of failures.
This was the case for pyrolysis of
municipal waste, pyrolysis of used tyres, gasification of
flax residue, gasification of bark and carbonisation of
different forest and plant residues. The positive results
obtained until now in the subsector pyrolysis, gasification
and carbonisation of the Energy Demonstration Programme have
not been very satisfactory notwithstanding the severity of
the selection procedure. This illustrates very well the big
difficulties encountered by new technologies or new
applications of known technologies in this sub-sector in
order to succeed in a breakthrough on the level of economic
rentability, while sustaining the technical reliability.
Nevertheless, the unsuccessful projects have not been useless
since they put emphasis on the technical and economic
problems which still have to be overcome. Other projects are
still in progress or still have to be implemented which could
improve the overall performance. More specifically, in case
of success, the demonstration of forest residues pyrolysis in
409
fluidized bed could play an important role in the optimum
utilization of the forest resources, especially in the
Southern countries of the Community.
For more information please contact :
Commission of the European Communities,
Directorate General of Energy,
200 rue de la Loi
B-1049 Bruxelles
W-wood
A-agrcultural
U-urban
1-lndustriaJ
Typ of watt
Figure 2: Distribution
Figure 1 : Annual distribution of
by type of waste
proposals
submitted
selected
410
2.86%
1.43%
22.86%
24.29%
1.43%
3.57%
5.00%
25.71%
2.86%
2.14%
7.86%
^
H
^
F R 32
IR 2
IT 36
NL 11
PO 3
UK 4
BE 7
DK 5
FRG 34
GR 4
SP 2
Figure 3: Distribution of submitted proposals by country
411
THE USE OF WOOD AS FUEL IN MALAYSIA
W HOI1 and A V BRIDGWATER
Forest Research Institute of Malaysia D epartment of Chemical Engineering
Kepong
Aston University
Selangor
Aston Triangle
52100 Kuala Lumpur
Birmingham B4 7ET
Malaysia
UK
Summary
The efficient use of wood in the solid, liquid and gaseous forms can contribute towards
the fuller utilisation of the nation's natural resources. In Malaysia, only wood in its
solid form is used as fuel. Fuelwood is still an important energy source for the rural
populace and is consumed in substantial quantity for the production of rubber smoked
sheets, tobacco curing, brick making, drying of timber as well as for charcoal
production. The paper highlights the principal wood-based energy industries in the
country where wood is still the predominant source of fuel.
INTRODUCTION
Since time immemorial, man has learnt to use fuel for warming up his dwelling and for
cooking his food. In the early days, wood in the solid form provided all the energy needed for
both domestic and industrial uses. In the course of development the use of solid wood as a
source of energy has undergone considerable change. At present, wood is also used for the
production of gaseous and solid fuel.
Perhaps the role of fuelwood as an energy source is closely linked with the process of
industrialisation. As society progresses, man becomes less dependent on wood as a source of
energy because modern industrial installations require the use of large concentration of fuels
which can be stored and easily transported. Wood fuels did not meet these requirements and
they were gradually replaced by oil. Furthermore the progress in the development of wood as
a source of timber have converted these once wood fuels into an important source of valueadded products making them too valuable to be used as fuel. Only wood waste and residues
that could not be utilised by current technology are currently used as fuel.
In Malaysia, wood only accounts for about 10% of the total primary commercial energy
of the country (Anon, 1986). The total amount of fuelwood in the country in 1986 is estimated
to be in the region of 500 000 tonnes. Although the contribution of fuelwood to the overall
energy requirement of the country is not very significant, wood is an important and
predominant source of energy in many of the rural industries of the country. These industries
include:
a)
Smoking of rubber sheets
b)
Curing of tobacco leaves
c)
Brick making
d) D rying of timber
e)
Wood charcoal production
The above industries alone account for almost 90% of the total wood energy
consumption of the country. Perhaps one of the main reasons for the popularity of wood as a
source of fuel in the rural industries is the abundance in the rural areas and a relatively cheaper
fuel when compared with other sources of fuel available in the country. The relative cost of
fuel in the country is shown in Table 1 (Hoi, 1987).
AVADLABDLITY OF WOOD FUEL
The main supply of sources of fuelwood for the rural industries in the country are
Rubberwood (Hevea brasiliensis) obtained from replanting schemes and wood residues and
logging wastes in the form of off-cuts, slabs, trimmings, edgings, tops, loops, branches and
Currently FRIM Research fellow at Aston University
412
defective logs from the wood based industries and logging operations.
Availability of rubberwood
The economic lifetime of a rubber tree is about 25-30 years. At the end of its economic
life, a typical rubber tree has a height of about 18 m, a diameter of about 70 cm at ground level
and an average dry weight of about 3.6 tonnes with composition summarised in Table 2.
Composit ion of Rubber
Trees at the end of their
Economic Life
Table 1 Comparative Cost of Energy

in Rural Industries
Table 2
Enerpv
source
Components
Diesel
Charcoal
Wood, wet
Coal
Calorific value Fuel cost

CU/GJ1
fGJ/tei
44.3
30.5
12.5
29.3
3.55
1.74
0.70
1.74
Leaves
Leaf-stalks
Twigs
Small branches
Side branches
Main branches
Main stem
Roots
TOTAL
Drv weipht
kg
%.
67
9
105
163
410
1258
1032
547
3591
1.9
0.3
2.9
4.5
11.4
35.1
28.7
15.2
100.0
The area of planted rubber plantations in Malaysia is about 1.67 million ha. About 3%
of the planted area is replanted every year (Anon, 1987) yielding about 3.6 million tonne of
wood. Out of this amount of wood available, it is estimated that only 10% is used as timber
and 15% is consumed by the rubber smoking, brick, tobacco and the charcoal industries. The
remaining 75% of the rubberwood available is left in the replanting area to be burned later.
Hence the amount of rubberwood available for fuel or other further down-stream processing is
very substantial (Ambrin et al, 1987).
Availability of wood residues and logging wastes
Within the forestry sector, the timber resource of the country generates the necessary
revenue for development while the land provided opportunities for gainful employment and the
creation of new wealth. When large tracks of forest have to be cleared within a relatively short
period, huge amounts of wood wastes are generated. Studies conducted by the FAO/UNDP
(1973) indicated that only an estimated 22% of the gross volume of trees above 61 cm
diameter, or less than half of the potential net volume of marketable trees, is removed. A recent
study on forest residues in Peninsular Malaysia estimated that the percentage of removal of logs
can range from 60% to 65%. From this study, it can be deduced that at least 35% of wood in
the form of stumps, roots, branches (of 6" and below) remain in the forest with a composition
of 55% stumps and roots, and 45% branches. This will differ from species to species, the
size, age and condition of the trees. This method of harvesting yields a wood potential of
about 1.2 million t/y with an estimated energy value of about 18 trillion Joules and a market
value of about MR$ 50 million annually.
In the saw milling industry, further residues are generated in the form of sawdust, slabs
and edgings. Recovery of green timber in the sawmill generally can vary from 35 to 45%
depending on the size, quality and sawmilling practice. The approximate breakdown of the
residues produced is as follows:
Bark
10%
Sawdust
20%
Slabs and edgings 70%
The estimated volume of the sawmill waste is estimated to be in the region of 1-1.5
million tonnes. In general the amount of wastes available for energy production is summarised
in Table 3.
413
Table 3 Estimated wood-waste available for energy in the country
Activity
Type of waste
Rubberreplantingscheme
Logging activities
Sawmill recovery
Rubberwood billets
Stumps, roots, branches
Bark, sawdust, slabs, edgings
Amount of waste
(million t/v)
2.7
1.2
1-1.5
THE USE OF WOOD AS FUEL IN RURAL INDUSTRIES

As mentioned earlier, the use of wood as a source of fuel in the rural industries in
Malaysia has been standard practice since the early days of the industries. The devices by
which fuelwood is actually burnt are generally based on traditional designs and the use of
locally available material. To keep investment low, designs are kept as simple as possible.
The main rural industries using wood as fuel are discussed below.
Smoking of rubber sheets
Natural rubber is produced from latex tapped from the rubber tree. To produce sheet
rubber, the latex has to be dried by exposing them to flue gas generated from the combustion of
wood in the smokehouse. The smokehouse is capable of drying about 25 tonne of rubber
sheets per batch operation. The walls of the smokehouse are built of bricks and asbestos and
are about 6 m high. The furnace is a simple brick-lined stove located at ground level.
Rubberwood is burnt to produce the flue gas for drying the sheets (Hoi and Low, 1986). The
hot flue gas will then rise passing through the wet rubber sheets hung horizontally by rattan
rods. During the process, moisture is removed from the sheets. The wet gas then leaves the
smokehouse through the ventilation vents situated between the roof and the walls. The amount
of air passing through the furnace is regulated by simple damper plates at the entrance of the
furnace. The total time required for drying in a typical smokehouse can vary from 4-10 days
depending on the age of the smokehouse (Enno and Hoi, 1987).
Based on the wood consumption and the rubber production, about 1.5 kg to 2 kg of
rubberwood is needed to produce a kilogram of smoked sheets. The fuelwood cost represents
about 5% of the value of thefinalproduct.
Tobacco curing
Fresh tobacco leaves harvested directly from the field has a moisture content of about
70%. In order to produce good quality tobacco, the leaves have to be dried immediately in a
tobacco curing barn. The walls of the bam are made of asbestos. The furnace is a simple
burner in the form of a chamber located at the base of the bam. Rubberwood is fired through
the furnace door when air from combustion is available. The hot flue gas passes through the
bam through a series of distribution heat exchanger pipes that eventually lead to the chimney.
Heat from the flue pipes is transferred to the air inside the bam which in turn dries the tobacco
leaves inside the bam. The process of drying can take between 4 to 6 days. Measurements
made by MARDI showed that about 8-10 kg of fuelwood is required to dry 1 kg of the final
product (Daham, 1987).
Brick-making
The most common method of firing bricks in Malaysia is by the updraft kiln method.
The kiln has no permanent top, but the outer wall, base and fire tunnels are permanently built
with bricks. The walls on either side are buttressed and the comers are heavily constructed.
Access into the kiln is through a doorway at the end walls. The doorway is filled temporarily
with closely laid bricks (without mortar) during the kiln operation.
After the process of preparing the wet bricks, the green bricks are carefully loaded into
the kiln. Small spaces are left in between the bricks in order to allow hot gases produced from
the fire at the base to rise. Rubberwood is placed in the firing tunnel and is fired, gently at first
to allow water to escape from the bricks until the kiln reaches a certain temperature. This is
414
indicated by a red glow at the top of the kiln at night. The sink of the bricks (after shrinkage)
against the permanent side walls is an indication of the firing process. Generally the firing
period is between 4 to 10 days. A typical amount of fuelwood required to manufacture 1 kg of
brick is 0.3-0.4 kg (Hoi, 1987).
Heat for the sawmilling industries
The basic use of wood as a fuel in the sawmilling industry for generating steam in
boilers has been a common practice in Malaysia. For most Malaysian wood species, the gross
calorific value of oven-dried wood is about 18 MJ/kg. High lignin and resin contents in wood
such as for some dense species will result in a higher calorific value. Moisture in the wood
will also decrease the calorific value of the wood. In a typical case, air-dried wood with a
moisture content of 10% has a gross calorific value of 16 MJ/kg. For freshly sawn wood this
value is around 10 MJ/kg (Tan, 1985). Because of the lower heating value of green wood,
preliminary drying is always preferable although not always practical. In a typical sawmill the
energy requirement per unit of the product is summarised in Table 4.
Table 4 Fuelwood requirement per unit product
Product
Sawmilling
Plywood
Equivalent wood bumt/m3 production

160-340 kg
400-600 kg
Conversion into charcoal

In certain parts of the country, the high cost of transporting wood over long distances
will diminish the relative low cost advantage of wood as fuel. In Malaysia, the economic
distance between the source of wood and the demand centres is about 100 km (Hoi et al,
1986). However, the economic value of wood can readily be upgraded if it is converted into
charcoal. Charcoal has about twice the calorific value of wood but a fifth of its volume. This
enables it to be transported over longer distances for use. Furthermore, because it is a cleaner
fuel compared to wood, it will command almost 10timesthe price of wood in the major towns.
The production of charcoal in Malaysia has been practiced for centuries. The methods
vary from the simple sawdust pit method to the relatively efficient beehive kiln method. The
sawdust clamp method is a cottage type industry and is generally located in areas where labour
cost is cheap (Hoi, 1983). Although it is simple and inexpensive to build it is a highly labour
intensive industry. The quality of the charcoal obtained is not very good and it is sold as
domestic charcoal. About 6.5 tonne of wood is required to yield 1 tonne of charcoal.
Bener quality charcoal can be obtained by the beehive kiln method (Hoi, 1986). This
method is the most popular and is used to produce domestic mangrove charcoal and industrial
charcoal. Beehive kilns are therefore located either in coastal areas with mangrove forest or in
rubber growing areas. About 5 tonnes of green wood are required to produce about one tonne
of charcoal by this method. The concept of producing charcoal by the transportable metal kiln
was introduced into the country about 5 years ago. This method is suitable for small scale onsite production (Hoi and Putri, 1988). A number of sawmills and land development agencies
are using these kilns to convert their wood residues into charcoal. About 4.5 tonnes of wood
are required to produce 1 tonne of charcoal (Hoi et al, 1986). Currently about 60 000 tonne of
charcoal is consumed annually mainly for industrial applications (such as for the reduction of
steel, activated carbon and the chemical industries). Only about 20% of the charcoal produced
in the country is used for domestic cooking. The amount of fuelwood required per unit
production of the three industries is summarised in Table 5.
CONCLUSION
The amount of wood wastes available is around 5.4 million t/y, so only a small
percentage is utilised. The rest is left in the field either to be disposed of by burning or by
natural deterioration. Hence the amount of unexploited wood resource is very substantial. The
total amount of wood wastes used as fuel in the country is summarised in Table 6.
415
Table 5 Fuelwood Requirements
Industry
Fuelwood required/unit production
Rubber smoking
1.5 - 2.0
Tobacco curing 8.0 - 10.0
Brick making
0.3 - 0.4
Charcoal making 4.5 - 6.5
kg/kg of dry rubber sheet

kg/kg dry leaves
kg/kg brick
kg/kg charcoal
Table 6 Estimated
Total
Wood C onsumption
Industries
Rubber smoking
Tobacco curing
Brick making
Charcoal production
TOTAL
Million t/v
0.5
0.1
0.1
<L3_
1.0
In the last decade, very little attention has been focussed on the potential of harnessing
energy from the forest because of the availability of cheap fossil fuels in the country.
However, as the fossil fuels in the country are very limited, it will only be a matter of time
before the non renewable resources will be depleted. It has therefore become increasingly
urgent for the government to look for alternative resources to satisfy her future energy needs
(Salleh and Hoi, 1983). Recently, there has been renewed interest all over the country to
reassess the possible contribution of wood to future energy requirements. While the
ingredients are already there, means have to be taken by all concerned to exploit the potential
fully by intensive research and development efforts. Only then will the long term objective of
the government be fully realised.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11
12
13
Anon (1986). Yearbook of statistics 1986. D epartment of Statistics, Government of

Malaysia, Kuala Lumpur, Malaysia.
Hoi, W and Baharuddin, Y (1987). Wood as an alternative source of energy. Paper
presented at the Asian Physics Symposium, October 1987, Kuala Lumpur, Malaysia.
Anon (1987). Lapuran perangkaan tahunan tanaman semula 1987. RISD A, Kuala
Lumpur, Malaysia.
Ambrin Buang and Mohd. Nazuri Hashim (1987). Current analysis of the rubberwood
industry with special emphasis on marketing. Proceedings of the Second Rubberwood
Seminar, December 1987, Kuala Lumpur, Malaysia.
FAO (1973). A market analysis of Malaysian wood products. Technical Report No.6,
FO:DP/MAL72/009 Rome, Italy.
Hoi, W and Low, C (1986). The use of fuelwood in the smoking of
rubbersheets. Report of consultancy on wood energy use in Malaysia. UND P, 1986,
Rome, Italy.
Enno Heijnermanns and Hoi, W (1987). Preliminary report of energy use in tghe
natural rubber industry of Malaysia. Forest Research Institute Malaysia, Kuala
Lumpur, Malaysia.
D aham Mohd. Daud (1987). Pengawetan tembakau dengan menggunakan gas cecair
petroleum. Paper presented at National Tobacco Conference, December 1987m, Kuala
Lumpur, Malaysia.
Hoi, W (1987). Fuelwood trees for rual industries. Paper presented at Confernece
of Multi Purpose Tree Species, December 1987, Kuala Lumpur, Malaysia.
Tan, Y E (1985). Calorific value of some Malaysian Timber. The Malaysian Forester,
28: 148-153.
Hoi, W K, Ali S and Megathewar (1986). Small-scale charcoal from small holders in
Malaysia. Paper presented at Rubber Planters' Conference, October 1986. Ipoh,
Malaysia.
Hoi, W (1983). Country status on charcoal production and technology, Paper
presented at experts consultation on charcoal technology, FAO, Bangkok, Thailand.
Hoi, W (1986) Charcoal production from beehive kilns. Paper presented at
International Union of Forestry Research Organisations Conference, Yugoslavia, 1986.
416
14
15
Hoi, W and Putri, F (1988). Wood eneigy activities in Malaysia. Paper presented at
Regional Workshop on Biotechnology, February 1988, AIT, Bangkok, Thailand.
Salley, and Hoi, W (1983). Research in biomass energy - Problems and
Prospects. Paper presented at the consultation of wood energy programme in Asia and
Pacific region. FAO, 1983, Rome, Italy.
417
SELECTED ASPECTS, EXPLANATIONS AND STATEMENTS IN ACCORDANCE AND ANALOGY
TO THE BIT GRANULATION-TECHNOLOGY
J.M. DISS and F.W. HOCHHEIM
Directorate General and GENERAL Management
of the incorporated company B.I.T. SA, GR. D. L., L-4807 Rodange, PO Box 9
Summary
Unlike the situation in primary energies,
some of the significant
advantages of secondary energies (e.g. fuel pellets made from biomass
wood waste) are relatively unknown and consequently little utilized.
Biomass, especially ligneous materials, is eminently exploitable and
the heating capacity expressed in energy flow can be quite remarkable.
With an energy conversion efficiency of almost 80% and a favourable
cost regime, BIT fuel pellets are an actual and competitive form of
secondary energy. It is, however, necessary to consider the supply
structure of the biomass wood-waste ('green circuit') and to locate
the plant close to forestry resources and woodworking industries.
Therefore the biomass wood-waste industry will be increasingly
directed to refuse management.
1. INTRODUCTION
The conversion technology for generating fuel pellets from biomass
wood-waste, on which BIT granulation technology is based, has been in use
for at least ten years mainly in France. It has been used continuously and
successfully for this period.
The technology has been used for the
cost-effective and environmentally benign conversion of forestry and woodworking refuse into wood-waste secondary energy. New applications of this
technology can be used to increase energy savings and to transform ligneous
materials as well as wood waste to useful fuel.
Consequently the BIT pellet user will benefit from the following
advantages :
low investment;
good care of boilers ; warm-heaters and generators operating conditions
and life are improved;
easy operation; automatic feeding of fuel pellets is included;
low cost of maintenance and service;
high energy efficiency (82%) on heating capacity 4000 kcal/kg to
4200 kcalAg leads to 80% of specially designed boiler, warm-heater
and generator.
Several central granulation plants have been
in uninterrupted
operation since 1978 without any problems.
There are also many fuel pellet fired heating plants in uninterrupted
operation without displaying major problems.
418
2. PRICE COMPARISON BETWEEN FUEL PELLETS AND PRIMARY ENERGIES
A price comparison between secondary and primary energies is quite
difficult given the fluctuations in primary energy prices. Unlike primary
energy prices, the price of secondary energy generated from wood-waste, wood
chips and fuel pellets has not varied greatly during the period from
September 1981 and January 1989. The cost of secondary energy has been
gradually increasing but at a moderate rate.
The cost of all energies must now be related to the price of fuel oil
which is currently relatively cheap. However, up to the first quarter of
1989, although fuel oil does enjoy some advantage, the price of fuel pellets
is very competitive.
The
study
'Raw Materials
from Agriculture
and Forestry
for
Briquettizising and Firing in Heating Plants' was supported by BMFT and
performed by TU-Munich.
The conclusion of this study, published in the BINE report No.11, June
1988, states that to be competitive the price of fuel pellets generated from
biomass would need to be at least half of the current price.
Therefore those making investment decisions on purely economic grounds
would definitely opt for fuel oil under present market conditions. However,
if one considers aspects other than pure economics there are several factors
which could militate in favour of fuel pellets :
high operating safety without interruptions or breakdowns ;
safety of feeding and extraction systems ;
safety of residues;
non-polluting environmental effects ;
high quality and efficiency of conversion technology leads to energy
savings;
desirability of utilising technologies which generated fuel pellets
from biomass derived from wood-waste and refuse.
These later points may
government regulations.
become increasingly
important with
evolving
3. INCREASING IMPORTANCE OF REFUSE MANAGEMENT IN SUPPLYING

BIOMASS OF LIGNEOUS MATERIALS
An examination of the possibilities for ligneous biomass in various
cities and communities has led BIT to conclude that the annual production
capacity of generated fuel pellets is approximately 20 000 tonnes.
In our view it is necessary for communal and urban authorities to
regulate the further processing and enhancement of biomass from wood-waste.
This should be accomplished by collecting and combining wood-waste biomass
from forest and waste resources.
This concept of collection and containment would be consistent with
the establishment of 'green circuits' within cities and neighbouring
communities.
Wood-waste biomass supplied from the 'green circuit' and transformed
to fuel pellets represents a real alternative to the compost wood-waste
conversion technology.
The importance of this technology is more evident where wood-waste is
derived from refuse. Separating and enhancing the wood-waste biomass is
preferable to incineration.
There is certainly a strong case for supporting fuel pellet secondary
energies as a support for primary energies.
419
However, the economic situation (DM 100-150/m3 of biomass wood-waste
in the Federal Republic of Germany) is currently overriding environmental
and waste use arguments.
This technology will undoubtedly improve as efforts are concentrated
on the limiting problems.
We hope that the presentation 'Selected Aspects, Explanations and
Statements in Accordance with the BIT Granulation-Technology' will give
encouragement
to those
proposing
this
type of
technology
because
environmental and energy saving problems are common throughout the
Community.
420
THERMOCHEMICAL DENSIFICATION OF BIOHASS A KINETIC APPROACH TO PROCESS DEVELOPMENT
D.P. Koullas, N.S. Abatzoglou, and E.G. Koukios

National Technical University of Athens, Greece
SUMMARY
Hot densification of conifer sawdust is investigated. The experimental conditions were 0.25-4 h, 100-400 bar and 80-215C. The
effect of temperature, briquetting pressure and time of compression
on total process weight loss, volatiles loss, briquette density end
briquette moisture content is examined. Moreover, the calorific
value of the solid fuel produced is determined and the energy efficiency of the process is calculated. Process yields and product
characteristics are mathematically expressed as a function of process input parameters. Under the experimental conditions examined
the volumetric energy density of the product is four times than that
of original biomass. Furthermore, it was found that the pressure
applied during compaction has a major effect on the physical, chemical and energetic aspects of the process.
1. INTRODUCTION
Hot densification belongs to the'group of technologies which utilize
biomess as energy source thermochemically (ie. direct burning, pyrolysis, gasification) (1). The object of briquetting is to produce a solid
bio-fuel with higher Volumetric Energy Density {VED), and better transport, handling and combustion properties (2), (3), (4).
During hot densification of lignocellulosic materials, complex competitive physicochemical phenomena are taking place (e.g. development of
thermoplasticity, hydrolysis, production of anhydrosugars) (5),(6). These
phenomena depend on the pressure, temperature, time, and, in several
cases, on other parameters of densification.
Tne object of this work is the understanding of the mechanism of hot
densification and the development of mathematical models linking the process yields with the various densification parameters.
421
2 . EXPERIMENTAL
The raw materiel of thermochemical densification was conifer saw
dust. The sawdust was densified in a heated mould by a laboratory hydrau
lic press. The densification temperature, pressure and time varied
between 80215C, 100400 bar and 0.254 h, respectively. The bulk den
sity of both the raw material and the product (briquette) were determined
geometrically. Moisture contents were found according to ASTM (D 1037).
Total process weight loss, organic volatiles loss and weight loss after
weight stabilization at ambient humidity were also determined (7). The
volatiles loss were calculated from the weight decrese of the dry matter.
The calorific value of the solid fuel produced was analyzed according to
ASTM (D 271).
A part of our experimental data (7) is presented in Table I and II.
As it can be seen in Table I. significant volatiles loss is observed
above 130"C. This means that there is a security limit, up to which there
is no loss of organic combustible matter. The evaporated water can be
partially reabsorbed, since loss after weight stabilization is 34.5*
(Table I). Of course, the final briquette moisture after weight stabili
zation is smaller than that of the raw material (Table I), since compres
sion reduces the porosity. This information is useful to one who wants to
have high process yields. It should be noted that above 250C the combus
tion of the briquette takes place.
Regarding briquetting time, one could claim that around 23 h the
values of major densification parameters are stabilized (Table I). The
latter remark is valid for all pressures examined. This means that at
constant temperature and pressure after certain time there is an optimal
utilization of the porosity (ie. the specific surface) for bonding. This
is expected, since at prolonged times "secondary reactions" dominate;
these reactions are slower than the "primary" ones (8).
Briquettes produced around 170C and 200 bar have high density
(Table I), ie. very good cohesion, if briquette final moisture content is
considered as measure of compaction and, therefore, of ita resistance to
mechanical stress (9),(10). These conditions can be considered as opti
mal, since at higher temperatures volatile loss increases. Moreover,
higher pressure on the one hand results in increased energy demand and,
on the other hand, does not significantly increase briquette density.
The briquette VED is four times higher than that of the raw materiel
(Table II). From Table II it can also seen that gross process energy
efficiency is rather high.The same is valid for the net energy efficiency
(1st Law of Thermodynamics) (7). This encourages the application of this
process. These remarks are valid for other raw materials too (e.g. olive
kernel) (10).
Regarding mathematical modelling, equations (1) and (5) are derived
from the experimental data (6):
yro 0.9620.0379*xt40.0180*XP+0.0911*xT+0.00215*xt**
0.111*,*0.0687*** +0.0422*xat
+0.0166*xap0.234*x=T +0.0177*xt*Xp*xT
where,
yTO: * process gross total yield (100total loss, see Table I).
(1)
422
t
(2)
Xt
4
P100
Xp* 3
(3)
300
T353
V_
(4)
488353
y D (lexp(0.00834*t)) + (lexp(0.00002*P))+T<>o:'s=
(5)
where,
y D : % process dry yield
and
t: compression time, h
: pressure,
bar
: temperature,
For the construction of the above models a nonlinear regression

FORTRAN programme based on the LevenbergMarquardt algorithm was used.
For all cases, the convergence conditions were satisfied if, on two suc
cessive iterations the residual sum of squares estimates had a relative
difference equal to zero. As mentioned earlier the occuring physicochemi
cal phenomena are too complicated. This explains why equations (1) and
(5) are different. But, it should be noted that they are not as different
as they seem to be, since the exponential term can be analyzed to a poly
nomial according to Taylor series. This means that equations (1) and (5)
are more or less related. Mathematical expressions predicting water loss
during densification or the stabilization moisture have not been found,
most probably, due to the complexity of the phenomena; from equation (1)
one can conclude that temperature linearly or at second power plays a
very important role in densification. Interactions such as temperature
pressure or temperaturetime should not be neglected.
423
Table I: Process characteristics and properties of the briquette produced
Tempe
rature
L o s s
Pressure Time Density
Total
"C
Atm
80
80
80
80
80
130
130
130
130
130
130
170
170
170
170
170
170
215
215
215
215
215
100
100
100
200
200
100
100
100
200
200
200
100
100
100
200
200
200
100
100
100
200
200
g/cm3
1
2
4
2
4
1
2
4
1
2
4
1
2
4
1
2
3
1
2
3
0.29
0.92
0.90
0.89
1.07
1.06
0.83
0.83
0.84
1.11
1.12
1.18
0.98
0.96
1.06
1.19
1.21
1.1
2.8
4.0
2.4
2.9
8.0
7.5
7.6
6.8
6.6
6.9
0.25
10.5
10.7
10.7
10.4
10.4
9.7
1.22
1.24
1.24
1.27
17.1
24.2
24.8
24.4
26.7
Moisture
Vola after weight content
tiles stabi 1ization
0
0
0
0
0
0
0
0
0
0
0
0.6
0.9
0.8
0.6
0.7
0.3
3.0
2.8
2.2
2.6
4.4
3.7
3.4
3.4
3.3
3.4
6.6
7.1
7.4
7.0
7.3
6.8
7.3
14.8
22.3
22.9
22.4
25.0
9.9
9.6
7.1
6.4
6.7
8.5
4.9
4.9
4.9
4.6
4.6
4.6
4.1
3.9
3.5
3.8
3.5
3.3
2.7
2.4
2.5
2.3
2.3
14.3
15.0
14.3
17.0
Furthermore, briquette density can be described by the

exponential equation:
a*exp(b*P)
where.
p: density, g/cms
a 0.52 0.97
b 0.00060.0007
r 2 0.60 0.99
depending on the briquetting conditions
following
(6)
424
Table II: Briquette Volumetric Energy Density (VED). Heat of Combustion
(HC) and Net Energy Efficiency (NEE).
Temperature
Pressure
Time
"C
bar
cal/cm5
130
130
170
170
170
170
200
300
100
100
100
300
4
4
1
2
4
4
1270
5390
5570
4550
4530
4860
5300
VED of
Briquette
HC
cal/g
4430
4565
4565
4640
4720
4580
4570
Efficiency
(a)
NEE
(b)
103
103
105
107
103
103
93.5
94.6
91.6
92.9
90.2
(a) Efficiency VED of briquette / VED of raw material.

(b) NEE - useful energy / Energy Input (7)
4. KEb'EHENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
FAST Occasional Paper (1981). Energy from Biomass Technologies:

State-of-the-Art Review. No.10.
Reed. T. and Bryant, B. (1978). Densified Biomass: A New Form of
Solid Fuel. Report. U.S. Solar Energy Research Institute. Golden.
USA.
Koukios, E.G., Mavrokoukoulakis, J.G. and Abatzoglou, N.S. (1982).
The Densification of Biomass. Proc. Conf. on Soft Energy Sources
141-150. Thessaloniki. Greece.
Koukios, E.G. and Mavrokoukoulakis, J.G. (1981). Some aspects of
biomass densification. Proc. 3rd Symposium on Biotechnology in
Energy Production and Conservation. Paper 7. organized by Oak Ridge
Lab. USA.
Runkel, R.O.H. and Witt, H. (1953). zur Kenntnis des thermoplastischen Verhaltens von Holz. 3. Mitteilung. Holz als Roh-und Werkstoff
11 457.
Wenzl, E.F.J. (1970). The Chemical Technology of Wood Academic Press
255.
Abatzoglou, N.S. (1982). Densification of Biomass. Dipl. Eng. Thesis. NTU Athens.
Pyle, D.L. and Zaror, C A . (1984). Heat Transfer and Kinetics in the
Low Temperature Pyrolysis of Solids. Chemical Engineering Science
39(1) 147-158.
Mobarak, F.. Fahmy. Y. and Augustin. H. (1982). Binderless Lignocellulose Composite from Bagasse and Mechanism of Self-Bonding. Holzforschum 36(3) 131-135.
Koullas. D.P. and Koukios, E.G. (1987). Hot Briquetting of Wheat
Straw. Proc FAO/CNRE Workshop on Handling and Processing of Biomass
for Energy, (ISES Conference Parallel Session), Hamburg. FRG.
425
Preparation and use of charcoal : vater slurries
C. ESNOUF*, S. GAUDEHARD*,
G. ABTOMIHI**, 0. FRANCOIS**, C. HEZERETTE***
* CEXAGREF.BP 121.92164.Antony Cedex.FRANCE. ** universit de Technologie de Conpigne.
BP233.60206.Compiegne Cedex.FRANCE. *** CTFT.45b.av.de la Belle Gabrielle.94130.
Noqent s/Narne.FRANCE
SumiarY
The ai of the work is to design and develop a whole process of charcoal slurries production
for use in siali and medium size boilers and lov speed diesel engines. Two possible flowsheets
have been tested : without ash renoval, a binary charcoal/water iiixture contraining 571
charcoal, exhibiting a LCV of 16900 KJ/Kg and a dilatant behaviour has been obtained. Ash
renoval,
including acid treatment and selective aggloiieration leads to a ternary
lixture, containing 471 of charcoal and 12S fuel-oil, of a LCV of 18700 KJ/Kg, exhibiting a
pseudo-plastic behaviour and meeting the pollution standards requirements.
Preliminary combustion tests shov better burning properties for ternary Bixtures.
Economic estiiiate show that slurries would be coiipetitive with a fuel oil at 7.5 EC/GJ.
Significant cost reduction can be obtained in the future in formulation optimization, and
pyrolysis liquids valorization. Anyway, tie grants presently needed by farmers for
competitivity are less than for other agricultural policies.
1. INTRODUCTION
Common agricultural productivity trend shows that european agriculture produce and will
produce more and more surpluses. In year 2000 the area corresponding to surpluses will probably
represent 151 of present agricultural area (1). Short rotation forestry is proposed for those
areas, but a very large market must be found for such a large wood production. Household
and flats heating would be consistent with it, but bioiass is not a fuel easy enough to handle.
Charcoal : water slurries considerably improving biomass storage, transportation and handling,
might therefore be a right solution.
The aim of the work presented here is to design and develop a whole process for such slurries'
production and use in small and medium size boilers and in low speed diesel engines.
The paper present results on ash removal, slurry formulation, preliminary burning tests and
economics.
Slurries must satisfy several objectives, of somewhat contradictory nature :
The minimum lov calorific value (LCV) required for the liquid to be usable in the current boilers
retrofitted is 16700 KJ/Kg.
The slurry must satisfy fluidity specifications : it must be stable (no solids deposit) and its
viscosity must not exceed 2 Pa.s (2000 cp) for a shear rate of 100 s .
The slurry must respect standards against atmospheric pollution : less than 0.24 g/HJ must be
discharged from plants under 3 HW.
For small scale boilers, intermittent operation needs easy ignition characteristics for the fuel.
Details on the way to obtain those results are given in (2).
2. SLURRIES FORMULATION AND PROPERTIES :
Two possible formulations bave been considered and tested, a charcoal/water slurry without
ash removal, and a ternary mix cleaned charcoal/water/fuel. The first steps of the line are the same
: the raw material is short rotation coppice (SRC), poplar or eucalyptus, including bark
&?
(5021 water
content)
ODT wood
>
Drying ~ ^ 1
0.3
ODT wood
(15%
water
content)
0.82 J'water ^ <
air i
,1.15 volatileBurned1*Electricity
air
Pyrolyses ^f
Production
N
s n _ T ,
,
^0.33 charcoal
<i
Crushing mill
charcoal 80,
NO DEASHING :
water
./ addi ti ves
(
Q wet ball mill
bimodal granulometry : 420 IA
r
ACID AND SELECTIVE AGGLOMERATION CLEANING
rHCL
rQ
.water
N>
ON
.O
wet ball mill 813/1

hydrophobic
liquid : fueloil
water + additives
charcoal : water : additives slurry
57 : 42 : 1
Figure 1
purified
*
charcoal + fuel
<
charcoal : water : fuel slurry

47 : 40 : 12
bio ultracarbofluid (bioUCF)
sfc&gSi
PgSoaJ
acid + water + ashes
427
even though it is rich in ash. The wood chips are pyrolyzed in a CemagrefFramatome pyrolyser vith
recycling of volatile latter, which enables maximum charcoal yield.
The line is presented in figure 1.
Details on paraietric studies for fonulation optimiza tion are given in (2).
typical slurry obtained fro a bimodal granulometry(70t of lean diameter 4 and 301 of
ean diaieter 2^)contains 571 charcoal, 421 water, It of Tamol (naphtalene sulfonate) as dispersing
agent and 20 to 50ppm of carboxyiethyl cellulose ("Hercules") as stabilizer.
Such a slurry has the specifications required as it has an effective lover calorific value
(taking into account the heat a vaporization of vater) of 16900 KJ/Kg and a viscosity of 1900 cp
at 100 s . The Theological behaviour of the slurry is dilatancy (apparent viscosity increases
with the shearing rate).
When ash removal is included, the production line is sore complex (see figure 1). To achieve
satisfying residual ash content, acid and selective agglomeration cleaning lust be coibined (details
in (2)).
The hydrophobic liquid used here is domestic fueloil which has the advantage of enhancing the
final energy content of the slurry.One may also envisage light fractions of crude oil not currently
marketed(presently used mixed with heavy fuels) or light crude oils.
The tvo cleaning steps are complementary,since selective agglomeration preferentially
eliminates the silica and the alumina.Neutralization is not necessary since separation of the
agglomerates liberate the acid aqueous phase.The agglomerates are just rinsed until a neutral pH is
obtained.
A typical ternary ultracarbofluid ("bioDCF") contains 47 of charcoal, 121 of fueloil,
401 vater, 0.8t of a dispersing agent (nonionic vetting type, such as Cemulsol) and 20 ppm of
stabilizer. The viscosity is 1900 cp at 100 s" 1 and the Theological behaviour is pseudoplastic
vhich is a positive effect of tremendous importance. The slurry has a LCV of 18700 KJ/Kg, 751 of
which is due to the charcoal, and an ash content of 0.8i.
Preliminary combustion tests have been performed on a 100 KM furnace. Burning properties are
much better for a bioDCF than for binary slurries (conversion efficiency of 0.98 as compared to
0.82 at optimum air excess). Flame stability and ignition facility vere satisfactory for
bioDCF. Detailed experimentation have still to be carried out.
3. ECOHOHC ESTIMATE :
Binary mixtures estimates vere presented in (3). A preliminary estimate is presented here for
bioDCF.
The size of production unit is determined by the forestry density around it, to optimize
the transportation/scale economics ratio. A 0.1 density shovs that a 2700 T/day of slurry size of
unit is an optimum. For such a capacity, the capital costs are broken dovn as follows (table I).
Wood
reception Drying Pyrolysis Milling Gasbumer
and
and and turbo Total
storage
slurry alternator
Capital
costs
in 10 ECU
19
5.7
9.1
of total
32
15
Table I
18.5
60.3
31
13
100
428
The production cost is broken down as follows : the standing charges and staff costs
represent 11.71 of total cost ; the operating costs, additive, HCL, and fuel oil, represent
24.91 of total ; the wood transport and storage represent 13.4t of total and the wood itself,
50t of total cost.
As a conclusion, the production cost of bio-DCP is estiiiated at 850F/T (120 ECU/T), that is to
say 6,5 ECD/GJ. Considering the present official OPEC price for crude oil (18 $/bbl), bio-DCF is
nearly twice the price of doiestic fuel. As coiipared with the binary slurry, the cost is not
significantly higher (6.5 and 6.3 ECD/GJ).
The lain iteis taking up that price are the wood, and the fuel and additive. So, finding
alternative additives and hydrophobic phases is of treiendous importance for cost reduction.
Considering other possible iiproveients, an increase in short rotation coppice fro 13 T/ha to
17 T/ha would save a significant 81 for bio-DCF and 111 for binary ikes.
A pyrolysis liquids valorization could also lean a significant cost decrease ; the lost
siiple way is to sell their energy content on-site, through steai generation for instance. This
would represent a 10< reduction for bio DCF and a 13.51 for binary lixes. Of course, any
lore valuable strategy aiongst the eierging technologies for pyrolysis liquids use (upgrading to
otor-fuel for instance) will represent a significant iaproveient.
The coiparaison with other fuels lust be iade in tens of final energy cost, that is
to say including the boiler's capital cost and efficiency and the boiler operating tiae per year
(the hypothesis here is 4000 h/year). In the case of bio-DCF, the boiler is not equipped with ash
reiover and dust recovery in siokes.
The coparison of bio-DCF with light fuel oil is shown on figure 2 ; it can be seen that
the bio-DCF would be coipetitive for a light fuel oil cost of around 7.8 ECD/GJ, that is to say
around 40$/bbl crude oil. For binary slurries, the coipetitiveness would be obtained for a price of
6.5 to 7.4 ECO/GJ.
These results can be teiipered in teres of comon agricultural policy in Europe ; table II
shows the grant to faners needed for present coipetitiveness with fuel oil and it appears that the
proposed energy line is very interesting.
Wheat
export
Ethanol
binary slurry
production production present advanced
bio-DCF
present advanced
3000-4800 7000-8000 5000-12000 2800-4500 1100-2000 3700-4500 2300-3400

Table II
Cost of different agricultural policies
required in FF/ha -year
grant
In addition, exportation of the technology to developing countries is envisageable since the

cost of raw aterial is lower there (fron 100 to 280 FF/T SRC) and this cost represents 50 to 70S of
the final cost price. Low speed diesel engines would represent a significant larket there.
429
bioOCF and light fueloil costs as a function
of, oil price, boiler size
U / G J
_...
^^.
A i , =:::::*
-:- ~
*x x
+"""'
., :::::
.r
+:':"';::::::::;
: ::::::::::
""f""
:::#F ""T
ty..''
4 MW
2 . 5 MW
_...
j +
:
_l
, , ,,
, . , .
1 MW
500
KW
Light fueloil cost (EC/GJ)

Figure 2
4. CONCLUSION :
Two types of slurries satisfying the specification have been obtained. Econoiiics are already
interesting in tens of agricultural policy
and of exportation
to developing countries,
but they could be iiproved by pyrolysis liquid valorization and choice of other conponents in
fonulation. The burning properties in boilers and engines bave also to be studied now.
5. REFERENCES :
(1) BECKER J.J (1986). Etude des dbouchs nergtiques de l'Agriculture en coipliient des
dbouchs agricoles traditionnels. Thse de Doctorit universit Paris Dauphine
(2) ANTONINI, G, i al (1988). Fomulation and Theological properties of charcoal liquid fuels
Euroform New Energies, Saarbrcken Vol 3 pp 629 631 N.S Stephens t Associates.
(3) ESNOOF. C , LESANT. V. (1988) New Process of suspension Pyrolysis and use of charcoal
slurries id Vol 3 pp.635637.
430
TREATMENT OF PYROLYSIS OIL WITH COMPRESSED CARBON DIOXIDE
V. BRANDANI, G. DEL RE, G. DI GIACOMO and D. FLAMMINI

University of L'Aquila, Dept. of Chemistry Chemical Engineering & Materials
1-67040 Monteluco di Roio, L'Aquila, Italy
Summary
This paper deals with the possibility of predicting phase
behavior
of systems containing compressed carbon dioxide and pyrolytic oils
- complex multicomponent mixtures of very different organic compoundsin a wide range of pressure and temperature.
A systematic approach based on vapor-liquid equilibrium data of binary
and ternary systems containing carbon dioxide is described together
with the main characteristics of the equation of state used as theoretical model of the whole system.
The results can be utilised to study the technical-economical feasibility of a supercritical solvent extraction process for separation and
upgrading of different bio-oils derived from wood pyrolysis and/or
liquefation processes.
1. INTRODUCTION
Bio-oils derived from wood pyrolysis and/or liquefation processes are
complex mixtures of many organic compounds varying greatly in size, molecular structure and polarity.
The recovery from pyrolytic bio-oils of
useful products is worthly to be considered especially if it can be
regarded as a significative step of an integrated up-grading process. In
fact, pyrolytic bio-oils require, in general, to be up-graded since they
rarely meet the standards for commercial fuels. On the other hand,depending
on the type of wood and on the operating conditions of pyrolysis, bio-oils
are usually characterised by an high percentage (from 10 to 60%) of phenol
and phenol omologs (1) which are by far the most valuable product of wood
pyrolysis. When these compounds are not recovered as chemicals they are
usually destroyed during the fuel up-grading process.
431
The use of dense (liquid or supercritical) carbon dioxide as solvent
is rapidly increasing in several important areas as enhanced oil recovery
(EOR), supercritical fluid chromatografy (SFC) and supercritical fluid
extraction (SFE). In comparison to other conventional separation techniques
like distillation and liquiliquid extraction, SFE has the advantages of
higher efficiency, easy of recovery of the solvent and improved transport
properties.
Carbon dioxide is also environmental acceptable, inexpensive
and readly available. Its critical temperature is 304 and its critical
pressure is 73.8 bar. A s a consequence, carbon dioxide is completely
miscible with many nonpolar liquid hydrocarbons as well as with low
molecular weight hydroxil compounds under mild conditions of pressure and
temperature (2). Phenol and phenol omologs are not miscible in all propor
tion in dense carbon dioxide, but their solubility is large enough (2,3,4)
to allow us to consider dense carbon dioxide as proper solvent for the
recovery of phenolic compounds from pyrolytic biooils.
The feasibility of such a process and its optimization is based on the
possibility of describing, from a thermodynamic point of view, the phase
behavior of the systems carbon dioxidebiooils which is, in general, a
multicomponent multiphase mixtures with an high number of very different
compounds and one to four cohexisting phases. From a systematic point of
view, one is faced with a series of problems which are quite similar to
those studied from many years by people involved with heavy petroleum
fractions and bitumen characterization:
identification of the mixture's components;
knowledge
of
components ;
the
thermodynamic
and
transport
properties
of
choise of a proper thermodynamic model (Equation of State) capable

describing accurately the complex phase behavior of the system;
pure
of
collection (from literature and/or from laboratory) of data required

model parametrization;
for
reduction of the system to an equivalent but less complex system of

pseudocomponents.
few
In this paper we describe with some details a combined experimental

and
theoretical
approach which can be usefully
applied
to
the
thermodynamic characterization
and phase behavior prediction of pyroly
tic biooils and biooilscarbon dioxide mixture. We also report some
preliminary results on the treatment of pyrolysis oil with compressed
carbon dioxide.
432
2. CHARACTERIZATION MODEL
Classical
models for the characterization of complex petroleum
fractions are based on measured properties of pure compounds and/or
pseudoCompounds such as boiling point and specific gravity. Recently new
correlations have been developed which require,
for each petroleum
fraction (pseudocomponent), more sophisticated informations: NMR, elemental
analysis, and IR spectroscopy. However, for the investigation of the fea
sibility of our separation process it must be pointed out that much at
tention has to be paid to the problem of binary and pseudobinary
interac
tion parameters.
The approach proposed is similar, in principle, to that used by Alessi
et al. (5) and by Yu et al. (6) for heavy ends characterization and super
critical carbon dioxidebitumen phase behavior. It is based upon the
attainment from the biooil of five homogeneous fractions. This makes it
possible to define and evidence some pseudocomponents for which one
determines
the average molecular weight.
Then,
pseudobinary
and
pseudoternary equilibria data between fractions and carbon dioxide can be
experimentally determined at laboratory level: solubility of each fraction
(or pure component) and solubility and selectivity of their binary mixture
in supercritical carbon dioxide are used as equilibrium data. In addition,
when other vaporliquid equilibrium data (bubble and dew points, PTx, PTy,
PTxy and PvT) are available from the literature for pure and binary
mixture, they can easely inserted in the procedure for determining binary
interaction parameters.
As thermodynamic model for the whole system carbon dioxidebiooil we
use an equation of state (EOS) which, following Ldecke and Prausnitz (7),
has been obtained by using the equation of MansooriCarnahanStarling
(8)
for the repulsive term and that of Soave (9) for the attractive term in
combination
with
a density dependent
mixing
rule
proposed
by
Panagiotopoulos and Reid (10). This equation, which is characterized by
three adjustable parameters for each binary or pseudobinary system, has
been applied successfully to the prediction of phase behavior of carbon
dioxidelemon oil system at pressure from 30 to 110 bar and at temperature
from 308 to 323 (11).
The
three
binary interaction parameters for each
binary
or
pseudobinary system containing carbon dioxide are calculated from the
experimental
solubility data by minimising the following
objective
function:
s = .(y
li
where
exp
y .)?
(1)
cal
y
and y . are experimental and calculated mole fractions in the
exp
cal
vapor phase and is the number of experimental data. To find the numerical
values of the parameters which characterize binary interactions existing
433
between pure and pseudocomponents the following objective function:
S = .(y
y
)? + .(Y
J2
ii exp
cal
il exp
cal
(2)
is minimised. Here, in addition to y e x D and y c a ^ we have Y e x D and Y c a i

which are experimental and calculated mole fractions of one solute in vapor
phase on carbon dioxide free basis.
3. EXPERIMENTAL APPARATUS
The solubility of a single pure or pseudocomponent and of their binary
mixture in supercritical carbon dioxide are obtained by using the single
pass flow apparatus. A detailed description of this apparatus and its
operation mode have been reported in a previous paper (11). It has been
designed to operate up to 1000 bar and 473 and can be used without any
modification as a semicontinuous extraction laboratory plant. It is used
in combination with an optical cell of few cubic centimeters (Nova Swiss)
which allow us to verify the number of cohexisting phase at the same opera
ting conditions of the single pass flow apparatus.
Before starting with the systematic experimental and theoretical study
described in the present papar, we used our laboratory extraction plant to
extract with supercritical carbon dioxide phenol compounds from a sample of
pyrolytic biooil obtained
from the fluidised bed reactor of Raiano
(Italy). We operated at 313 and 300 bar obtaining an extract which,
after depressurization and separation of carbon dioxide, was analysed for
phenol and phenol omologs content. We found in appreciable amount phenol,
cresols, xilenols and other substitutes.
REFERENCES
(1)
CHURIN,
E.,
MA GGI,
R.,
GR
A NGE, P. and DELMON, B.
(1987).
Characterization and Upgradind of a Pyrolytic Oil. Pyrolysis as a
Basic Technology for Large AgroEnergy Projects, 1516 October, 1987
L'Aquila, Italy
434
(2) DA NDGE.D.K., HELLER,J.P. and WILSON,K.V. (1985). Structure Solubility
Correlations: Organic Compounds and Dense Carbon Dioxide Binary
Systems. Ind. Eng. Chem. Prod. Res. Dev., 24,162166.
(3) VA N LEER,R.A. and PAULAITIS.M.E. (1980). Solubilities of Phenol and
Chlorinated Phenols in Supercritical Carbon Dioxide. J. Chem. Eng.
Data, 25,257259.
(4) LEE,R.J. and CHAO.K.C. (1988). Extraction of 1Methylnaphtalene and m
Cresol with Supercritical Carbon Dioxide and Ethane. Fluid Phase
Equilibria, 43,329340.
(5) A LESSI.P., CORTESI,., FERMEGLIA.M.,FONTANA,M. and KIKIC.I. (1989).
Heavy Ends Characterization Method Using Gas Solubility Data. 5th Int.
Conf. on Fluid Properties & Phase Equilibria for Chemical Process
Design, April 30 May 5, 1989, Banff, Alberta, Canada.
(6) YU.J.M., HUANG,S.H. and RADOSZ.M. (1989). Phase Behavior of Reservoirs
Fluids: Supercritical Carbon Dioxide and Cold Lake Bitumen. 5th Int.
Conf. on Fluid Properties & Phase Equilibria for Chemical Process
Design, April 30 May 5, 1989, Banff, Alberta, Canada.
(7) LDECKE, D. and PRA USNITZ,J.M. (1985). Phase Equilibria of Strongly
Nonideal Mixtures from an Equation of State with Density Dependent
Mixing Rules. Fluid Phase Equilibria, 22, 119.
(8) MA NSOORI.G.A ., CA RNA HA N.N.F..STA RLING,.E. and LELA ND.T.W. (1971).
Equilibrium Thermodynamic Properties of the Mixtures of Hard Spheres.
J. Chem. Phys., 54, 15231525.
(9) SOA VE,G. (1972). Equilibrium Constants from a Modified
RedlichKwong
Equation of State. Chem. Eng. Sci., 27, 11971203.
(10) PANAGIOTOPOULOS.A.Z. and RED,R.C. (1986). Multiphase High Pressure E
quilibria in Ternary Aqueous Systems. Fluid Phase Equilibria, 29, 525
534.
(11) DI GIACOMO,G., BRANDANI.V., DEL RE,G. and MUCCIANTE.V. (1989). Solubi
lity of Essential Oil Componenents in Compressed Supercritical Carbon
Dioxide. 5th Int. Conf. on Fluid Properties & Phase Equilibria for
Chemical Process Design, A pril 30 May 5, 1989, Banff, A lberta,
Canada.
435
ACnVATED CARBON FROM EUCALYPTUS KRAFT LIGNIN
J.J. RODRIGUEZ, T. CORDERO, J. RODRGUEZMIRASOL, A. SIMON and A. BATAI .1 KR
Departments of Chemical Engineering and Mechanical Engineering.
University of Malaga.
29071 Malaga (SPAIN).
Summary
Preparation of activated carbon from acidprecipitated eucalyptus kraft lignin i s
studled, following a twostep process consisting in CO2 partial gasification after
carbonization in N2 atmosphere. Char yield and composition a s well a s porosity
and surface area development against temperature and solid holding time have
been investigated In the carbonization step. CO2 activation h a s been carried out at
800C, a bumoff range up to 80% being covered. The porous structure of the
resulting products h a s been studied. Essentially microporous carbons showing a n
increasingly developed mesoporoslty have been obtained. Apparent surface area
values up to 1600 m ^ / g were reached. A 5 0 k g / d (referred to raw material) pilot
plant using a screwconveyor system h a s been constructed.
1. INTRODUCTION:
The development of lignin applications a s a raw material i s being widely
investigated in recent years. One interesting way is pyrorysis and carbonization to obtain
chemicals (1,2] and a char which can be u s e d as substrate for the preparation of carbon
materials [36].
In this paper, we study the preparation of activated carbons from eucallptus kraft
lignin by a twostep procedure consisting In Inert atmosphere carbonization followed by
CO2 partial gasification.
2. EXPERIMENTAL:
Labscale experiments have been carried out in a stainless steel cylindrical reactor
16 c m length and 8 c m l.d. electrically heated. The s y s t e m h a s a time/temperature
programmer which allows to control temperature and heating rate. Gases ( N2 or CO2 ) were
continuously passed at a 10 1/h (STP) flow rate. Thermogravimetric experiments were also
accomplished using a model Thermoflex Rlgaku thermobalance.
The carbonized products were analized for elemental composition ( C, H, N, S )
using a 2 4 0 C PerkinElmer apparatus for C, , and a JuliusPeter for S. Ash content was
also determined in every sample.
The raw material w a s eucalyptus kraft lignin supplied by the Empresa Nacional de
Celulosas, S.A. from its lignin precipitation pilot plant.The precipitating agent w a s H2SO4
at a controlled pH and the lignin w a s centrifuged and dried. The final product h a s the
following typical composition: 53.7% C, 4.5% H, 0.1% N, 1% S, 30.5% O and 10.2% ash
content. The relatively high ash content is most probably due to precipitate enmeshment
and can be easily reduced by diluted acid washing. A s will be emphasized later, this is a n
Important variable in the carbonization process and t h u s we have peformed experiments
with different ashcontent lignin.
Characterization of the porous structure of the products have been carried out from
77 N2 adsorption isotherms using a Sorptomatic 1800 ( Carlo Erba Strumentazione ).
3. RESULTS:
Figure 1 s h o w s the TG and DTG curves obtained for lignin at a 5 C / m l n heating
rate. The TG s h o w s a n Initial weight loss attributed to moisture followed by a plateau
region up to about 2 0 0 C. At this temperature, devolatilizatlon begins and extends up to
436
about 600C where a constant 55% weightloss level is reached. The DTG exhibits a small
maximun due to moisture loss and a wide peak from 200 to 500 C with a maximun at
370 C.
CD
200
400
600
800
1000
TCC)
Fif. 1 . TG and DTG curves obtained for lignin at 5*C/min heating rate.
In labscale carbonization experiments, we observed that when working with

lignin samples of low ash content, a plastic phase formation takes place at a relatively low
temperature ( 200230C, depending of the ash content ). Lignin swells and an agglomerate
product of pseudo glassy appearance is finally obtained. This would represent a serious
technical problem and also could affect negatively to the future porosity development.
Then, we investigated the conditions to avoid or reduce this problem. Experimental
evidence was obtained in the sense that it becomes less Important as heating rate decreases
and ash content Increases. B ut even at very small heating rates (<5C/min) an ash content
higher than 4% Is necessary to acoid fluid phase formation. Above 8% ash content the
problem becomes negligible even at the highest heating rate Investigated (30C/min).
According to these results, it seams convenient to carry out the carbonization step
with a relatively high ash content lignin ( 810% ). Nevertheless, this would lead to a very
high ash level in the activated carbon which may be detrimental from a quality point of
view. Then, a washing opperatlon has to be Included, the situation of which throughout the
whole procces has to be carefully investigated as we have to consider two main aspects:
Easy of removal of ashes, which depends on chemical changes occurring throughout
carbonization and activation and the potential catalytic effect of some inorganic
components mainly in the CO2 gasification step. In the present stage of our research we are
working according the following scheme:
437
LIGNIN
PRECARBONIZATION
350 C, N,
WASHING
2 X oq. H 2 S0 4
ACTIVATION
7 0 0 9 0 0 C, C0 2
CARBONIZATION
7 0 0 9 0 0 C, N ,
(~10%a.c.)
ACTIVATED
CARBON
The results obtained on the carbonization experiments revealed that the most
important loss of volatile matter occurs within the 300500 C range and a nearly constant
yield close to 40 % ( referred to organic matter ) is reached beyond 700 C. The carbon
content of the final products becomes very close to 95 % at this temperature. An important
feature is the evolution of S content, which goes from 1 % in the initial kraft lignin to less
than 0.5 % at 500 C and 0.25 % at 900 C.
The apparent surface area of the carbonized products shows an increase up to 800
C followed by a decrease in the 700900 C range, which becomes specially significant at
900 C. Decrease In apparent surface area could be explained as the result of increasing
rearrangement of parallel layers of carbon atoms.
Figure 2 shows the N2 adsorptiondesorptlon isotherms corresponding to the 700
and 800C chars. B oth exhibit a shape characteric of microporous solids. This thermal
range was adopted as the optlmun for carbonization. At 700C, the devolatilization process
requires no more than one hour and the apparent surface area of the resulting carbon
becomes close to 500 m 2 / g , reaching a value of 600 m 2 / g at 800C.
200
I
al
IS)
M
E
o
150
* *
700C Char
800 e C
Char
100
0,2
0,4
0,6
0,8
1,0
P/PO
F i g . 2 . A dsorptiondesorption isotherms of N 2 at 77 of chars: open points,
adsorption; closed poi nts, desorption.
438
C 0 2 activation of the carbonized samples lead to essentially microporous
products, but the micropore distribution is increasingly wider as burn-off increases,
according to the shape of the N2 isotherms and the D R and ocs plots. Figure 3 shows the N2
adsorption-desorptlon isotherm of the activation product corresponding to a 55% bum-ofT.
An apparent surface area close to 1000 nfi/g was obtained at 27 % burn-off which increased
up tol500 m 2 / g at 70% bum-off.
1200
0 4
0 6
P/PO
Fig. 3.
Adsorption-desorption isotherm of N 2 at 77 of the activation

product corresponding to a 55X burn-off: open points, adsorption;
closed points, desorption.
Pilot plant studies are at present at the plant start-up stage. The pilot plant has two
main sections ( carbonization and activation ), the furnace being in both cases of screwconveyor type and electrically heated. An intermediate paddle crusher allows to grind the
char before CO2 activation. This becomes convenient as same degree of agglomeration is
observed in the carbonization step.
ACKNOWLEDGMENT;
The authors wish to express their gratitute to the Empresa Nacional de Celulosas,
S.A. for providing the financial support for this research. T. Cordero also acknowledges to
the Spanish CICYT-D GICYT for a R+D grant.
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
JEGERS, H.E. and .KLEIN, M.T (1985). Ind. Eng. Chem. Process Des. Dev., 24 173
NUNN, T.R et al, (1985). Ind. Eng. Chem. Process Des. Dev. 24 844
OTANI, Cet al, (1984). J.Chim. Phys., 81 887
OTANI, Cet al., (1986). Ceramica, 32. 315
POLI
D ORO, H. et al., (1986). Ceramica, 32. 181
OTANI, C. et al., (1988). Proc. Carbon'88, p. 648. Newcastle uponTyne.
439
ACTIVATED CA RBONS FROM CHROMIUMTA NNED LEA THER WA STE.

MA. MARTINEZ-SANCHEZ,
C ORGILES-BARCELO,
J.M. MARTIN-* and
F. RODRIGUEZ-REINOSO*.
INESCOP. Asociacin de Investigacin de las Industrias del
Calzado y Conexas.
Elda. Alicante.
Spain.
'Departamento de Qumica Inorgnica e Ingeniera Qumica.
Alicante.
Spain.
SUMMARY
The preparation of COa activated carbons from chromium
tanned leather waste has been used as a way to reduce
the volume of this residue and to find a practical
application.
The effect of some preparation variables
(temperature, soaking time, heating rate, etc.) on the
adsorption characteristics of the carbons has been
studied using N 2 (77K) and COa (273K) as well as mer
cury porosimetry.
The microporosity does not change
much during activation in COa, very likely because of
the blocking caused by the Cr203 particles. Since the
volume of macropores is very high in all carbons, in
creasing with burnoff in COa, they could be useful in
adsorption from solution processes.
I. INTRODUCTION
The tanning and footwear industries produce a large
volume of chromiumtanned leather waste which contains an
average 6 wt% of Cr203 , introduced in the leather during
the tanning process with chromium (III) salts (1). A t
present, this waste does not have any practical application
and in fact, its elimination is very problematic because of
economical and ecological considerations.
It is therefore
important to find a way of elimination of the waste in which
useful materials could be obtained.
This paper presents a
such new way of elimination by producing activated carbons.
This approach has the advantage of considerably reducing the
volume of the waste and, additionally, of producing adsor
bent carbons with adequate adsorption capacity towards gases
and solutes in aqueous solution.
II. EXPERIMENTAL
The leather waste used as precursor in this work was
of black boxcalf type with aniline finish.
The leather
was cut in 2x2x2 mm cubes in order to obtain granular ac
tivated carbons although, in some cases, shreded leather
was also used.
The leather was carbonized in a tubular
furnace under a Na flow (80 cm3/min) at different tempera
440
tures (773 and 1123K), heating rates (1.5 and 5K/min) and
soak time (2,5 and 10 h ) .
The carbonized material was
activated in a flow (80 cm3/min) of C0 2 at 1098K for 228 h.
The nomenclature of the samples includes: precursor, car
bonization conditions (2 digits) and time of activation.
The characterization of the porous texture of the
carbons was basically carried out by adsorption of N2(77K)
and C02(273K) using a conventional gravimetric system fitted
with silica spring
balances; mercury porosimetry was also
used for the larger size pores.
III. RESULTS
The chemical analysis of the leather shows that this
material may be useful for the preparation of activated
carbons since it has a 45 wt% of elemental carbon. The
leather has an ash content of about 6 wt%, most of which is
Cr 2 0 3 .
This high content of chromium in the leather could
be considered as an inconvenience for the preparation of
activated carbons, but it was shown that the whole amount of
chromium remains as Cr203(2) in the final carbons, this
being a very stable oxide.
The carbonization process of chromiumtanned leather was
studied in a previous report (3) as a function of tempera
ture; the process was almost completed at 1000K, with a
yield of 23%, similar to that found for many lignocellulosic
materials (4). For this reason, a carbonization (in nitro
gen) temperature of 1123K was used in most cases.
The
carbonized leather was activated in a flow of COa, under
different experimental conditions.
There follows a short
analysis of the role of some of the variables used in the
preparation of the activated carbons.
. Carbonization heating rate. The N2(77K) adsorption
isotherms (Figure 1) corresponding to the carbons prepared
using 1.5 and 5K/min carbonization heating rate are charac
teristic of essentially microporous solids. The analysis of
these isotherms (and the
corresponding
C0 2
at 273K
isotherms) was carried out using the DubininRadushkevich
(DR) equation (5). The results obtained are listed in Table
1, where the volume of mesopores larger than 7.5 nm and
macropores obtained from mercury porosimetry have also been
included. The data show an increase in microporosity for
the 5K/min heating rate but almost no change in the volumes
TABLE 1.
Carbon
C8M8
C8R8
H.R.
(K/min)
1.5
5
Some data for carbon
Global
Yield
(wt%)
17
13
N2
0.30
0.32
V(cm:V g )
micro
meso
C0 2
macro
0.25
0.29
0.84
0.89
0.10
0.13
441
of meso and macropores (the high value of macropore volume
of these carbons should be noted); on the other hand, the
global yield is larger for the 1.5K/min heating rate.
Figure 1. N2/77K adsorption isotherms

B.- Carbonization time.
(Table 2).
The global yield
increases with increasing carbonization temperatures but
the microporosity remains almost constant from 2 to 10h;
there is however an important decrease in meso and macroporosity for the carbons prepared by 10h carbonization.
TABLE 2.
Carbon
C8L8
C8M8
C8N8
t(h)
2
5
10
Some data for carbons.
Global
Yield
(wt%)
14
17
18
V(cm3/g)
micro
N2
CO2
0.30
0.30
0.28
0.25
0.25
0.25
meso
macro
0.11
0.10
0.05
0.80
0.84
0.66
C - Carbonization temperature.
(Table 3) . The yield
is larger for the higher carbonization temperature. There
is almost no change in the microporsity but a decrease at
1123K in mesoporosity takes place.
TABLE 3.
Carbon
T(K)
Global
Yield
(wt%)
C5L8
C8L8
773
1123
11
14

V(cm3/g)
micro
meso
N2
0.31
0.30
CO2
0.24
0.25
0.20
0.11
macro
0.86
0.80
442
D.- Activation time.
(Table 4). With increasing activation time, there is a widening of the microporosity.
However, for long activation periods there is a decrease in
the micropore volume and an increase in the volumes of meso
and macropores.
This may be a consequence of both the
destruction of a proportion of micropores and the progressive accumulation of ash (carbon C8M28 has 55 wt% ash content) in the interior of the carbon particles.
TABLE 4.
Carbon
C8M2
C8M8
C8M12
C8M28
t(h)
2
8
12
28
Global
Yield
(wt%)
22
17
15
9
N2
0.23
0.30
0.33
0.26
micro
C0 2
0.23
0.25
0.27
0.19
V(cm3/g)
meso
macro
0.04
0.10
0.06
0.22
0.63
0.84
0.79
1.02
IV.- DISCUSSION
The micropore volume of the activated carbons prepared
from chromium-tanned leather waste does not change much for
the different variables introduced in the carbonization and
activation processes, being about 0.30 cm3/g (equivalent
surface area: 900 m 2 / g ) . This may be surprising when comparing with other carbon precursors but it may be explained in
terms of the high Cr 2 0 3 content.
Cr 2 0 3 particles may be
blocking the entrance of a relatively large proportion of
narrow pores; although there are additional data confirming
this hypothesis (3), the effect of the Cr 2 0 3 could be indirectly shown by using both pickled leather (without
chromium) and "extracted" leather (after chromium extraction) as precursors for the carbon.
P/Po
Figure 2. N2/77K adsorption isotherms
443
TABLE 5.
Carbon
Leather
S8M4
C8M12
C8M8
D8M12
Pickled
Granular
Powder
Extracted

Activation
Yield
(wt% daf)
58
54
54
50
V micro (cm3/g)
Na
C0 2
0.08
0.33
0.35
0.85
0.06
0.27
0.28
0.51
Figure 2 includes the N2(77K) adsorption isotherms for

the powder carbons prepared from pickled leather (S8M4),
chromium "extracted leather (D8M12) and leather (08M8); for
the sake of comparison the isotherm for a granular carbon
from leather (C8M12) has been included.
In all of these
cases the CO2 burn-off for the ash free carbon is around
55%.
According to Figure 2 and Table 5, carbon S8M4 has a
very low adsorption capacity and this indicates that the
tanning process favours the formation of the basic structure
needed to form a proper activated carbon.
On the other
hand, carbon D8M12 exhibits a very high adsorption capacity
(about 2500 m 2 /g in equivalent surface area) and a wide
micropore size distribution.
Consequently, it is possible
to conclude that the Cr203 particles are partially blocking
micropores in carbons from chromium-tanned leather; if a
portion of these particles is eliminated by previous extraction of the leather, the adsorption capacity is considerably
increased.
One important aspect of activated carbons prepared
from chromium-tanned leather is the high volume of macropores this being important for applications such as adsorption from solutes in aqueous solution, since the macropores
would facilitate the access of the solute to the interior of
the carbon particles.
REFERENCES
1.
2.
3.
4.
5.
LANGERWERF, J.S.A
J. Soc. Leather Technol. Chem. 69,
166 (1985).
MARTIN-MARTINEZ, J.M., RODRIGUEZ-REINOSO,
MARTINEZSANCHEZ, M.A. and ORGILES-BARCELO, C.
Int Conf.
Pyrolysis and Gasification. Luxembourg. 1989.
MARTINEZ-SANCHEZ, M.A., ORGILES-BARCELO, C , MARTINMARTINEZ, J.M., RODRIGUEZ-REINOSO, F. and TORREGROSA,
R., Proc. Int. Conf. Carbon. Newcastle upon Tyne.
p.280. 1988.
LINARES-SOLANO, A
LOPEZ-GONZALEZ, J.D., MOLINA-SABIO,
M. and
RODRIGUEZ-REINOSO, F.,
J. Chem. Technol.
Biotechnol. 3_0, 65 (1980).
DUBININ, M.M.
"Progress in
Surface and Membrane
Science." Ed. D.A. Cadenhead. Academic Press. New York.
1, 1 (1975).
444
MOTOR FUELS FROM PYROLYTIC LIGNINS
J. Piskorz, P. Majerski, D. Radlein and D.S. Scott
Department of Chemical Engineering, University of Waterloo
Waterloo, Ontario, Canada N2L 3G1
Summary
Pyrolysis of wood by the Waterloo Fast Pyrolysis gives a high yield

(70% to 80%) of a homogeneous pyrolysis oil. This oil can be readily
separated by extraction into two fractions, one containing mainly
water soluble compounds, and one containing components derived from
the lignin content of the wood.
Such a "pyrolytic lignin", derived
from a sawmill waste of mixed coniferous wood and bark, was subjected
to catalytic hydrognation in a bench-scale catalytic flow reactor.
The bench scale catalytic reaction apparatus has some novel features,
and these are described. The reactor operates as a continuous plug
flow unit and is constructed so that a controlled axial temperature
gradient can be imposed. Successful hydrognation runs were carried
out in this non-isothermal rector which gave high conversions of up
to 78% of carbon fed to a hydrocarbon distillate. Very little coke
formation was observed. The product distillate was approximately 60%
aliphatic and 40% aromatic in character.
1. INTRODUCTION
In an earlier publication (1), it was reported that the conclusion
reached by an International Energy Agency (IEA) study group under the
Direct Biomass Liquefaction Project was that the atmospheric pressure
flash pyrolysis process was a cost effective and technically feasible
method for the production of liquid fuels from wood and peat. However, if
hydrocarbon-based transportation fuels were the desired product, further
processing of the crude liquid pyrolysis oils was needed to produce
marketable gasoline or diesel range products. This IEA report has since
become more generally available (2).
In our laboratories one of the most successful atmospheric flash
pyrolysis processes for conversion of biomass to liquids has been developed over the past ten years (the Waterloo Fast Pyrolysis Process or
WFPP).
In our earlier publication with researchers at Battelle, Pacific
Northwest Laboratories (1), the pyrolytic liquid obtained from the flash
pyrolysis of peat employing WFPP technology was used as a feedstock for
the successful catalytic hydrotreating reported then.
The present work
describes the results obtained using a modified hydrotreating apparatus
when a lignin fraction of biomass is used as a feedstock. The lignin used
in this work is one of the products which can be obtained from our atmospheric flash pyrolysis process, details of which can be found in earlier
publications (3). When wood or other biomass undergoes rapid pyrolysis
about 80% to 85% of the lignin present is depolymerized, vapourizes and
445
appears in the liquid product. This material is aromatic in character and
of much lower molecular weight than the native lignin. The characteristics of one such lignin have been described in a previous article (4).
The fraction which we have labelled as "pyrolytic lignin" can be
recovered from the crude pyrolytic oil, which is a homogeneous single
phase liquid, by extraction with water. This extraction removes the watersoluble carbonyl compounds, sugars etc. which are derived from the decomposition of the hemicellulose and cellulose fractions, and leaves a precipitate of material derived largely from lignin.
This precipitate is
readily removed by centrifuging or filtration, and can be washed and dried
if desired to give a light brown powder product. However, for use as a
feed for hydrotreating, drying was not necessary. Details of the separation procedure and of the fractions recovered have been given elsewhere
(5).
Yields of pyrolytic lignin are normally about 16% to 22% of the feed
when wood is pyrolyzed (that is 22% to 28% of the crude pyrolysis oil).
Lignin yields will vary with the nature of the biomass used as feedstock.
It should be noted also that the aqueous extract from the above lignin
recovery step is a source of several valuable acids, aldehydes and ketones
derived from the carbohydrate fraction of the biomass (5).
The lignin fractions recovered from processes in which the conversion
of cellulose or hemicellulose is the main objective represent a low value
by-product at the present time. For example, the conversion of cellulose
to glucose for fermentation to fuel alcohol b v most processes leaves a
lignin residue of little present value. Similarly, if fast pyrolysis is
used to produce oxychemicals or sugars, then a pyrolytic lignin by-product
will result. Any conversion of these lignins to higher value-added products than their current use as a low grade fuel would be an economic
advantage for any of these biomass conversion processes.
The lignin obtained from fast pyrolysis, or from microbiological
processes, should be a good candidate for hydrotreating.
It is rich in
aromatic structures which are in a less highly condensed form than is
normally produced by more severe conversion processes such as conventional
pulping.
Indeed, it could be anticipated that the difficulty of hydrotreating a lignin fraction might be directly related to the severity of
the biomass conversion process used.
2. EXPERIMENTAL
A continuous packed bed catalytic reactor was used, modified from
that described by Elliott and Baker (6). A schematic of the apparatus is
shown in Figure 1. The reactor itself had a capacity of 96 ml and was
only about one-quarter the size of that used by Elliott and Baker.
The
pyrolytic lignin feed could be readily liquefied by heating, but a controlled minimum temperature was desirable because of the thermal sensitivity of the material. These requirements were met by the use of a unique
free-piston feeder. The feed vessel was surrounded by a heating jacket in
which thermostatically controlled heating fluid was circulated. The feed
vessel contained a free piston which separated the liquefied lignin from
water or other appropriate displacement fluid. Feed rate was controlled
by a twin head HPLC pump which drew the displacement fluid from a reservoir and which could deliver from 0.25 to 24.0 ml/ min of liquid.
The catalytic reactor had a two zone furnace which allowed an axial
non-isothermal temperature gradient to be imposed.
Operation was cocurrent, upflow. Liquid product was collected under pressure in two traps
with intermediate cooling. Details of operating conditions are given in
the next section.
WATER
PUMP
A
H2
Figure 1. Continuous hydrogenation-hydrodeoxygenation apparatus.
447
10
6 000
5 0003
O
o
4000
3000
2000
1000
nF-i. i- L i u J L
*-* '
hA
6
10
12
14
TIME (min)
Figure 2. Total ion Chromatograph of pyrolytic lignin from hog fuel 5. Dimethoxy methyl acetate; 9. Phenol; 10. Trimethyl cyclopentenone;
11,11',11" - substituted methoxy phenols.
io
13
o
u
17
2
O
2 0 0 0 b-
yjL
2
3
TIME ( m i n )
14
J IS 16
tl
zs 000
o
6000
O
_, 4000
<
O 2000
z
28
iLJJJAiiJUw
7
TIME (min)
Figure 3. Total ion Chromatograph of light organic product (Run 3) from

hydrotreating of pyrolytic lignin -- more volatile fraction
1. Butane
7. Cyclohexane
13. Ethyl benzene
2. Pentane
8. Heptane
14. 2-xylene
3. Ethyl cyclopropane
9. Methyl cyclohexane 15. 4-xylene
4. Hexane
10. Toluene
16. Nonane
5. Methyl cyclopentane 11. Octane
17. Propyl cyclohexane
6. Benzene
12. Ethyl cyclohexane
18. Propyl benzene.
448
The raw material for the tests described here was a sample of hog
fuel from the Pacific north-west. Hog fuel is the waste cuttings generated by sawmills, and normally contains a high percentage of softwood
bark, in the case of the present sample, about 80%. The sample used consisted of a mixture of waste from two species, Amabilis fir and Western
hemlock, which are commonly harvested and processed together.
The hog
fuel was dried to 9.5% moisture, ground to -1 mm and then pyrolyzed at
525 C and atmospheric pressure in a sand fluidized bed. Apparent vapour
residence time was approximately 0.45 seconds.
The crude pyrolysis oil
was water extracted to give a yield of pyrolytic lignin of 21.2% of the
hog fuel fed (both on a moisture free basis).
Analysis of this lignin
fraction is given in Table 1.
The pyrolytic lignin composition was investigated by means of GC-MS
analysis and by
C NMR spectroscopy.
A typical GC-MS chromatogram is
shown in Figure 2, the peaks shown a tentatively identified in the GC-MS
spectra are mainly methoxy and dimethoxy phenols, and substituted methoxy
phenols e.g. 2-methoxy-4-(l-propenyl) phenol. The NMR spectra shows some
differences in structure of this lignin as compared to those obtained from
hardwoods such as poplar (4). The guaiacyl/syringyl ratio is high, consistent with the lignin from the softwood component of the feed. A significant amount of carbonyl groups are also indicated, a feature which is
almost completely absent in hardwood lignins.
Presumably, these arise
from the high extractives content of the bark, and in particular the
tannins, resinous and waxy fractions which would contain carboxylic acid
or ester linkages.
3. RESULTS
The results for two upgrading runs are given in Table 2. In each of
these runs the same catalyst was used without replacement or regeneration
and it had already been in operation for over six hours. In both runs, a
constant flow of hydrogen was maintained and total reactor pressure was
14 MPa. The catalyst used was sulfided commercial Co-Mo pellet supplied
by Katalco Corp., and 65.7 grams were initially charged to the reactor.
The reactor was filled with lignin, the desired axial temperature gradient
established, and flow started which was recorded as zero time.
The results in Table 2 for the two runs show a high conversion of the
feed to a liquid organic fraction, 64% and 61% respectively, representing
a carbon conversion of about 78% to liquid hydrocarbons. The oxygen content of this light organic fraction was about 0.5%, and oxygen removal was
about 85% as water. Only about 1% of heavy residue remained, which was
readily soluble in methanol.
The second test (Run B) was carried out at twice the feed rate but
otherwise essentially the same reaction conditions as the previous run.
Very similar yields were obtained even though the space velocity was
doubled. The short-fall in the overall recovery of products (4% to 9% of
feed) appears to be due to the loss of volatile hydrocarbons in the C Cg fraction when the liquid product was depressurized.
The light organic product had an elemental analysis of C - 88.48%,
H - 11.06% and 0 (by difference) - 0.46%.
The H/C atomic ratio is 1.50,
suggesting an appreciable aromatic content. The results of GC-MS analysis
of the light organic fraction are shown in Figures 3 and 4.
Material
eluted in the first five minutes consisted of normal and cyclic alkanes to
C Q , as well as simple aromatics. Small amounts of phenols eluted next and
the final group of compounds were largely alkanes, both straight chain and
branched, from C-,? t o C?6
Peak numbers shown in Figures 3 and 4 are
identified in Figure 3.
449
10000
Z5 8 0 0 0
o
o
32
6000
33
34
40O0
_J
<I
2 0 0 0
35
iL
13
12
15
TIME (min)
10000
8 000
3
)
6 000
7
0
4000
_l
<
2000
36
37
A-
16
17
I
18
19
I
20
TIME (min)
Figure 4. Total ion Chromatograph
hydrotreating of pyrolytic lignin
32. Octadecane; Tridecane
35.
33. Eicosane; Hexadecane
36.
34. Eicosane, Tetradecane
37.
of light organic product from

less volatile fraction
Docosane; Eicosane, 7hexyl
Docosane; Eicosane, 7hexyl
Docosane; Heptadecane, 9octyl
^ ^ *
60
Jf^*^^
li
Lu
^/^
^ s *
50
j r
3?
UJ
aS"^
40
2
3
_l
O
^JL
it
30
>
u
_l
Q
^M
/
20
<
CO
10
0 "
20 45
70 95
120 145 170 195 220 245 270 295 320 345
BOILING POINT C O
Figure 5. Simulated distillation curve for light organic product from
hydrotreating of pyrolytic lignin (Run 3 ) .
450
The
CNMR spectra of the light: organic fraction was also measured.
A clean separation of two major groups of hydrocarbons was obtained, that
is, aliphatic and aromatic, with almost no indication of any oxygen con
taining structures.
Integration of the aliphatic peaks, most of which
were characteristic of nalkanes, indicated that 61.7 0.8% of the carbon
was aliphatic. Therefore, the substantial fraction of aromatic carbons,
about 38%, suggests that the light organic fraction is more similar to a
kerosine than to a diesel fuel. A dditional peaks in the NMR spectra indi
cated the presence of some naphthenic structures also, or of other con
densed aromatic or hydroaromatic structures.
A simulated distillation of the light organic fraction was also
carried out using the SIMDIS chromatographic method (Sulpeco Inc. Petrocol
3710 column with qualitative calibration mix) according to A STM method
D3710. The resultant cumulative boiling point curve to 345C (the maximum
calibration point) is shown in Figure 5.
This analysis was carried out
some months after the preparation of the lignin derived hydrocarbon
liquid, and it was estimated that 5% to 10% had been lost, representing
the most volatile fraction.
Figure 5 shows that about 65% or more was
below 345C BP with about 50% boiling within the gasoline range.
With
fresh product and more careful recovery of volatiles, it is estimated that
about 60% of the product would be gasoline range hydrocarbons containing a
high percentage of simple aromatic compounds, and cyclic alkanes.
The
heavier fraction boiling above 225 C would be largely straight chain
alkanes and might be suitable for use as a component of diesel fuels.
The successful hydrotreating of this lignin fraction from the pyroly
sis of a waste wood and bark mixture suggests that similar lignins from
other processes, such as that recovered during fuel alcohol production
from lignocellulosics, might also be similarly upgraded with good yields.
4. A CKNOWLEDGEMENTS
The authors would like to express their thanks to the Natural
Sciences and Engineering Research Council of Canada for the financial
support of this work.
REFERENCES
(1)
ELLIOTT, D.C., BA KER, E.G., PISKORZ, J., SCOTT, D.S. and SOLA NTA USTA ,
Y. (1988). Energy and Fuels, 2, 234235.
(2) ELLIOTT, D.C., BA KER, E.G., OSTMA N, ., GEVERT, S.B., BECKMA N, D.,
SOLANTAUSTA, Y. and HORNELL, C. (1989).
A
" technical and economic
analysis of direct biomass liquefaction" Paper 45, IGT Symposium on
Energy from Biomass and Wastes XIII, New Orleans, Feb. 1317.
(3) SCOTT, D.S., PISKORZ, J. (1985). Bioenergy 84; Egneus, H.; Ellegard,
A. Eds. Elsevier Applied Science, London, Vol. Ill, 1522.
(4) RA DLEIN, D., PISKORZ, J., SCOTT, D.S. (1987). J.A nal.A ppi. Pyrolysis
12, 5159.
(5) PISKORZ, J., SCOTT, D.S., RADLEIN, D. (1989). A CS Symposium Series
"Production, Analysis and Upgrading of Pyrolysis Oils from Biomass"
E.J. Soltes, Ed. American Chemical Society, Washington, D.C.
(6) ELLIOTT, D . C , BA KER, E.G. (1987). Energy from Biomass and Wastes X;
Klass, D.L. Ed., Institute of Gas Technology, Chicago, 765784.
451
Table 1
Analysis of Pyrolytic Lignin from Hog Fuel
Yield, % of feed, mf
21. 2
Moisture content, *
18.,0
1..16
Density, gm/ml.
Elemental Analysis, % mf
C
H
o (by diff.)
73..22
5,.95
20,.8
Moderately Soluble in methanol, pumpable at 60'C
Continuous Fixed Bed Catalytic Upgrading of Lignin from Hog Fuel

Moisture 18.OX, C - 73.22, H - 5.95 mf
400/240
415/230
Duration, minutes
182
94
Amount fed, grams
102.1
102.6
Water
35.0
34.0
Light organic:s
53.7*
50.9
Total liquid product
88.7
84.9
1.3
1.3
Liquid + tar produced
90.0
86.2
Cases :
CO
traces
traces
co2
2.76
3.08
CH4
2.63
2.24
C2H4
traces
traces
C2H6
0.80
0.70
0.72
0.63
0.76
0.63
7.67
7.28
Run Number
Temperature 'C, outleit/inlet
Yields, grams
Heavy residue
3H8
c4+
Total recovery
95.7X
91.IX
X mf feed as light organica
64X
61X
* C - 88 .48, H - 11.06
452
ROLE OF CHROMIUM OXIDE IN THE TEXTURE OF

CARBONS FROM LEA THER
J.M. MARTIN-MARTINEZ, F. RODRIGUEZ-REINOSO, . MARTINEZ-SANCHEZ* and
C ORGILES-BARCELO".
Departamento de
Qumica Inorgnica e Ingenieria Qumica.
Alicante.
SPAIN.
*INESCOP. Asociacin de Investigacin de las Industrias del Calzado y Conexas.
Elda. Alicante.
SPAIN.
SUMMARY
A series of carbons has been prepared by carbonization
in nitrogen followed by activation in carbon dioxide
of chromiumtanned leather.
The porous texture of
carbons has been characterized by adsorption of N2
(77K) and isobutane (261K).
There is a progressive
increase in porosity upon activation with CO2 up to
about 50% burnoff followed by a decrease for larger
extents of burnoff. This is due to the progressive
increase in the Cr20 3 content of the carbons. Both
Xray diffraction and scanning electron
microscopy
show a homogeneous distribution of Cr 2 0 3 particles
through the carbons and in addition the mean
particle
size increases with burnoff. The CraC>3 particles block
the entrance of the micropores of the carbon but at the
same time they act as skeleton for the structure of the
carbons which have appropiate mechanical resistance.
I. INTRODUCTION
A previous report (1) has shown that chromiumtanned
leather can be used for the preparation of activated carbons
having a large volume of macropores and equivalent surface
areas around 1000 m 2 /g.
The carbons had a very high ash
content, most of which were chromium compounds, and it
should be admitted that this inorganic matter must somewhat
affect the texture and adsorption properties of the carbons.
Finding the role of the chromium compounds in these carbons
is not an easy task since those compounds could be in the
interior of the narrow pores.
This paper presents the
results found using different experimental approaches, in
the study of the effect of the chromium compounds in both
the structure and the adsorption properties of carbons
prepared from leather.
II. EXPERIMENTAL
A series of carbons covering the 770% burnoff range
have been prepared from chromiumtanned leather by car
bonization in nitrogen at 1173K for 5h followed by activa
tion in carbon dioxide at 1098K for 460h. The nomenclature
453
of the samples includes followed by the burnoff in C0 2 .
The carbons have been characterized by adsorption of N2(77K)
and isobutane (261K) using a conventional McBain type
gravimetric system.
Scanning electron microscopy (Philips
515) and Xray diffraction (Philips PWR 1840) were used in
this study.
111. RESULTS A ND DISCUSSION
The adsorption of N2(77K) and isobutane (26IK) can be
used to show the development of porosity produced in the C0 2
activation process of the carbonized leather.
Figure 1
shows the evolution of micropore volume obtained by ap
plication of the DubininRadushkevich (DR) equation (2) to
the adsorption data as a function of burnoff. There is
an increase in micropore volume from carbon P7 to carbon
P58, decreasing thereafter; carbon P7 exhibits a small
molecular sieving effect towards isobutane, as expected in
a carbon with low burnoff (3). However, if the volume is
expressed per gramme of ash free carbon, the micropore
volume continuously increases. This different behaviour is
not surprising considering the large ash content of the
carbons, especially for high C0 2 burnoff. The char has 21%
ash content and it increases (see figure 2) with activation
time, especially for burnoff larger than 50%. Consequent
ly, the high ash content for carbons P64 and P70 seems to be
responsible for the drop in micropore volume observed in
Figure 1. It should be noted that the ash content measured
on the carbons is coincident (see Figure 2) with that deter
mined theoretically by assuming that all inorganic matter of
the leather remains during the activation process.
,/77I
0,7
0.2
~1
20
40
BO
80
Bumoff r
Figure 1. Variation of micropore volume with burnoff
454
80
70
60
A THEORET IC VA LUES
EXPERIMENTAL V A LUES
50
40 H
30
20
IO
0
20
40
60
00
BURNOFF (X)
Figure 2. Evolution of ash content with burnoff

In order to understand the evolution of adsorption
capacity of the carbons for large burnoff it is important
to know the chemical nature of the ash and its evolution
during activation.
Xray fluorescency and difraction,
together with scanning electron microscopy (SEM) may provide
the information required. The SEM pictures for the char
obtained at 1173K show prismatic particles uniformly dis
tributed (see Figure 3b); EDA X analysis showed that these
particles were basically constituted by chromium. Xray
diffraction for the char showed the presence of aCr 2 0 3
crystals, being the only chromium compound in the carbons.
Figure 3 includes the SEM pictures corresponding to
the leather, the char and one activated carbon.
Figure 3a
shows the fibrous aspect of the leather, with no Cr 2 0 3
particles on the surface since the leather was treated
during tanning with Cr(III) coordination compounds. When
this leather is carbonized (Figure 3b) the surface
shows
the presence of porosity which is developed upon activation
(Figure 3c); in both the char and the carbon Cr 2 0 3 particles
are seen in the pictures.
The mean Cr 2 0 3 particle size
(calculated from the Xray diffractograms) increases with
burnoff as shown in Table 1. Such an increase is more
noticeable in the first stages of activation and it takes
place to a lesser extent after 50% burnoff, when the in
crease in ashcontent is more important.
TABLE 1. Some data for carbons
Carbon
Char
P7
P25
P39
P58
P64
P70
d (nm)
(2=65.1)
26.8
26.8
29.9
33.8
34.9
36.1
37.4
455
The SEM micrographs of Figures 3b and 3c show a considerable concentration of Cr 2 0 3 crystals around and inside the
macropores. Since it is not possible to observe Cr 2 0 3
crystals inside the small pores due to limitations of the
technique, the influence of Cr 2 0 3 on the adsorptive capacity
of the carbons may be analysed taking into account the
adsorption of N 2 (77K) on the ashes obtained from carbon P70
which gives a BET surface area of 7 m2/g , this means that
even although the ash content is very high for carbons with
large burn-off the contribution to total micropore volume
is very small (lower than 0.002 cm 3 /g). Since the micropore
volume for carbon P70 is 0.21 cm3/g and 0.70 cm3/g if the
carbon is considered to be ash free this large difference
must be due only to blocking of the micropores by Cr 2 0 3
crystals formed during the heat treatment taking place on
activation in C0 2 .
Figure 3. SEM pictures for leather and carbons
456
An additional test would be to extract the Cr 2 0 3 from
the carbons This is not a simple task because after trying
different chemicals and finding that KBr0 3 was the most
effective, only 41% of Cr 2 0 3 could be removed from the
carbons.
As a typical example, Figure 4 includes the Xray diffractograms and Figure 3c and 3d the corresponding
SEM pictures for carbon P58 before and after extraction with
KBr0 3 respectively. There is a noticeable reduction in the
number of Cr 2 0 3 particles in the surface of the carbon after
treatment and a reduction in crystalinity (the mean particle
size decreases from 34.9 nm in P58 to 27.5 nm after partial
extraction of C r 2 0 3 ) . On the other hand, Figures 3c, 3d and
4 show that there is an important change in the texture,
with a decrease in large porosity and some cracks after
KBr0 3 treatment.
In addition, the carbon has a much lower
mechanical strength after extraction and the adsorption
capacity is almost nil.
This seems to indicate that although the Cr 2 0 3 particles are blocking the micropores in
the original carbon it also acts as a rigid skeleton maintaining the structure of the carbon.
P58
SO
40
P58 after Cr03

extraction
Figure 4. X-ray diffractograms for some carbons

REFERENCES
MARTINEZ-SANCHEZ, M.A., ORGILES-BARCELO, C , MARTINMARTINEZ, J.M., RODRIGUEZ-REINOSO, F. and TORREGROSA,
R., Int. Conf. Carbon. Newcastle upon Tyne. p.280.
1988.
DUBININ, M.M.
"Progress in
Surface and Membrane
Science". Ed. D.A. Cadenhead. Academic Press. New York.
, 1 (1985).
3. RODRIGUEZ-REINOSO, F. "Carbon and Coal Gasification".
Eds. J.L. Figueiredo and J.A. Moulijn. Martinus Nijhoff, Dordrecht, p.601 (1986).
457
INFLUENCE OF THE POROSITY OF CARBON IN_Fe/Carbon CA TA LYSTS
J.M. MA RTINMA RTINEZ
and M.A . vA NNICE*
Departamento de Qumica
Inorganica e Ingeniera Qumica.
Universidad de Alicante. A LICA NTE. SPA IN.
* Department of Chemical Engineering. The Pennsylvania State
University. University Park, PA 16802. USA .
Summary.
Two activated carbons from olive pits were prepared by
carbonization and subsequent activation
in COE for f8
(carbon A ) and 82 hours (carbon B> to produce different
micro and macroporosi ty. Both carbons were used to sup
port Fe 3 (C0)ie and both
gave
welldispersed
Fe/C
catalysts which retained small Fe crystallites under
reaction conditions. A sprepared
samples
(no initial
reduction) were active but a high temperature reduction
at 673K increased
the TOF for Fe whereas the TOF
remained
the same for BFe. A lthough catalytic behavior
was similar in general, the BFe catalyst produced
much
less
ChL,,
which
may
reflect
an effect due to
microporosi ty.
1.INTRODUCTION.
The suitability of iron catalysts to convert syngas to
hydrocarbons
is
well known
(1).
Bulk Fe is employed
commercially, but iron supported on carbon <2>, silica (3) and
alumina (4) has been frecuently studied. However, it is dif
ficult to obtain very small Fe particles on oxide supports be
cause the precursors do not reduce easily. Thus an inert sup
port with no surface oxygen groups, such as carbon, may be
atractive, especially when combined with the use of iron car
bonyl clusters such as Fe 3 (C0)i e and Fe(C0)s (5). On the other
hand, Jung et al. (2,6) found that carbons with large surface
areas favoured the formation of welldispersed
iron. Highly
dispersed, unpromoted Fe/C catalysts can be prepared which
have high activity and higher that expected
olefin/paraffin
ratios
(6B). This indicated
that the microporosity of the
carbons might play a role in obtaining highly dispersed
Fe
(9). However, Kikuchi et al. (10) concluded that the iron par
ticle size is not a strong function of the carbon surface
area. Because there are controversial papers on this topic,
the major aim of this study was an analysis of the
influence
of the porosity and the pore size distribution in carbon on
the dispersion and kinetic behavior of carbon supported
iron
catalysts.
S. EXPERIMENTA L.
It is well known that the activation of 1ignocellulosic
458
materials in C 0 B or steam produces carbons whose porosity can
be easily and gradually changed (11,12). Thus, olive pits were
carbonized in N e at 1123K for 2 h., then activated in C 0 e at
109BK for t*B h. (Carbon A yield = 71'/.) and 82 h. (Carbon
yield = 36'/.). Both carbons were treated in H e at 1273K for 12
hours to remove sulfur. Carbons were granular with a particle
size between 0.5 and 0.S mm. Carbons A and were charac
terized by N e adsorption at 77K in a high precision, high
vacuum volumetric system. Mercury porosimetry complemented the
analysis of the porous texture of the carbons.
Catalysts with 34 wty. iron were prepared using F e 3 ( C 0 ) l e
cluster dissolved in dry, degassed tetrahydrofurane (THF). The
carbonyl was dispersed on the carbons, which had been degassed
at IO** kPa for 16 h at 673K, by an incipient wetness impreg
nation under anaerobic conditions. The samples were then
evacuated at 300K to remove excess THF. The catalysts nomen
clature shall be Fe and BFe. The catalysts were reduced in
H e at 673K for 16 h, then H e desorption (13) and CO chemisorp
tion at 195K and 300K allowed the evaluation of Fe dispersion
in both the fresh and used (after use in the syngas reaction)
catalysts. It has been proposed that the optimum measure is CO
adsorption at 195K to avoid carbonyl formation and CO dis
sociation and the use of an adsorption stoichiometry of CO/Fe
= 1/2 (2, 14) .
Kinetic data were obtained at 0.1 MPa, usually under dif
ferential
reactions conditions, using a Perkin Elmer Sigma 3
gas Chromatograph. Both asprepared (A Pno reduction step) and
high temperature reduced
(HTR 16h at 673K) samples were
studied. Each set of kinetic data was obtained after a 20 min.
exposure to the reactant gases
(H s /C0 = 3 ) . The mass of
catalyst used in each experiment was 0.4 g.
3. RESULTS A ND DISCUSSION.
Supports. Figure 1 shows the N e adsorption
isotherms at
77K for carbons A
and B. The application of the Dubinin
Radushkevich (15) and the BET method (16) to the data gave the
surface areas <S> and micropore volumes (Ve.) in Table 1, which
also includes the C 0 S micropore volumes. Mercury
porosimetry
curves are given in Figure 2. A cross sectional area of 0.162
a
nm was used for N e at 77K and its liquid density was 0.B08
g/ml. Carbon A
shows a narrow microporosi ty (N s and C 0 B
micropore volumes are quite similar), a poorly developed
mesoporosity, and a small macroporosi ty; the distribution of
porosity in carbon A is therefore very narrow. However, carbon
was much more micro and macroporous than carbon A although
the mesopore volume remained almost unchanged. Consequently
the pore size distribution of carbon is well extended.
Chemisorption. Table 2 shows the H e desorption and CO up
takes (values have been corrected
for adsorption on the
support).
In general, hydrogen adsorption gives low surface
coverages on very small Fe particles (2,6,14). CO adsorption
on Fe at 195K is tipically less than that at 300K because of
the different stoichiometry and absence of carbonyl
formation
(2). Three of the four catalysts conform to this pattern, and
the unusually high uptake on the BFe (fresh) sample may be
due to CO retention in very small micropores during degassing.
459
Consequently the porosity of these carbons, especially
the
microporosi ty,
does
not affect
to the iron dispersion
significantly.
The used catalysts were also characterized
by chemi
sorption; values are given in Table . Hydrogen desorption
remains almost unchanged
after the reaction and there is
little change in CO chemisorption at either temperature for
the ftFe catalyst, so the iron crystallites do not sinter
during the syngas reaction. The C0/195K chemisorption is smal
ler than that of C0/300K for catalyst BFe, and the C0/300K
uptake increases after the syngas reaction. The microporosi ty
of the carbons seems to prevent the sintering of iron and when
the porosity widens, the CO in these very small micropores may
be removed more easily by evacuation. Small extents of
gasification under reaction conditions could widen these
pores. The absence of mesoporosity in the carbons might also
play an important role on the distribution of iron, however,
this point need a more detailed study (IB).
Kinetic behavior. The CO hydrognation was carried out on
both A P and heattreated iron catalysts. The most significant
results are included in Tables 3 and t. The AP catalysts have
a lower activity for CO conversion to hydrocarbons than the
HTR catalysts, especially for Fe. The A PA Fe catalyst shows
a somewhat lower TOF (turnover frecuency values) than the AP
BFe sample, so the presence of wide porosity in the carbon
may favour the initial
iron particle size distribution in
carbon pores because the TOF is very sensitive to Fe crystal
lite size (2,6). A fter HTR the Fe catalyst becomes much more
active and has a larger TOF that the BFe sample. However,
the rather high CO conversion levels may generate temperature
gradients which have some effect on the activity. Regardless,
the
porosity of these carbons stabilizes the small Fe
particles. Some of these differences in TOF values may due to
different
concentrations of active sites on the carbon
surface, which can stabilize small Fe particles and provide a
"dstructure" of Fe, which is zerovalent and superparamag
netic (17,SO).
There is an increase in activation energy for the
catalysts after the HTR treatment, but the hydrocarbons chain
growth parameter (a) at 5*8K, calculated from the lineal plot
of the A ndersonShulzFlory equation (19), does not change for
the BFe catalyst while that for the Fe sample
increase
somewhat. Select i vi t ies of the catalysts, shown in Table h,
have been taken at similar CO conversions. The Fe sample is
less selective to olefins and produces more methane than the
BFe catalyst. Consequently the selectivity to olefin produc
tion is more favoured when the microporosi ty widens.
Conelusions. The porosity of the carbon as a support for
iron can affect initial dispersion and stabilize small Fe
particles. When the porosity
is narrow a HTR treatment is
beneficial and it increases the activity, and in some cases,
it can increase the o lefin/paraffin ratio.A lso, a widening of
the porosity may lead to iron catalysts that produce
less
methane.
Acknowledgements. This work was supported by the USSpain
Joint Committee for Scientific and Technological Cooperation.
460
REFERENCES.
1. Dry, .E. "The Fischer-Tropsch Synthesis". Catalysis :
Science and Technology. J.R.
Anderson and M. Boudart eds.
Springer, Berlin. 1, 159 (1981).
2. Jung, H.J., Mulay, L.N., Vannice, M.A., Stanfield,
R.M.
and Delgass, W.N., J. Catal. 76, 208 (1982).
3. Ida, T., Tsuiki, H., Ueno, ., Tohji, ., Udagawa, Y.,
Iwai, . and Sano, ., J. Catal. 106. 248 (1987).
4. Ruckenstein, E. and Sushumma, I., J. Catal. 97., 1 (1986).
5. Phillips, J. and Dumesic, J.., Appi. Catal. 9, 1 ( 1984) .
6. Jung, H.J., Walker Jr., P.L. and Vannice, M.A., J. Catal.
75. 416 (1982).
7. Jones, V.K ., Neubauer, L.R. and Bartholomew, L . . , J
Phys. Chem. 90., 4832 (1986).
8. Sommen, A., Stoop, F. and var der Wiele, ., Appi, Catal.
lit. 277 (1985).
9. Schmitt, J L. and Walker Jr., P.L
Carbon 9, 791 (1971)
10, 87 (1972).
10. Kikuchi, E. and Morita, Y , J. Catal. 57, 27 (1979).
11. Rodriguez-Reinoso,
F., Martin-Martinez, J.M.,
Molina
Sabio, M. and Lopez-Gonzalez, J.D., Carbon 23. 19 (1985).
12. Rodriguez-Reinoso,
F., Martin-Martinez, J.M. , MolinaSabio, M., Torregrosa, R and Garrido, J., J. Colloid Interf.
Sci . 106. 315 (1985).
13. Ameise, J.A., Schwartz, L.H. and Butt J. B., J. Catal. 72.
95 (1981).
14. Venter, J., K aminsky, M., Geoffroy, G .L. and Vannice M.A.,
J. Catal. 103. 450 (1987).
15. Dubinin, M. M. and Radushkevich, L.
Proc. Acad. Sci.
USSR 55, 331 (1947).
16. Brunauer, S., Emmett, P.H. and Teller
, J. Am. Chem.
Soc. 60, 309 (1938).
17. Chen, A.A., Vannice, M.A. and Phillips, J., J. Phys. Chem
91. 6257 (1987).
18. Martn-Martnez, J.M., and Vannice M.., To be published.
19. Snel, R. and Zwart, J., Appi. Catal. 22, 337 (1986).
20. Chen, A.A., Philips, J., Venter, J.J. and Vannice, M.A.
J. Catal., In press.

(ml/g)
"By
A.
Nv
\
_Av
2-
8 / Po
Figure 1
\
-~-
A logD
Figure 2
461
TABLE 1
Adsorption Data for the Carbons
Vc.DR (cm 3 /g)
Carbon
A
VMercury poros. (cm 3 /g )
S
(m B /g)
N a /77K
C0 B /273K
1098
1420
0.39
0.51
0.37
0.40
mesopores
macropores
0.08
0.10
0.23
0.46
TABLE 2
Chemisorption on Fe/C Catalysts (pmDle/g c . t )
(after 16h at 673K in H B flowing at 40 cm 3 /g)
Catalyst
Fe
wt%
He
C0/195K
C0/300K
Fe (fresh)
BFe (fresh)
3.12
4.00
15.7
27.0
132.1
310.2
159.
206.9
0.E9
0.29
0.47
0.86
Fe (used)
BFe (used)
3.12
4.00
17.2
29.8
136.4
196.5
167.7
90.2
0.32
0.41
0.49
0.55
CO/Fe D(Fe./Fe )"=
<> A t 300K.
<<" From C0/195K, CO/Fe. = 0.5.
TABLE 3
Catalytic Behavior of Fe/C Catalysts
(P = 0.1
MPa, H E / C O = 3, = 54BK)
A <nmole/g F .s)
Catalyst
APAFe
APBFe
AFe
BFe
CGconv.
HC C/.)
CO TOF
to HC
EH C
( s" 1 . IO 3 ) ( k J/mole)
C0B
HC
CH<*
2.24
7.62
8.37
21.99
6.74
19.68
2.80
4.38
1.3
3.8
63
65
0.46
0.55
18.86
10.88
60.16
35.98
56.73
28.08
13.62
6.05
9. 9t>
3.8=
87
87
0.56
0.57
* Based on C0/300K values on fresh samples.

"* Based on C0/195K values on used samples.
TABLE 4
Select i vi t ies in the CO Hydrognation Reaction
( = 0.1 MPa, He/CO =3)
Catalyst
T(K>
HC C/.)
Cl
C2
C2
C3
APAFe
APBFe
548
523
2.24
3.86
64
46
11
4
15
18
AFe
BFe
508
538
12.43
9.25
67
44
5
10
12
13
C3
C4
2
8
2
9
2
8
0.88
0.46
7
13
3
3
3
8
2
9
0.80
1 .44
C5 (C2+C3)
462
DEVELOPMENT AND CONSTRUCTION CF A SAMPLING LINE
FOR WOOD PYROLYSIS EMISSIONS
J. LACHENAL and J.M. TOLEDO
Laboratoire National d'Essai, 5 rue Enrico Fermi, 78190 Trappes, France
C. MEZERETTE and A.M. VERGNET
Centre Technique Forestier Tropical, Departement du C.I.R.A.D.
45bis, Avenue de la Belle-Gabrielle, 94736 Nogent sur Marne Cedex, France
Summary
In France and throughout the world, charcoal-making equipment mainly
consists of partial combustion kilns with no provision for smoke
recovery.
Thus,
70% of the initial mass is discharged into the
atmosphere. This situation results in atmospheric pollution and poor
energy conversion yields.
At the request of the French Ministry of Environment, the CTFT
and the LNE undertook a study to characterize pyrolysis emissions, in
order to determine pollution resulting from charcoal-making. Initial
experiments showed that standard methods for emission sampling were
not appropriate for pyrolysis effluents. Accordingly, the LNE and the
CTFT jointly developed a system specifically designed for the
isokinetic sampling of a representative fraction of the emission. In
this method, gases and condensable compounds (pyroligneous matter and
tars) are separated for subsequent chromatographic analysis and their
relative proportions are quantified. The flow velocity is monitored
continuously in order to regulate the sampling flow.
BACKGROUND
The thermochemical reduction of wood to charcoal using a partial
combustion kiln produces a large amount of fumes in the immediate vicinity
of the kiln.
At present the French Ministry of the Environment is revising the
legislation on charcoal burning
(formerly classified as 104 in the
nomenclature of classified establishments) and is seeking to harmonize the
permitted discharge thresholds for each pollutant (or family of pollutants)
in various industrial processes.
There does not appear to be any European legislation as yet in this
field.
The equipment
for producing
charcoal mainly
comprises partial
combustion kilns which do not recover either the smoke or the other waste
products released during the pyrolysis of the wood, which are no longer used
since the advent of synthetic chemistry.
EFFECTS OF THE NEW REGULATIONS
The regulations lay down waste product thresholds for dusts and gases
(in effluents discharged into the atmosphere) and for liquid effluents. At
463
present it is impossible for all French production units to comply with
them.
The only known way of complying with these thresholds would be to
install incinerators for burning all the constituents of the smoke. However,
this solution has two disadvantages, viz :
its cost, which restricts it to installations above a certain size;
the need to know in advance some of the properties of the raw
effluents so as to determine the combustion chamber size.
Purification technology specific to this industrial sector must be
developed if the great majority of the existing plants in France are to
survive.
There have already been some interesting pilot projects, such as the
electrofilter with a water film.
However, if we are to develop new equipment and check its effectiveness we must acquire a perfect understanding of the metrological techniques
for the pollutants concerned.
JUSTIFICATION FOR THE WORK
In France, the measuring of waste by weight is clearly defined in two
standards (AFNOR X43-003 and X44-052) (1, 2 ) . There is a sampling apparatus
specific to each of these standards (see Figures 1 and 2 ) . They both work on
the principle of a heated filter medium located at the head of a suction
line, which is of known capacity and adjustable so as to maintain isokinetic
conditions during sampling.
These two items of apparatus were used for a series of on-site
measurements made during 1986 to quantify the effluents from charcoal
production. This project was the preliminary to a large-scale programme to
study the nature of the fumes.
Since no precise numerical data were
available at the time, the purpose of the project was to obtain information
prior to drawing up regulations and designing new processing systems.
The programme was carried out by a number of scientific bodies, the
most prominent being :
Centre Technique Forestier Tropical (CTFT)
Laboratoire National d'Essais (LNE)
Electricit de France (EDF)
Centre Interprofessionnel Technique d'Etudes de la Pollution
Atmosphrique (CITEPA)
Various papers were published as a result of this project (3, 4, 5 ) .
The tests comprised sequences of sampling and analysis during each of
the known phases of a carbonization cycle in a partial combustion kiln.
However,
difficulties were encountered in obtaining reproducible and
completely representative samples for each of the phases under observation.
A critical examination of the means and methods used produced the following
findings :
With regard to the kiln:
The fume output is of low velocity (2-3 m/s) , and there is a
substantial liquid discharge (water or pyroligneous liquid).
As a result, measuring the gas velocity with a Pitot tube and a
manometer unit generally produces figures which are too high or completely
incorrect, since the orifices for measuring the pressure become clogged.
464
With regard t o the sampling apparatus (Figures 1 and 2 ) :
1'
2'
3'
4'
5'
Probe
Cyclone
Filter
Finned cooler
Electric heating unit
9
Condenser
Dehydrator
Spirometer
Manometer
Flow regulation valve

Flow regulation unit
Counter (optional)
Thermometer
F i g . 1 . D iagram i l l u s t r a t i n g AFNOR X 43003 method
Diaphragm
|
Regulating
/ va lve
Fig. 2. Diagram illustrating A FNOR X 44052 method
Since the gas is transferred from the inside of the chimney to the
filter medium through a heated tube (a probe) with a nozzle at the open end,
it was noted that :
the heating is insufficient to convert the water into vapour before it
reaches the filter medium, so that it is filtered very quickly, the
sampling period being less than five minutes ;
465
this heating affects the products sampled and radically modifies their
proportions, producing cokfaction and deposition on the inner surface
of the probe;
the very nature of the sampling equipment prevents recovery of the
condensates, except with the first apparatus (see French standard
X43-003). However, as mentioned above, the figures for the material
recovered are too low and distorted.
With regard to the gas sampling line:
This was installed to process the gases from the kiln before they are
analysed by chromatography
(CPG) (4). The apparatus consisted of a
succession of condensers. It quickly became apparent that the quantity of
products to be processed required greater volumes and that the rapid cooling
of these gases (heavy tar-like hydrocarbons) quickly clogged the sampling
line and modified the measured outputs used for calculating the mass flows.
The findings from this series of preliminary tests are therefore of
two types :
we obtained a numerical evaluation of the main waste products
discharged into the atmosphere from partial combustion kilns;
we learned that it is essential to have sampling methods specific to
the effluents given off during wood pyrolysis.
DEFINITION OF THE PROJECT

To meet this need for a reliable metrologicai tool to quantify the
gaseous discharges from these carbonizing kilns, close collaboration was set
up between the CTFT and the LNE.
A project was drawn up on the basis of the observations made during
the preliminary tests to determine the main characteristics of the ideal
apparatus, and it is for the two laboratories to test the options as they
are selected.
This apparatus must :
sample a known volume of gas for a sufficiently long period to be
representative of the emissions from the kiln, which might be from 90
to 120 minutes;
separate the condensates from the rest of the gaseous fraction and
record their relative proportions in the effluents ;
guarantee isokinetic conditions during sampling;
make it possible to quantify the constituents of the condensates, tars
and other organic pollutants (6) .
In addition to operating this sampling line, it appears essential to
measure the velocity of the fumes, the relative humidity of the gases and,
if possible,
their composition,
to determine precisely the isokinetic
calibration.
Lastly, the analysis of the condensates must be based on the whole of
the sample, without losses due to difficulties in cleaning the equipment.
THE SAMPLING LINE
The preliminary tests quickly revealed the appropriate location for
each part of the line :
466
a sampling p r o b e , of small diameter and angled at the end, not heated
but insulated;
as small a transfer line as possible, also insulated;
a condensation u n i t ;
a flat filter maintained at a certain temperature,
with a porosity
compatible with the flow regulator;
a device for regulating the intake volume;
an airtight pump;
a dry gas counter.
The condensation
unit must be able to trap all the liquid and
particulate phase: water, organic pollutants (acids, methanol, furfurylic
compounds, phenolic compounds and t a r s ) .
Various contact elements such as
Raschig rings and glass spheres were not satisfactory (incomplete recovery
of the sample) and were abandoned in favour of vessels of the simple washer
type followed by sinteredplate vessels.
These collected all the tars. A n
electrostatic filter was also tried,
but although this process traps the
components satisfactorily,
it also alters them by oxidation,
and was
therefore not adopted.
The flat filter must trap material by filtering the gases after
condensation.
Its retention capacity must be high. Tests showed that 0.5U
was sufficient.
Its chemical composition should not affect the products
which pass through it. Glass fibre or PTFE are suitable.
If condensation is optimized, this filter becomes the indicator of the
efficiency of the upstream processes (in general the fraction recovered is
equivalent to 1 0 3 % of the condensate) .
It is simply maintained at a
temperature too high for residual condensation,
which might cause abnormal
clogging of the filter.
The purified gases are sampled in sequence downstream of the counter.
The pressure and temperature parameters are also recorded to correct the
volumes extracted.
The sampling line in its final form is represented diagrammatically in
Figure 3.
Temperature sensor
Filter
holder
/
I
F 1 x*
I
""i"
Gas
, Simpli no
Gas meter
Manometer
*pump
1"9
Compressed air
J
Chimney flow
measurement
Trap for condensed particles
Regulation for isokinetic sampling
F i g . 3 . Diagram i l l u s t r a t i n g the sampling l i n e for p y r o l y s i s emissions
467
This was validated in the course of several sessions of measuring the
emissions from a Magnientype partial combustion kiln with a capacity of
2 m3 (7) . The task was to improve the calculation of the energy and mass
balances by including losses due to waste discharged into the atmosphere.
The results obtained made it possible to verify the theoretical balance to
within 5%, which confirmed that the line was suitable for sampling and gave
reproducible results.
The velocities were measured using a pitot tube linked to a micromano
meter. A sequential declogging device was used to monitor these data almost
continuously and to deduce from them the kinetics of the flow.
Humidity is measured regularly by an ancillary condensation device. A
set of adjustable nozzles at the head of the probe are used to determine the
precise calibration for the offtake (isokinetic).
This calibration is
readjusted constantly during the sampling, which may continue for several
hours. It is preferable to carry out a series of samplings in order to
quantify the flows more accurately as pyrolysis proceeds.
CONCLUSION
This sampling line for wood pyrolysis emissions operated
the CTFT and the LNE can be used:
jointly by
to study the kinetics of the occurrence of pollutants as carbonization

proceeds ;
to determine the chemical properties of the pollutants emitted;
to quantify accurately the mass discharges from the pyrolysis plant
(during carbonization and roasting) and to deduce from these the
emission factors ;
to check the efficiency of the waste treatment systems.
So far a large number of measurements have been carried out on site
and confirm the suitability of the layout we have adopted.
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Norme
Franaise
Homologue
43003
Methode
de
dtermination
ponderale des particules solides entranes par les gaz de combustion.
Norme Franaise Homologue X 44052 Prlvement de poussire dans
une veine gazeuse.
CITEP
A monographie:
Carbonisation du bois et pollution atmosphrique
1986.
MEYER, C.
Determination
des
rejets
atmosphriques
lors
de
la
carbonisation partielle. Mmoire de fin d'tudes. CTFT 1986.
GIR
A RD, P.,
MEYER, C , FONTELLE, J. P. and BOILLOT, M. Caractrisation
des missions de carbonisation en four combustion partielle. Mise au
point de systimes de traitement des fumes de carbonisation.
4me
Conference Europenne 1115 May 1987, Orlans.
VILLENEUVE, F.
and VERGNET, A .M.
Techniques analytiques applicables
aux liquides at aux gaz de pyrolyse de la biomasse tropicale. Bois et
Foret de Tropiques, cahier scientifique no 9 1988.
SH
A H, N., GIRA RD, P.,
MEZERETTE, C.
and VERGNET, A .M.
Engineering
performance evaluation to characterise
metal charcoal
kiln,
for
optimisation of wood energy conversion.
5th European Conference:
"Biomass for Energy and Industry", 913 October 1989, Lisbon.
468
FURNACE FOR BIOFUKLS THERMAL UTILIZATION
W.BLASIAK,.ZETHRAEUS,R.COLLIN
Royal Institute of Technology
Department of Heat and Furnace Technology
S-10044 Stockholm, Sweden
W.GAJEWSKI,J.ZAJDEL
Technical University of Czestochowa
Institute of Heat Machinery
42-200 Czestochowa, Poland
Summary
The work presents a new type of wood wastes incinerator.
Incinerator can be used to utilize different kinds of wood
wastes
which
might
be
contaminated
by
pieces
of
noncombustable wastes like bricks, stones or metallic
parts. Low quality non-uniform wood wastes can be burnt in
the
incinerator
without
any
previous
separation,
segregation or cleaning process. The incinerator prototype
as a typical combustor was investigated using a sectional
hot water boiler as a waste heat boiler.
1. INTRODUCTION
Two of the applicable utilization methods for wood wastes
are combustion or gasification. However, simultaneously the
heat from the combustion process must be used in the
existing factory heating system. In case of wood wastes and
if we can not expect very efficient preprocessing systems
(as is normally the case
in small factories) the
combustion process is difficult to run mainly due to
different wastes structure, big water content depending on
the season, and due to big contents of non combustible
waste like sand, stones, bricks, metallic parts and so on.
Taking into account these circumstances and the fact that
the waste composition changes within a very wide range even
during one day it is obvious that any kind of incierator
will have to work in very difficult conditions from the
point of view of the combustion process stability.
2. DESIGN OF THE COMBUSTOR
The combustor, shown in Fig 1, consists of a vertical
cylindrical combustion chamber (1), a conical ash chamber
(2), a chamber for initial drying of wastes (3), a flue gas
offtake (4) and an external recirculation channel for the
hot flue gas (5). Raw wastes are fed gravitationally by
means of a standpipe (6) into the initial-drying chamber
and finally into the combustion chamber. Air is supplied as
primary air, secondary air and complementai air.
469
Primary air is tangentially supplied into the upper part of
the combustion chamber. Secondary air is supplied by a
suitably shaped channel into the upper part of the drying
chamber, being simultaneously the driving force for the
swirl in the waste entry. Complementai air can be supplied
into the ash chamber in order to burn off the coarse
fraction of wastes. To ensure a correct
pressure
distribution
inside
the combustor, guaranteeing
the
possibility of gravitational feeding, it is very important
to keep proper velocities and air flow ratios for given
geometrical dimensions of the combustor. Especially it is
necessary to avoid overpressure near the standpipe inlet.
The simple design of the combustor gives possibility to
apply a simple gravitational feeding system which is also
its main advantage. Wastes supplied through the standpipe
(6) undergo a process of segregation i.e, the fines are set
in rotational motion and the rest of them falls down. The
wastes are dried, degasified and partly burnt up during the
time of falling down. The fines are burnt up mainly inside
the drying and combustion chamber during their more or less
rotational motion, while the coarse wastes are burnt up in
a fixed bed on the distributor (11) inside the ash chamber.
In the latter case oxygen supply is both by secondary air
and by complementai air which infiltrates through the fixed
bed. In case of an even more simplified design of the
combustor the ash chamber can be eguipped with an ash door
(10) which can be used for ash removal and for adjusting
the amount of air sucked into the ash chamber. In case of
high moisture content of the wastes recirculation of flue
gas by means of the secondary air flow is realized. Flue
gas is ejected by the jet of secondary air (8) flowing
freely through the flue gas channel (4). This kind of
design in principle works as a jet pump. The amount of flue
gas recirculated in this manner can be adjusted by changing
the secondary air nozzle (8) position. To utilize the heat
of wastes combustion the combustor was connected to the
internal heating system of a small sawmill factory. The new
combustor is combined with the existing boiler so as to
maintain the same total performance of the whole heating
system as before the new combustor installation, using
simultaneously much less of the basic fuel.
3. WASTES PROPERTIES
Typical properties of the wastes (sawdust, chips of
pinewood and sprucewood) utilized in the small industrial
scale prototype of the combustor are presented below:
Chemical constitution of the dry substance: C=0.5,
H=0.96, 0=0.439, N=0.001;
- Moisture content: W=0.2-0.5;
Ash content: A=0.01;
Net calorific value: Qw=(7.4-13.4) GJ/kg;
- Bulk density gw=(150-180) kg/m3
Total content of volatiles 0.75-0.8.
470
4. PROTOTYPE INSTALLATION OF THE COMBUSTOR IN THE HEATING
SYSTEM.
The hot water boiler was used as a waste heat boiler
utilizing the heat in the gases coming out of the
combustor. The flue gas was led from the exhaust of the
combustor via ducting into the boilers chamber. To achieve
the neccessary heat output in order to maintain the boiler
rating the changes in combustion orgainzation and in the
heat transfer processes had to be considered. The hot water
boiler was characterized by the following parameters; type
of boiler - hand firing sectional hot water boiler,
calorific throughput - 0.3 MW, heating surface -32 m 2 ,
water pressure - 0.5 MPa, water temperature in the outlet
and inlet respectively 95C and 70C, outlet flue gas
temperature - 200C, thermal efficiency of the boiler, 0.79, kind of basic fuel - coke (net calorific value - 29
GJ/kg), fuel consumption - 47 kg/h. Calculated total flow
of flue gas was 570 nm3/h (excess air factor 1.5). On the
basis of the chemical composition of the wastes the amount
of air and flue gas for the same value of excess air factor
were determined as respectively 4.7 nm3/kg and 5.6 nm3/kg.
air I
MS^h
Fia 1 : Scheme of the combustor
471
Taking into account heat losses due to radiation (sr=0.2)
and due to incomplete combustion (sn=0.05) the temperatue
of the wastes combustion was found using the relation
between the flue gs enthalpy (Jfg) and temperature. The
calculated values of the adiabatic waste combustion
temperatures, t c w are presented in table 1 :
Table 1
(excess air)
1.3
1.5
2.0
2.5
Jfg
8757
8773
8812
8857
1130
1000
800
700
[kJ/kg]
t c w [c]
Assuming that the flue gas is cooled to the outlet

temperature 200C and the total thermal throughput of the
boiler Qj_, will be kept up as well, the wastes consumption
B w was calculated and presented in table 2, where a is the
ratio between flows of flue gas for wastes and coke.
Table 2
1.3
1.5
2.0
2.5
Qb [MW]
0.3
0.3
0.3
0.3
146
149
158
166
727
836
1140
1466
2.1
2.4
3.5
5.1
[kg/h]
Vwfg
a2
[nm 3 /h]
As shown by a 2 in table 2, a retrofit to 100% waste firing

would dramatically increase the pressure drops and flue gas
volumes. To avoid a change of draft fan in the flue gas
system, the boiler was therefore cofired with a coke
supply of (1517) kg/h (previously 47 kg/h) and the
remainder of the fuel input supplied by wastes.
5. RESULTS OF COMBUSTOR PROTOTYPE RUNNING
According to the calculations it is possible to run the
combustor together with the hot water boiler only if the
combustion in the boiler is run by means of coke (1020
kg/h). In this situation using quite dry wood wastes
w=0.25 (experiments were carried out during summer) it is
possilbe to achive the rated output of the boiler. If there
is no coke combustion in the boiler the temperature is too
low for the combustion of fines transported by flue gas
from the wood wastes combustor. Running parameters of the
combustor during experiments are presented in table 3.
472
Table 3
Amount of wood wastes
96 kg/h
Temp, of flue gas in the outlet of the combustor
1000C
Excess air number
1.5
Air flow (total)
( 4.7-5)nm3/kg
Flue gas flow from the combustor
5.7 nm3/kg
Net calorific value of wood wastes
10.5 GJ/kg
Moisture content
25 %
Amount of coke
(10-20) kg/h
Because of the higher flue gas flow some troubles with a
slight overpressure inside the boiler were noticed. This
was due to the too small capacity of the draft fan which
was running under maximal performance. It is necessary to
stress that no changes were done in the existing system.
Also some fluctuations inside the combustor occurred
especially during startup. After some time the heat
accumulated in the combustor walls and mass of wastes
accumulated inside the ash chamber protected very
sufficiently the stability of the combustion process.
473
INVESTIGATIONS OF TOXIC COMPONENTS IN PRODUCTS FROM
SEWAGE SLUDGE PYROLYSIS
MUNICIPAL WASTE
DIPL. CHEM. H. ROSSLER, DR U. PROSCH, PROF.DR W. KAMINSKY
Universitt Hamburg
Institut Fur Technische und Makromolekulare Chemie
D-2000 Hamburg 13, Bundestrasse 45, Federal Republic of Germany
1. Summary
An increasing amount of municipal waste and sewage sludge has led to
new efforts in waste removal management since appropriate recycling
technologies are not available on an industrial scale at the moment.
The pyrolysis process developed in Hamburg,
using a fluidized bed
reactor, achieves the conversion of organic waste material into gas,
oil and solids. The fluidized bed reactor with a capacity of 20 to
50 kg/h is indirectly heated by four radiation tubes. The pyrolysis
gas is partly condensated in packed columns; the remaining part is
used for fluidizing the quartz sand bed. The excess gas leaves the
plant continuously and is burnt in a torch.
The content of toxic
components such as PCBs, PCDDs, PCDFs and heavy metals in pyrolysis
products determine the suitability of the process and utilization of
the pyrolysis products. Our investigations concentrate on the analysis
of pyrolysis oils in relation to the highly toxic components such as
PCBs, PCDDs and PCDFs, as well as the analysis of solid products
relating to heavy metals.
2. PYROLYSIS OF MUNICIPAL WASTE

2.1
Characterization of Educt and Material Balances
The source of the material used is an urban collection of municipal

waste in Hamburg-Bergedorf. Table 1 shows the composition of the plastic
waste in relation to several classes of plastic; Table 2 elucidates the
elementary composition.
TABLE 1. (in weiight '
Polyolefines
Polystyrene
PVC
Other plastics
Inorganic residues
Water
TABLE 2. (in weight '

57
19
13.7
4.8
5.3
0.2
%
%
%
%
%
%
Carbon
Hydrogen
Chlorine
Nitrogen
Other elements
79..1
11
7..8
0..5
1..6
%
%
%
%
%
The high content of PVC respectively chlorine is obvious. Therefore we

expected the formation of chlorinated organic compounds. We carried out
three pyrolysis experiments altogether at temperatures of 690C, 735C and
790C. Table 3 shows the material balances of the experiments performed.
474
TABLE 3. Pyrolysis products (in weight %)
Temperature
680C
735C
790C
Hydrogen
0.195
0.318
0.703
Methane
4.895
10.563
17.496
Ethene
5.378
9.644
9.782
Ethane
2.96
3.351
2.992
Propene
4.058
3.648
1.324
1,3-Butadiene
0.79
0.949
0.442
Alicycles
3.271
2.797
0.55
Other aliphates < C6
4.794
1.886
0.334
Other aliphates > C7
6.557
0.015
0.006
Benzene
3.274
7.933
13.783
Toluene
1.818
3.244
5.555
Styrene
5.278
6.047
3.105
Other Alkylbenzenes
1.046
2.969
-4.283
Indane
0.178
0.221
0.144
Indene, Methylindenes
0.713
1.274
1.342
1.372
3.836
Naphthalene
0.381
Alkylnaphthalenes
0.188
0.672
0.899
Biphenyl, Alkylbiphenyl
0.238
0.284
0.575
Anthracen, Phenanthren
0.4
0.658
Other aromatic compounds
0.123
0.82
2.24
17.403
10.357
11.152
4.159
5.583
6.435
Tars
Carbon black
Carbon monoxide
2.45
6.589
2.377
Carbon dioxide
5.973
9.699
1.273
Water
2.5
4.0
2.647
HCl
7.98
7.98
7.98
Other components
2.516
1.202
1.53
Inorganic ash
5.27
Products from Dolomit
-5.8
Sedimentation, loss
11.414
5.27
-14.6
5.497
5.27
-1.2
1.106
Sum
100
100
100
Mass of pyrolysed waste
165.6 kg
135.15 kg
130 kg
475
2.2
Analysis of Toxic Compounds
In spite of the high percentage of PVC respectively chlorine, the

concentrations determined are below the detection limit, at least within
permissible limiting values. Table 4 shows a prospect of PCDD, PCDF and PCB
concentrations in high boiling pyrolysis oils (values in p g A g ) In low
boiling oils PCDD, PCDF and PCB are not detectable.
TABLE 4. PCDD, PCDF and PCB concentrations in high boiling pyrolysis oils
(values in yg/kg) ; (n.d. = not detectable)
Temperature
Sum TCDD
2,3,7,8, TCDD
Sum PeCDD
1,2,3,7,8 PeCDD
Sum HxCDD
1,2,3,6,7,,8 HxCDD
1,2,3,7,8,,9 HxCDD
1,2,3,4,7,,8 HxCDD
Sum HpCDD
OCDD
Sum TCDF
2,3,7, 8 TCDF
Sum PeCDF
2,3,4, 7 ,8 PeCDF
Sum HxCDF
1,2,3,6 ,7,8 HxCDF
Sum HpCDF
PCB according DIN 51527
680C
735C
790C
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
2.1
1.7
16.9
0.38
13.7
0.39
3.2
0.3
5.3
1500
n.d.
n.d.
n.d.
n.d.
n.d.
4.5
n.d.
1.5
n.d.
n.d.
n.d.
n.d.
<1000
n.d.
n.d.
n.d.
n.d.
n.d.
14.1
n.d.
4.6
0.2
0.4
n.d.
n.d.
162
The distribution of heavy metals in pyrolysis products demonstrates

the abundance of heavy metals in solid products. The investigations were
carried out by atomic absorption spectroscopy.
TABLE 5. Distribution of environmental heavy metals

(% f.s. = % of whole feedstock)
Temperature
mg/kg
680C
% f.s.
mg/kg
735 C
% f.s.
790CC
mg/kg % f.s.
Distribution of lead
Reactor residual
Cyclone solids
Slurry fraction
High boiling oils
Water
Organic distillates
Feedstock :
Municipal waste
Quartz sand
Added substance
547
779
485
10
0.9
0.2
407
0.5
2.7
202
113.4
20.1 1000
8.5
537
0.8
23.1
0.003
0.2
0.05
0.2
99.7
0.12
0.18
407
0.5
2.7
49.8
163
25.2
805
15.7
19
1.4
42
0.001
0.3
0.06
-
52.8
18.5
0.3
2.8
0.001
99.64
0.13
0.24
99.84
0.16
407
0.5
476
TABLE 5. (Contd.)
Temperature
mg/kg
680 C
% f.s.
mg/kg
4.4
117
210
10
0.3
0.05
4.2
13.9
16.8
1.1
0.01
0.05
0.4
49
220
10
0.14
0.15
89
0.02
0.9
99.75
0.02
0.23
89
0.02
0.9
735C
% f.s.
790 C
mg/kg % f.s.
Distribution of cadmium
Reactor residual
Cyclone solids
Slurry fraction
High boiling oils
Water
Organic distillates
Feedstock :
Municipal waste
Quartz sand
Added substance
0.5
5.6
29.4
2.7
0.002
0.2
0.3
54
73.9
29.1
0.08
99.63
0.03
0.35
89
0.02
0.4
5.7
4.8
8.8
0.00
99.97
0.03
3. PYROLYSIS OF SEWAGE SLUDGE

We carried out three experiments in pyrolysis of sewage sludge at
temperatures of 620C, 690C and 750C in our miniplant. The percentage of
chlorinated biphenyls in the feedstock according to Ballschmitter (2) is
demonstrated in Table 6.
TABLE 6. Polychlorinated biphenyls in sewage sludge

PCB Isomer
28
52
101
138
153
180
mg/kg
0.07
0.04
0.06
0.08
0.09
0.04
Table 7 shows the percentage of polychlorinated biphenyls in the high

boiling pyrolysis oil of the experiment at 690C.
TABLE 7. Polychlorinated biphenyls in pyrolysis oil
Isomer (detection limit 0..05 m g A g )
mg/kg
Trichlorbiphenyl
Tetrachlorbiphenyl
Pentachlorbiphenyl
Hexachlorbiphenyl
Heptachlorbiphenyl
Oktachlorbiphenyl
Nonachlorbiphenyl
0.292
0.331
0.447
0.317
0.097
n.d.
n.d.
477
93.5%
OO"
75.
Pb
4J
Id
50-
o
254.4%
0.4%
Charge
Residue
Soot
Oil
Fig. 1. Distribution of lead in sewage sludge pyrolysis

Pyrolysis temperature: 690C
478
Table 8 illustrates the contents of PCDD and PCDF in sewage sludge feedstock
and in high boiling oils in the 690C and 750C experiments.
TABLE 8. PCDD and PCDF in high boiling pyrolysis oils
(values in yg/kg)
Components
Feedstock
690C
750C
Sum TCDD
2,3,7,8 TCDD
0.03
n.d.
8.75
0.88
8.16
0.67
Sum PeCDD
1,2,3,7,8 PeCDD
0.15
n.d.
31.50
4.16
33.40
3.50
Sum HxCDD
1,2,3,6,7,8 HxCDD
1,2,3,6,7,8 HxCDD
1,2,3,4,7,8 HxCDD
1.64
n.d.
0.17
0.005
23.14
0.54
2.92
2.10
13.2
0.46
1.82
1.37
3.4
1.8
0.4
5.5
3.0
2.7
Sum HpCDD
1,2,3,4,6,7,8 HpCDD
OCDD
3.2
1.6
15.5
Sum TCDF
2,3,7,8/2,3,6,8 TCDF
0.122
0.02
2.58
0.26
2.72
0.27
Sum PeCDF
1,2,3,7,8/1,2,3,4,8 PeCDF
2,3,4,7,8 PcDF
0.166
0.012
0.10
2.38
0.14
0.10
2.16
0.24
0.12
Sum HxCDD
1,2,3,4,7,8/1,2,3,4,7,9
1,2,3,6,7,8 HxCDF
2,3,4,6,7,8 HxCDF
1,2,3,7,8,9 HxCDF
0.231
0.01
0.01
0.01
n.d.
0.40
0.04
0.06
n.d.
n.d.
0.58
0.06
0.05
n.d.
n.d.
Sum HpCDF
1,2,3,4,6,7,8 HpCDF
1,2,3,6,7,8,9 HpCDF
OCDF
0.7
n.d.
0.4
1.0
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
The distribution of heavy metals is analagous to the distribution of

municipal waste pyrolysis. Figure 1 illustrates the distribution of lead.
REFERENCES
(1)
(2)
U. PROSCH, doctoral thesis, University of Hamburg, 1988.

A. KUMMER, doctoral thesis, University of Hamburg, 1989.
479
RESEARCH ON TAR CRACKING AND APPLICATION OF TAR.

G. Olsen
Laboratory for Energetics

Technical University of Denmark
SUMMARY
Straw has been pyrolysed at 600C in a continous reactor
with s feed rate of 3 kg/h. The tar produced has been fed
through an empty reactor of varying size and temperature
and finally the gas was led through four washing bottles
where the condensate was accumulated.
The tar fraction
with boiling point between 100C and 200C was separated by
distillation and the amount, heat of combustion and
viscosity were analysed.
The tar fraction with boiling
point 100C - 200C as well as the total amount of condensate is reduced by increased cracking temperature and the
residue turns from sticky tar to powderish carbon black.
The gas volume increases with increasing temperature and
increasing residence time.
The gas composition is only
dependent on the cracking temperature.
BACKGROUND
Pyrolysing biomass produces incinerable gas, char and tar
in various amounts according to the pyrolysing conditions.
The char can be gasified and the tar cracked thermally or
cataly-tically into gas and carbon .black, leaving ashes as a
residue.
Instead of converting the biomass energy only
into incinerable gas by this procedure, the possibility of
producing liquid fuels is of great interest, as these fuels
have a wider range of applications and are easier to store
and distribute.
As a part of the biomass gasification research programme
at the Laboratory for Energetics, the possibility of
producing applicable tar by pyrolysing straw has been
investigated. The tar has been compared to diesel oil, as
it was meant to mainly substitute this fuel in internal
combustion engines if possible.
480
EXPERIMENTS
The experiments were performed to give information about
the amount and quality of tar according to cracking
temperature and residence time. The tar was produced by
pyrolysing straw at 600 C, 1 atm in a continuous reactor
with a feeding rate of 3 kg straw/h. The gas and tar were
fed through an empty reactor of varying size and tempera
ture and finally washed in acetone in four successive
washing bottles.
The system was dismantled between each
experiment in order to measure the amount of char produ
ced. The secondary reactors had the volumes of 1.5 1 or 10
1 and the temperature of the same reactors was set to 600,
800, 900, 1000 and 1100 C.
Condenser
Second reactor
Feec ing of
==H ' '"
Piston
sti*aw
1
V
is
_^_^
t
Pyrolysis
reactor
Four gas washing
bottles in series
Collection of char
Figure 1: Test equipment.

From the beginning it was quite clear that untreated tar
was not well suited as fuel for internal combustion
engines.
For this reason the condensate dissolved in
acetone was distilled at 1 atm and the fractions with
boiling point from 100200C were separated and weighed, as
was the residue.
Initially it has not been necessary to
know the composition of the distillates, whereas the heat
of combustion and the viscosity of the distillates were
more relevant and these analyses were therefore performed.
The gas volume as well as the gas composition was
measured for each experiment and the heat of combustion has
been calculated for the gas.
The part of the experiments in which the tar was produced
and collected lasted approximately 2 hours and in this
period no problems concerning the experimental equipment
were observed.
The condenser installed prior to the
washing bottles was cleaned between each experiment. A t
low temperatures of the secondary reactor, adhesive tar
condensed and started to close the condenser.
When the
481
temperature was increased to 800C and 900C, soot started
to build up in the upper part of the condenser, whereas the
condenser was clean at the very high temperatures.
The losses are found as condensed tar in the char
collector and tar leaving the washing bottles. The water
and water
soluble tar as well as the possible acetone
produced were not measured.
The colour of the condensate dissolved in acetone in the
washing bottles, turned from brown to black when the
temperature was increased. A t 1100C the condensate
consisted of carbon black and a colourless, transparent
liquid.
RESULTS
The amount of total condensate collected in the washing
bottles is reduced when the temperature of the second
reactor is increased as seen in Figure 2. It is remarkable
that the total amount of condensate does not exceed 6% of
the inserted straw.
Volume of second r e a c t o r : 1.5 1

i (g/kg straw)
50
Total condensate
3
20
10 -
H^-f
600
70O
8O0
900 1000
(C) Temp.
1100
Figure 2a: Distillates and residual versus temperature.
482
Volume of second reactor: lo 1
(g/kg straw)
60
Total condensate
( c) Temp.
O
6O0
700
800
900
1000
1100
Figure 2b: Distillates and residual versus temperature.

Accordingly, the gas volume increases when the tempera
ture of the second reactor is increased (Figure 3) . The
heat of combustion of the gas has its maximum at 800900C
because of the high content of CH 4 and C2H2/C2H4 (Figure 4
and 5 ) .
(1 g a s / k g straw)
700
Volume of
second reactor: 10 1
600
500
400
Volume of
second r e a c t o r : 1.5 1
300
200
No second r e a c t o r
100
( C) Temp.
k
O
600
700
Figure 3: Gas
800
900
VOLUME
lOOO llOO
versus tempersture.
483
Vol.*
Volume of second r e a c t o r : 1 . 5 1
30
2010
++-T
600
Vol.%
700
800
900
lOOO
CO
CO.
1100
Volume of second reactor: 10 1
40
2H2/C2H4
2H6
30
20
4-4-5
600
( C) Temp.
700 800
900 looo lieo
Figure 4: Ga s composition.
A t 6 0 0 , 800 and 900C t h e reactor t e m p e r a t u r e and t h e g a s
t e m p e r a t u r e w e r e t h e same for b o t h t h e 1.5 1 a n d t h e 10 1
second r e a c t o r .
N o difference in g a s c o m p o s i t i o n w a s
observed a t t h e s e e x p e r i m e n t s . T h e reactor t e m p e r a t u r e and
the g a s t e m p e r a t u r e w e r e t h e same for t h e 10 1 second
r e a c t o r , 1000 and 1100C e x p e r i m e n t s .
I n t h e 1.5 1 second
r e a c t o r , t h e g a s t e m p e r a t u r e showed a fall of a p p r o x i m a t e l y
50C at t h e v e r y h i g h t e m p e r a t u r e s ; 1000 a n d 1 1 0 0 C .
This
indicates t h a t t h e v o l u m e of t h e reator is n o t b i g e n o u g h
for t h e g a s t o reach t h i s t e m p e r a t u r e . T h e g a s c o m p o s i t i o n
in t h e 1.5 1 reactor w a s different from t h a t of t h e 10 1
484
reactor.
These observations
ference in temperatures.
are
explained
by
the
dif
(MJ/Nm )
20
18
16
Volume of second reactor: 10 1
14 .
No second reactor
12 .
Volume of second reactor: 1.5 1
o^r
O
6O0
700
800
900
1000
_^
Temp.
1100
Figure 5: Heat of combustion of gas.

The heat of combustion of the distillates is remarkably
high for all samples except for the experiment without
prolonged residence time (Figure 6 ) . The expected heat of
combustion was appr. 22 MJ/kg.
This is partially due to
the amount of acetone still remaining in the distillates,
but as acetone has a heating value of 28.5 MJ/kg, it can
not explain the values of 33 37 MJ/kg. The thermal
cracking and extended residence time must therefore convert
the pyrolysis tar to tar with higher heating value.
(MJ/kg)
Volume of second
reactor: 10 1
40
Volume of second
reactor: 1.5 1
30
20
No second reactor
IO
+r
6O0
Figure 6:
700
1
800
1
900
OOO
( C) Temp.
1100
Heat of combustion of distillates.
485
The viscosity was measured for five samples of distil
lates.
No second reactor.
Sample no.
Second reactor 1.5 1, 600C.
Sample no.
Second reactor 10 1, 600C.
Sample no.
Second reactor 1.5 1, 1000C.
Sample no.
Diesel oil.
Sample no.
The amount of acetone remaining in the samples after
distillation was measured by gaschromatography.
Sample no.
1
2
3
4
5
centistoke
4.890
3.267
2.453
4.056
3.049
g acetone/1 sample
3.5
74.2
116
60.4
Obviously, the acetone is very difficult to separate com

pletely from the tar by distillation. It does not neces
sarily give any problems with small amounts of acetone in
the distillates, but there will be a loss of acetone in the
system.
CONCLUSION
The tar distillates obtained by this series of experi
ments represents up to 3% of the energy introduced with the
straw. The efforts made to collect the tar and to separate
the tar fractions by distillation, indicate that producing
liquid fuels from straw is not profitable.
However the experiments showed that thermal cracking at
1100C can convert tar to gas and carbon black and because
of the latter, the gas is not perfectly clean even at this
temperature. Before introducing the gas to a gas engine it
has still to be cleaned.
The residence time, which was 67 sec. in the experiments
including the 1.5 1 second reactor and approximately 35
sec. in the experiments with the 10 1 volume second
reactor, seems only to have influence on the gas volume
produced. The reduction in total condensate is to small to
measure. The difference in gas composition and total
condensate accumulated in the experiments with 1000 and
1100C 2nd reactor temperature, is due to a difference in
gas temperature in these experiments.
The 1.5 1 second
reactor was not big enough for the gas to reach the reactor
temperature, whereas the 10 1 second reactor has a suffi
cient volume for the gas to reach the applied temperature.
486
THE FUEL PROPERTIES OF HYDROCARBON LIQUIDS

DERIVED FROM PYROLYSIS OF WASTE
PAUL T. WILLIAMS AND DAVID T. TAYLOR
Department of Fuel and Energy
The University of Leeds, Leeds, LS2 9JT (UK)
Summary
Pelletised municipal waste (RDF), wood, rubber tyre and crop waste was
pyrolysed at 500 C in a 200 cc static batch reactor in the presence of
nitrogen.
The derived hydrocarbon liquids were condensed in a cold
trap, dried and analysed for their properties as fuels in comparison
with crude petroleum oil. The properties of the derived oils varied
depending on the original waste material. Rubber tyre waste produced
a low viscosity oil with a CV of 42.0 MJ/kg, the oils derived from
wood, crop and RDF were viscous liquids with CVs of 21.1, 27.3, and
22.1 MJ/kg respectively.
Sulphur contents were lower compared to a
medium petroleum fuel oil.
FTIR was used for functional group
characterisation and showed the samples were complex with carboxylic
acids, alcohols, alkanes, alkenes, phenols, aromatic and polyaromatic,
ketones and aldehydes being identified. Molecular weight ranges of
the oils by SEC showed a range similar to petroleum oil and a shift to
higher
molecular
weights
was
observed on storage indicating
polymerisation. Simulated distillation of the lower boiling point
range of the oils by pyroprobe gas chromatography showed that similar
ranges to petroleum oil were found for the wood and RDF, whilst rubber
and crop oil had higher ranges.
INTRODUCTION
The main routes investigated for energy recovery from waste have so
far centered on heat recovery from incineration (1,2), gasification (3,4),
gas production from landfill sites (5,6) and pelletisation for substitute
solid fuel (7,8). However the production of liquid hydrocarbons from waste
material and their properties as fuels has received less attention. The
production of liquid fuels from waste has advantages over other forms of
energy from waste recovery systems, in that since the fuel is liquid it may
be stored and transported and hence the fuel product does not have to be
used at or near the recycling plant. The derived oils may be upgraded to
refined fuel or added to petroleum refinery feedstocks. Also the products
may be important for their use as refined chemicals, high concentrations of
potentially valuable chemical feedstocks such as benzene, toluene and
naphthalene (9) may make the economics of pyrolysis of waste a more
attractive proposition.
487
2. MATERIALS AND METHODS
The waste material pyrolysed, consisted of pelletised municipal waste
(RDF) from Eastbourne, Sussex UK, the wood waste was pine chips, the crop
waste was straw and the rubber tyre waste represented a mixture of heavy
and light duty automotive types, all metal core was removed prior to
pyrolysis.
The pyrolytic apparatus consisted of a 200 cc stainless steel reactor
heated by an electric ring furnace with nitrogen as the carrier gas.
The
waste was placed in the reactor and heated to 500 C at S C/min and held at
500 C until no significant release of gas was observed. The evolved gases
were analysed off line by packed column gas chromatography, the results of
which will be reported elsewhere. The hydrocarbon liquids were condensed
in a glass liner within an ice trap connected to the reactor. The liquids
were separated into an aqueous and oil phase by decanting, then stored in a
dessicator over silica gel for several weeks until the samples were dry.
The CV and sulphur content of the raw waste and derived oils were
determined by bomb calorimetry. Functional group, compositional analysis
was performed using Fourier Transform InfraRed (FTIR) spectroscopy with a
Perkin Elmer 1750 system.
The molecular weight range of the oils was
determined using size exclusion chromatography (SEC), the column used was a
Polymer Laboratories PL Gel 10/im, 500, 600mm 7.5mm with tetrahydrofuran
as the mobile phase, the system was calibrated with polystyrene standards.
The simulated distillation (10) was carried out using a modified method
incorporating pyroprobe gas chromatography (PGC). The derived oils are of
high viscosity and contain a high molecular weight fraction and thus are
difficult
to analyse by gas chromatography.
PGC at 500 C causes
volatilisation without decomposition of the lower boiling point fraction of
the oil, whilst the higher end is retained in the quartz sample tube within
the pyroprobe. The system used was a Perkin Elmer 8320 capillary GC
coupled to a CDS Pyroprobe 190.
Table I shows the gross CV and sulphur contents for the waste material
and the dried derived pyrolytic oil. Rubber tyre oil was of low viscosity
with a CV of 42.0 MJ/kg, comparable to medium fuel oil and lower sulphur
content.
Similar CVs for oil from tyre waste have been reported (11,12)
but higher reported sulphur levels of between 1.01 and 1.65% (11) and 0.75%
(12). Wood waste gave an oil with a CV of 21.1 MJ/kg and <0.1% sulphur,
this value compares with literature values of 22.2 MJ/kg and 0.11% sulphur
(13) and 28.5 M J Ag and 0.1% sulphur (14). The RDF gave a CV of 22.1 M J A g
and <0.1% sulphur which compares with municipal solid waste pyrolysis oil
with a CV of 26.5 MJ/kg and sulphur 0.10.3% (15) and RDF pyrolysis oil
associated with an aqueous phase with a CV of 18.9 MJ/kg and 0.1% sulphur
(16).
Wood, crop and RDF derived oils were more viscous than the rubber
tyre derived oil, the CV were suitable for the direct use of these oils as
low grade fuels with the advantage of low sulphur content when compared to
a medium fuel oil with a CV of 43.0 MJ/kg and up to 2.5% sulphur.
FTIR absorbance frequency spectra representing functional group,
compositional analysis of the waste derived oils compared to crude
petroleum oil from the North Sea Brent field are shown in figure 1.
The
presence of the C stretching vibrations between 2800 and 3000 cm1 and
C deformation vibrations between 1350 and 1475 cm1 indicate the presence
of alkanes. These appear clearly in the petroleum oil which is known to
contain alkanes and also in all the waste derived oils, the absorbance
between 2800 and 3000 cm1 is clearly shown although the 1350 to 1475 cm1
is less distinguishable for the wood and RDF oils. The presence of alkanes
488
Petroleum
4000
3000
2000
1600
1200
600
Frequency cm_1
Figure 1. FTIR spectra of pyrolytic oils.
Table I : CV and Sulphur of Waste Material and Derived Pyrolytic Oil.
MATERIAL
Rubber Tyre
Crop
Wood
RDF
RAW WASTE
DERIVED OIL
CV
CV
(%)
(MJAg)
(MJAg)
(%)
39.8
15.5
18.4
21.0
1.3
0.1
0.1
0.2
42.0
27.3
21.1
22.1
0.2
0.1
<0.1
<0.1
in wood and rubber tyre waste derived oils has been demonstrated in the
literature (9,16,17).
Single and polycyclic and substituted aromatic
groups are indicated by the absorption peaks between 675 and 900 cm-1 which
are present throughout all the samples but to a greater extent in the
rubber tyre and crop waste pyrolytic oils.
Phenols, and 2 to 4 ring
polycyclic aromatic hydrocarbons (PAH) have been identified in wood derived
oil (16,17).
Benzene, toluene and 2 to 4 ring PAH together with alkyl
489
- Crop
Wood
Tyre
RDF
RDF (Fresh)
Petroleum
3000
Mass
3000
Mass
Figure 2. Molecular weight histograms of pyrolytic oils.
derivatives have been identified in rubber tyre waste oil (9,18).

The
presence of O- vibrations between 3050 and 3600 cm-1 together with the
presence of C=0 stretching vibrations between 1650 and 1850 cm-1 indicates
the presence of carboxylic acids. These are most significant in the oils
derived from wastes containing a high proportion of cellulose
and
hemicellulose, i.e. the wood and the RDF which may contain up to 85% paper
(16). Carboxylic acids are also indicated, but to a lesser extent in the
crop and rubber pyrolytic oils. Carboxylic acids in wood derived oil have
been identified in the form of formic, acetic, propionic, and butyric acids
(16,17,19). The presence of the C=0 stretching vibrations with absorbance
between 1650 and 1850 cm-1 may also indicate the presence of ketones and
aldehydes since aldehydes have been identified in pyrolytic oil from wood
(16,19) and ketones from RDF (16). The absorbance peak between 1575 and
1650 cm-1 represents C=C stretching vibrations indicative of alkenes and
are represented in all the samples. A lkenes have been identified in oil
from wood (19) and municipal waste (15). The group of overlapping peaks
between 950 and 1325 cm-1 most promonent in the wood and RDF samples most
probably represent the presence of primary, secondary and tertiary alcohols
and also phenols due to the C-0 stretching and O- in-plane deformations of
these functional groups. A lcohols and phenols have been identified in wood
(16,19) and RDF (16) derived oils.
Figure 2 shows the molecular weight range of the stored pyrolytic oils
compared to Brent petroleum oil. Table II shows the highest molecular
weight recorded and the number and weight averages, which shows that high
490
500
C r o p ^ **
**" ....7
/ /
400
'
Tyre /
'
. "
/
/
/ . .'
//
200
h
//
/''
..'
300
^.
A'
r"
Wooi. y/
I?DF
yS7
,*
' Petroleum
100
^ _ ^ ^ ^ ^ j
20
40
60
80
% Recovered
100
Figure 3. Simulated distillation of lower boiling point

fraction of pyrolytic oils.
molecular weight fractions are present in all the samples albeit in low
concentration. Molecular weight ranges in oil from wood waste of over 2000
(20) and up to 10000 (15) have been recorded. Figure 2 also shows a sample
of RDF derived oil analysed after only 4 days compared to the sample stored
for several weeks, there is clear evidence of a shift in the histogram to
higher molecular weight compounds and Table II shows an increase in both
the number and weight average molecular weights, indicating polymerisation
of the sample during extended storage. Polymerisation of wood derived oil
has been observed after only 3 days storage (20) and cellulose derived oil
also exhibits polymerisation on storage (16). The polymerisation of waste
derived oils is a disadvantage in that storage for any length of time has a
deleterious effect on the oil, increasing the viscosity and consequently
the handling problems of these oils.
Figure 3 shows the simulated distillation range of the oils and
petroleum oil using pyroprobe GC. The results represent the simulated
distillation range only for those compounds that are volatilised below 500
C.
In all cases the first distillation fraction was higher than petroleum
oil, the middle distillate fraction most closely represented by wood oil
and to a lesser extent RDF oil. The highest distillation range was found
for crop waste oil and is reflected in the much larger molecular weight
491
Table II : Molecular Weight Data for the Pyrolytic Oil.
Material
Rubber Tyre
Crop
Wood
RDF (Stored)
RDF (Fresh)
Max. Re con
3200
3800
2700
3200
1950
MW
No. Average MW
335
397
326
314
261
Wt. Average MW
470
584
458
476
340
range and higher number and weight average molecular weights (figure 2 and
Table II). Since polymerisation of the samples has taken place during the
extended storage period, they will represent a higher boiling point
fraction than originally condensed from the reactor. The residue retained
in the pyroprobe after volatilisation represents the high molecular weight
fraction which is not analysed by this method and thus simple distillation
refining of the oils is made more difficult than at first indicated by
figure 3. The polymerisation of the samples also leads to difficulties in
defining the refinery processing applicable to these oils if they are
stored for extended periods.
4.ACKNOWLEDGMENTS
This work was supported by the UK Science and Engineering Research
Council under grant number GR/F/06074. We would also like to thank Leeds
university personnel, A. Wheeler, J. Taylor, D. Mills and G. Nedjad and Dr.
T. Rampling WSL and M. Eastwood E. Sussex C.C. for waste samples.
5. REFERENCES
(1) Clark J.A.J. I.Mech.E. Paper No. C08/88 (1988).
(2) Dent C. & Krol A.A. MSW conversion to Energy, Harwell HMSO (1987).
(3) Finney C S . S Garrett D.E. Energy Sources 1,3 (1974).
(4) Preston G.T. Waste Age 7,5 88-91 (1976).
(5) Richards K.M. Proc. Energy from Landfill Gas, Solihull OK Oct (1976).
(6) Biddle C.A.R. & Naylor E. I.Mech.E. Paper C13/88 (1988).
(7) Jackson D.V. & Tron A.R. Int.J.Energy from Wastes 6,1, 31-44 (1985).
(8) Porteus A. Refuse Derived Fuel 38-56 App. Sci. Pubs. London (1981).
(9) Collin G.in Jones J.L. & Radding S.B. ACS Syp.Sr.130 (1980).
(10) ASTM D 2887-84 (1988).
(11) Kawakami S. in Jones J.L. fi Radding S.B. ACS Syp.Sr.130 (1980).
(12) Suzuki M. & Sato H. Jpn.Kokai Tokkyo JP61/7387 (1986).
(13) White E. & Thomson M.in Jones J. fi Radding S. ACS Syp.Sr.130 (1980).
(14) Delmon B. et al, in Grassi G. S Zibetta H.,
Energy from Biomass-1,
Elseveir, London (1987).
(15) Pober K.W. s Bauer H. in Anderson L.L. S Tillman D.A. Eds. Fuels from
Waste, Academic Press, New York (1977).
(16) Rampling T.W. & Hickey T. WSL LR643(MR) HMSO (1988).
(17) Soltis E.fiLin S.in ACS Div. Fuel Chem. 32, No. 1-2 (1987).
(18) Kaminsky W.S Sinn H.in Jones J. & Radding S. ACS Syp.Sr. 130 (1980).
(19) Pakdel H. fi Roy C. in ACS Div Fuel Chem. 32, No. 1-2 (1987).
(20) Johnson D.K. fi Chum H.L. in ACS Div. Fuel Chem. 32, No. 1-2 (1987).
492
ENVIRONMENTAL AND PUBLIC HEALTH ASPECTS OF GASIFIER SYSTEMS
J. WILLOCX, consultant, Londerzeel (Belgium)
A. BUEKENS, professor, Vrije Universiteit Brussel (Belgium)
Summary
Gasifier systems usually consist of a reactor with feeding
and ash discharge devices,gas cleaning and cooling equipment and gas utilisation installations. Feed preparation
is also often accomplished at the same place.
During each of the process steps gaseous, liquid or solid
effluents may be generated causing damage to public health
or the environment on short or longer term if not properly
managed. In addition some of these activities may be associated with discomfort by inadmissible noise levels, unpleasant smells or dust emissions.
Most attention is however given to the intermediate products of gasification, which are separated as aqueous condensates or are contained in the solid residues. Part of
these products are potential water pollutants whereas
other may show carcinogenic properties.
1. INTRODUCTION
Gasifiers are used for producing a gaseous energy carrier
from solid combustibles in cases where the wanted form of energy may not technically or economically be produced by direct
combustion.
The principle of gasification is based on the combustion
process in which the air intake is lowered so that the produced
gases contain part of the energy of the fuel in the form of
combustible gaseous molecules, mainly carbon monoxide and also
small portions of lower hydrocarbons. Instead of air as the
reacting gas also steam, oxygen or air enriched with oxygen
and/or steam may be used.
The unwanted products of gasification, which are steam,
higher hydrocarbons and dust are separated in the gasifier
system and some of them may cause damage to public health or
the environment if not properly managed. Also other adverse
effects on the environment may be produced by gasifier systems,
including inadmissible noise levels, unpleasant smells or dust
emissions.
Gasifier systems usually consist of a reactor with feeding
and ash discharge devices, gas cooling and cleaning equipment
and a gas utilisation installation. Also fuel preparation may
be accomplished at the same place.
2. FUEL PREPARATION AND FEEDING
Gasifier fuels may include coal, peat, wood and wood
wastes, forestry and agricultural residues and wastes from
493
agricultural industries. Common operations for preparing fuels
such as drying, size reduction, size classification and size
enlargement may produce noise and dust. Carbonisation and
torrfaction of fuels may in addition give rise to odor pro
blems. Fuel feeding and handling may also be dust generating.
The adverse effects of these operations may in general only af
fect those working at the plant and not the environment, except
in cases of large scale operations, which are common at coal
gasification plants.
3. GASIFICATION
Reactors for gasification may be classified according to
the type of flow of the combustibles as entrained flow, flui
dised bed or fixed bed gasifiers. The latter, which are most
common, may be subdivided in updraft, downdraft and crossflow
gasifiers, indicating the flow direction of the gases in the
reactor.
During gasification the bulk of the solid fuel and the
reactants are transformed into permanent gases, steam, higher
hydrocarbons and dust or particulates, leaving the reactor as
a raw gas stream. At certain reactor types part of. the steam
and the higher hydrocarbons may leave the reactor as a conden
sate. At the bottom of the reactor a solid residue is dischar
ged consisting of mineral ash and char.
The higher hydrocarbons, often indicated as tars and oils,
are intermediate reaction products, which are formed in varying
quantities according to the properties of the fuel, the type of
reactor and the operating conditions. Also the characteristics
of the tars and oils are influenced by the same variables.
The tar and particulate concentration ranges in the raw
gas depend largely on the type of reactor. For fixed bed gas
ifiers the concentration of particulates is typically below
10 g/Nm whereas for the other types this value is usually ex
ceeded. The ar loadings are in most reactor types higher than
5 to 10 g/Nm , except for downdraft and crossflow gasifiers,
showing values of 10 to 100 times lower than the other types.
The dust and particulate loadings in the raw gas may be
specified as fly ash, char particles, soot, carbon black and
mineral vapors. Fly ash consists mainly of mineral matter. Char
particles represent pyrolysed or partly burned biomass that is
fine enough to be entrained in the raw gas stream. Soot or car
bon black is very fine pure carbon dust, a product of reverse
reactions or cracking of tar liquids, which may adsorb a number
of polycyclic aromatic hydrocarbons. Mineral vapors consist of
mineral matter boiled off in the oxidation zone.
The solid residue collected at the bottom of the gasifier
represents in principle the incombustible fraction of the fuel
but also considerable amounts of charcoal may be present. The
The disposal of such residues may need special care because of
the presence of airborne particles, which may contain polycy
clic aromatic hydrocarbons, carcinogenic substances, and be
cause of the fire risks.
The condensate collected from the reactor at certain ga
sifier types consists mainly of water but may contain consider
able amounts of acetic acid and other water soluble organic
compounds, such as phenol and furfural. Also small amounts of
494
benzene, napthalene, toluene and xylene may be present besides
trace quantities of compounds such as aldehydes, ketones, carboxylic acids, esters, phenols, polyhydrics, heterocyclic oxygen and nitrogen compounds, polycyclic aromatics and other.
Such condensate is environmentally suspect with regard to the
risk for water pollution in case of inadequate disposal and
they may also produce adverse health effects, including cancer.
It may also produce odor problems.
4. GAS CONDITIONING
Conditioning of the gas consists mainly of the separation
of tars and particulates from the raw gas and at the same time
cooling it in order to make it suitable for a given utilisation.
The systems available for gas conditioning may be classified as
wet, dry or semi-dry systems.
Wet systems include spray towers, wet packed beds and venturi scrubbers. They usually use water to collect the gaseous,
liquid or solid impurities, which implies extra waste water to
be disposed of. On the other hand cooling of the gas occurs at
the same time as cleaning and fire or explosion risks are
minimised or are non-existent.
In dry systems the impurities may be separated as a dry
material, which may be disposed of without the environmental
care needed for liquid effluents. However dry dust may be
hindering or even dangerous when handling and may also give
specific disposal problems. Examples of dry systems include
cyclones, fabric filters, dry packed beds and electrostatic
precipitators.
With semi-dry systems the residue disposal may be less
problematic but their use is generally limited to large scale
operations, for economic reasons.
The liquid wastes generated during gas cleaning and
cooling generally contain less oils and tars than the gasifier
condensate discussed in previous chapter. The nature of the
organic load may be similar with respect to the number of compounds but the presence of high boiling fractions tends to be
favored. Usually this waste contains also dust particles.
Disposal of considerable amounts of contaminated condensate in the environment without adequate measures may cause a
risk for water pollution. This may be due to water soluble
organics such as phenol, especially if the applied concentrations inhibit or destroy biological life. At lower concentrations some of the potential water pollutants may however be
biodegradable in water or soil.
Water pollution may also be caused by compounds such as
benz(a)anthracene or benzo(a)pyrene, which show carcinogenic
properties. Despite of their insolubility they may be dispersed
in water adsorbed on particles and be dangerous for human
health after bioaccumulation in the food chain.
In this respect the disposal of dust may need also special
attention because char particles may adsorb non-polar organic
compounds up to 20 to 40 % of their weight whereas this may be
higher for soot and carbon black. Such particles may be dispersed via the atmosphere and contaminate air and food substances.
In order to control such problems several solutions have
495
been proposed. An attractive solution solving two problems at
the same time, the disposal of char and of condensate, appears
to be the adsorption of the liquid wastes on the ash/char re
sidues, which may be combusted after drying. The condensates
may also be disposed of by evaporation of the water and recy
cling the dry residue to the reactor. Another solution could
consist of mixing the fuel with a combination of Ni/La and
CO., catalyst which reduces the production of higher hydro
carbons in favor of smaller molecules, especially hydrogen.
5. GAS UTILISATION
For driving internal combustion engines the raw gas needs
generally to be cleaned down to 1050 mg/Nm of solid particles
and 1001000 mg/Nm of tars and oils. With respect to the pol
lutants in the exhaust gases from producer gas engines it may
in general be stated that the problems will be smaller than
with gasoline engines because of more complete combustion and
a lower adiabatic combustion temperature. However it has been
reported that at low load producer gas engines generate higher
carbon monoxide and hydrocarbon emissions than when diesel fuel
is used. Other measurements show that in engines fueled with
producer gas the hydrocarbon emissions are generally lower than
for gasoline, as may be expected, but that the nitrous oxide
emissions are roughly the same. The issue may be complicated
by the changing gas quality and the manual adjustment of the
gasair mixing ratio which is often employed with producer gas
engines. The noise level may also be a problem with engine
operation.
If the gases are burnt for heating purposes a relatively
high tar and particulate content may be allowed since they will
in general be consumed in the burner by combustion. The major
environmental problems with burning the gases may result from
NO and SO in the exhaust gases. However the concern with
sulphur is of a smaller extent with gasification than with
direct combustion of the solid fuel since it is easier to
separate sulphur from fuel gases than from exhaust gases. The
sulphur problem may be especially reduced if fuels with low
sulphur content, such as biomass, are used.
6. CONCLUSION
This paper atten.pts to highlight the major environmental
and public health aspects of gasifier systems. The range of
aspects includes minor issues, such as noise, dust and odor
problems, and major issues, such as risks for water, air and
soil pollution, including cancer risks. The extent to which
these adverse effects may be produced depends on the type of
reactor, its capacity and operating conditions, the type of
feedstock, gas conditioning and gas utilisation.
LITERATURE
Brown, M. D., Baker, E. G., Mudge, L. ., Environmental
design considerations for thermochemical biomass energy,
Pacific Northwest Laboratory, Richland, Washington, 1986.
Buekens, ., Schoeters, J., Thermal methods in waste dis
posal, Part I : Pyrolysis and gasification, Commission of the
European Communities, Brussels, 1984.
496
Evans, R., Knight, R., Omnischak, M., Babu, S., Develop
ment of biomass gasification to produce substitute fuels, Pro
ceedings of the 1985 Biomass Thermochemical Conversion Contra
ctors Meeting, Minneapolis, 1986.
Knoef, H., Stassen, H., Hovestad, A., Visser, R., Environ
mental aspects of condensates from downdraft biomass gasifiers,
University of Twente, Enschede, The Netherlands, 1987.
N., Producer gas manual, Producer gas course, Bandung,
Indonesia, 11 18 March 1985.
., UNDP/World Bank guidelines for field monitoring of
small scale biomass gasifiers, The World Bank, Energy Depart
ment, Washington D.C., 1984.
497
CHARACTERIZATION OF WOOD CONSTITUENTS
BY PYROLYSIS - FIELD IONIZATION MASS SPECTROMETRY*
H.-R. SCHULTEN
Fachhochschule Fresenius, Department of Trace Analysis, Dambachtal 20
D-6200 Wiesbaden Federal Republic of Germany
Summary
Direct pyrolysis-field ionization mass spectrometry (Py-FIMS) is applied
to standard samples of wood constituents such as glucose, celiobiose,
cristalline and amorphous cellulose, birch hemicellulose, and birch lignin.
The thermal behaviour and chemical characterization of these polar low
molecular weight plant constituents as well as complex biomaterials by
thermal degradation coupled with soft ionization mass spectrometry is
shown. This high-vaccum (in-source) technique allows molecular weight
distribution profiles of thermally released material to be rapidly obtained
at both low and high mass resolution. The main topic is to demonstrate
that the thermally released chemical species are directly related to the
original structure of the starting material and artifact formation during
pyrolysis plays only a minor role under the selected experimental
conditions. Thus, for qualitative and quantitative investigations of
biomass, in particular dried, milled wood, the method can be utilized for
basic research on wood composition and quality control of biomass
conversion processes.
1. INTRODUCTION
The global search for alternative energy sources based on biomass and
current problems of tree damage have created an urgent demand for analytical
methods directly applicable to plant materials. The first requirement of such
methods is that they should provide an immediate "fingerprint" of the whole sample
with minimal preparation so that the sample may be identified by eye, library
searching or more sophisticated pattern recognition methods. The second
requirement is that it should be possible to identify relevant chemical species
present as biomarkers and perhaps responsible for the "fingerprint" differences and
variations found.
The importance of biomass as a renewable starting material has steadily
increased and in particular its pyrolysis and gasification processes play an
important role in the search for alternative energy resources. Around the year
2,000 biomass may already provide approximately 696 of the total primary energy
demand in the countries of the European Community (2). As biomass conversion
increases in importance so too will the applied analytical methods. The
responsibility assigned to such methods in predicting and steering the successful
outcome of large-scale chemical engineering operations could well become
enormous. The situation is complicated by the intrinsic variability of the naturally
produced feedstocks together with quality control of the desired products such as
charcoal, gases, liquid fuels. Much interest therefore attaches to the development
of rapid, reliable and comprehensive techniques which may be suitable for
application to both feedstocks and products initially in pilot studies and later in
automated factory environments (3).
Characterization of plant materials by Py-FIMS, Part VI. For Part V see ref.(l).
498
Conventional procedures for the analysis of such complex biomaterials
normally involve series of laborious steps including separations, chemical tests and
spectroscopic or other instrumental techniques. This process can be especially
time-consuming when only the differences between samples are of interest and the
chemical species responsible for the difference is completely unknown. Even where
fractions have been isolated containing the species of interest, the analytical
techniques may lack sensitivity or resolution.
An analytical scheme is introduced, based upon pyrolysis (Py) field
ionization (FI) mass spectrometry (MS) and pyrolysis gas chromatography/mass
spectrometry (Py-GC /MS) for the rapid profiling of plant material without sample
preparation. As demonstrated earlier (), the field ionization method provides
strong molecular ion signals for most organic molecules over a wide polarity range
with minimal fragmentation. Thus, the technique is well suited to the analysis of
complex mixtures with no prior component separation. In comparison with other
soft ionization techniques the FI method is relatively background-free, making it a
powerful tool for the recognition of small differences between sample spectra. The
sum of all spectra obtained during Py-FIMS gives a highly differentiated spectrum
of the total sample. Such a procedure has been applied to the analysis of
polysaccharides (5), chitin (6), plant mucilages (7), tobacco (8,9), humic substances
and soils (10-12) and biomass (13,14).
The present paper reports the application of the improved technique (15)
of temperature-programmed Py-FIMS to samples of plant materials such as wood
constituents.
2. MATERIALS AND METHODS
Wood constituents
The D-glucose (anhydrous dextrose, moisture 0.5%) and cellobiose (from
cellulose, moisture 0.10%) were research grade and purchased from Pfanstiehl
Laboratories Inc., Waukegan, Illinois, U.S.A. The specimen of amorphous (Sigmacel
Type 100) and crystalline (FMC Avicel, PH-102, 90 ium) cellulose were obtained
from the Institute of Wood Research, University of Montana, Missoula, U.S.A. The
milled birch wood lignin ands birch hemicellulose were gifts of the Federal
Research C entre for Forestry and Forest Products, Hamburg, FRG.
Pyrolysis-field ionization mass spectroscopy
For direct temperature-programmed Py-FIMS, approximately 100 .ug of
dried, ground raw material were placed into the quartz crucible of the modified
direct introduction system ( 12 ) of a Finnigan MAT 731 double-focussing mass
spectrometer. The sample was heated linearly from 50 C to 750 C within 10 min.
In general, the mass spectra were recorded electrically by repetitive magnetic
scans in the range m/z 100 to m/z 1200 and acquired by the Finnigan SS200 data
system. For accurate mass measurements, some spectra were recorded
photographically at high mass resolution (20,000; 10% valley definition).
3.
RESULTS AND DISC USSION

The results obtained by application of temperature-programmed Py-FIMS
to samples of glucose and cellobiose (as simple building blocks of wood), crystalline
cellulose, amorphous cellulose, birch hemicellulose and birch lignin are given.
Firstly, it was considered crucial to obtain Py-FIMS spectra of single
components, e.g. monomer and dimer hexose units of known structure, in order to
correlate the structure with the spectral peaks and the thermal processes involved.
Such a step is essential for tackling the much more complex and unknown
structures, e.g. plant materials such as wood, to be subsequently investigated.
499
Pyrolysis-field ionization mass spectrometry
a Glucose and cellobiose, the building blocks of cellulose
The time-integrated Py-FI mass spectra of D -glucose (mol. wt. 180) and
cellobiose (mol. wt. 3^2) are shown in Figures la and b, respectively. These mass
spectra are formed by summing the recorded spectra using the routine heating
procedure for pyrolysis of macromolecular samples (linear temperature rise from
50 to 750 C in approx. 10 min). As the soft ionization method employed yields
mainly molecular ions with little fragmentation, the spectra provide a direct
6-
133149
68
119
59
163
182
29
iXm ise
se
191216
|l<fl|tltl|>|
358
m/z
31
6e
144
s
i
s.
20
96
05 98
Lu
Fig. 1
204
252
258
28B j306
^'>>1 >I HI 11 .,,.,
15
380
358
400
a) Pyrolysis FI mass spectrum of Dglucose;

b) Pyrolysis FI mass spectrum of cellobiose.
458
588
500
molecular weight distribution profile of all components of the produced pyrolysate
within the mass range covered.
B oth spectra are characterized by weak molecular
ions at m/z 181 ((M+H)+ ion of glucose) and m/z 32 ( (M+* ion of cellobiose). In
Fig. la, the main peaks within the molecular
weight range of glucose are m/z 163
(,+)*, m/z 1** (M2 H 2 0) + , m/z 133 (,CHO)"1", m/z 116
(MCHjOoK The large lower mass peaks are producea by further water
eliminations
and direct bond cleavages. Notable is the relatively small m/z 126 (M
3xH 2 0) + peak in Fig. la which is the base peak in the cellobiose spectrum (Fig. lb).
Fragment peaks
of the dimer (2M) are seen in the glucose spectrum at m/z 306
(222)+ and m/z 293 (2MH 2 0CH,0) + . As expected, the same fragments at
m/z 306 and m/z 293 also appear in the cellobiose spectrum (Fig. lb ). In this
spectrum, however, additional signals due to 2, 3 and water eliminations at m/z 288,
270 and 252, respectively, as typical products of thermal processes are observed,
b) Crystalline cellulose
The summed FI mass spectrum and total ion current (TIC) profile obtained
on PyFIMS of the crystalline cellulose sample is shown in Fig. 2. This type of
1.0 ,
0.5
io
c
a :
O O
1 " &
50
100
200
Temperature I*C1
I
300
-//700
114
60'
4 3
tf3
?
28T3
208
30
348
3 6
tifili ^ h
'40
470
510
i
500
m/z
Fig. 2
Pyrolysis FI mass spectrum and thermogram (plot of the total ion current
(TIC) versus temperature) of crystalline cellulose,
profile will be referred to as a thermogram and the ion current is seen to start
around 230C, maximize at 305C and end at 335C heating. When the FI mass
spectra in this temperature range are summed, a timeintegrated FI mass spectrum
is obtained which summarizes the m/z (mainly molecular ion) contents of the
thermogram. The spectral pattern obtained is highly differentiated and free of
background revealing the advantages of this ionization technique. The major
pyrolysis products have peaks at m/z 162, 14 (base peak), 126, etc. Differences
observed between this spectrum and that of amorphous cellulose are described
below. The creation of such a timeintegrated survey spectrum also has the
advantage of telling the analyst which ions are the most significant thereby
allowing him to plot individual m/z values in the thermogram. The time
(temperature) of occurrence of these ion currents is important in deciding whether
a peak is probably a released volatile (low mass, low temperature, short time) or a
501
low mass pyrolysis product (high temperature , long time). This is illustrated by the
total and selected ion current plots of pine wood flour in the following paper (17).
c) Amorphous cellulose
The thermogram and timeintegrated survey spectrum of amorphous
cellulose are shown for comparison in Figure 3. The thermogram is somewhat
ro
t *
100
x ?. 05,
S =
S3
126
50
100
200
Temperature [C]
o
u
60
40
BS
98
et
W f JUifc
43 0
<~>.| ) . < . |
400
500
see
m/z
Fig. 3
Pyrolysis FI mass spectrum and thermogram of amorphous cellulose

experimental conditions as Fig. 2.
broader than that in the crystalline case (Fig. 2) as the start of the intense TIC is
around 195, maximum at 295 and end at 335C. The typical hexose signal at m/z
162 is less significant the intensity ratio m/z 162 / 144 (base peak) averages 16%
in the crystalline case (5 determinations) compared to 5% in the amorphous case.
This observation should be helpful in an estimation of naturally occuring cellulose
as reported, for instance, in soils (12). Moreover, m/z 126 is more abundant in the
amorphous case (74% compared with 51%) and, in addition, the amorphous
spectrum has a significant peak with m/z 114 (approx. 30% of base) which falls
below 15% of base peak in the crystalline case. The signal at m/z 114 is of
particular importance in the following discussion of polyoses in birch wood,
d) B irch Hemicellulose
Softwood xylans are characterized by arabinofuranose linked by
oC(l3)glycosidic bonds to the xylan backbone (16). The survey spectrum shown
in Figure 4 and is dominated by the base peak at m/z 114 and large ions in the
lower mass range e.g. at m/z 96, 86, 74 and 60. In addition to low abundant ions for
monomeric pyrolysis products of lignin, the small signals at m/z 210, 332 and 418
are due to lignin contamination (see e) below). The pentose molecular ion
(arabinose ) at m/z 150 and the product of direct water eliminations at m/z 132 are
clearly discerned but of relatively low abundance. Thus, it appears difficult to
identify hemicellulose on the basis of nominal mass peaks by PyFIMS alone.
502
60
40
74
96
138
164
140
MJL
UjJUulv
108
illiy|,rl|H,,|lî,,Di|
200
250
158
, |., I
300
"
350
"
40
45
508
Fig. <t Pyrolysis FI mass spectrum of birch wood hemicellulose.
100
2.0
418
8.3
34
5 9 6
.0
^(^Mtf^JJ^ÎfUlnHlMi
100
280
308
n/Z
Fig. 5
408
500
680
780
Pyrolysis FI mass spectrum of birch wood lignin.
880
|
908
503
e)
Birch Lignin
The survey spectrum of birch lignin is shown in Figure 5 and is
characterized by intense ions having signals of the nominal mass 180, 210 (base
peak), 332 and 418. Investigations by PyGC/MS and accurate mass measurements
using PyFIMS allowed the assignments of these lignin pyrolysis products. Coniferyl
alcohol (180.0786; C . Q H ^ O J ) , sinapyl alcohol (210.0892; CjjHÔ^) and
syringaresinol (418.1628; Cj^HjgO) were identified (18). In addition a lignin dimer
of yet unknown structure 332.26; C , O H 2 Q 0 6 ) was found. A further significant
spectral characteristic is the absence of any significant peaks between m/z 54 and
m/z 150. In the higher mass range above m/z 418, however, numerous FI signals up
to m/z 878 are registered. In general, the sensitivity of PyFIMS for thermally
stable lignin subunits is high, as can be derived, for instance, from the weak but
distinct FI signals at m/z 210, 332 and m/z 418 in the previous spectrum of
hemicellulose (Fig. 4). The method apparently has great potential for the detection
of lignin traces in preparations of wood and wood constituents.
4.
CONCLUSIONS
The results obtained from both two model sugars and of the three major
macromolecular components cellulose, hemicellulose and lignin clearly show that a
direct, characteristic relationship exists between the products of thermal
degradation monitored by PyFIMS and the original chemical structures of even
such complex biological materials as wood.
Raw feedstocks, intermediate fractions and finished products can be
directly compared and differences investigated where considered necessary. The
potential importance of the combined techniques in production is increased by the
suitability of the spectral data for direct incorporation into computerized process
monitoring and control systems. The method as described has consequences for
both research and production aspects of biomass conversion and the search for
alternative energy sources.
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
Simmleit, N. and H.R. Schulten (1989). Characterization of Plant

Materials by PyrolysisField Ionization Mass Spectrometry V: Pattern
Recognition of Spruce Trees An Integrated, Analytical Approach to
Forest Damage. Environ. Sci. Technol., in press.
Solar Energy R & D
Programme (1985). Results and Conclusions
19791984, Commission of the European Communities, EUR 10249 EN,
Directorate General () for Research and Development, Brussels,
Belgium.
Soltes, E. J. and T. J. Elder (1981). Pyrolysis. In: Organic Chemicals from
Biomass, I. S. Goldstein (Ed.), CRC Press, Boca Raton, U.S.A., pp. 64101.
Schulten, H.R., H. D. Beckey, H. L. C. Meuzelaar and A. 3. H. Boerboom
(1973). High Resolution Field Ionization Mass Spectrometry of Bacterial
Pyrolysis Products. Anal. Chem. 45, 191195.
Schulten, H.R. and W. Grtz T978). CuriePoint Pyrolysis and Field
Ionization Mass Spectrometry of Polysaccharides. Anal. Chem. 50, 428
433.
Kaaden, A. van der, Boon, J. J., de Leeuw, 3. W., de Lange, F., Wijnand
Schuyl, P. J., Schulten, H.R. and U. Bahr (1984). Comparison of
Analytical Pyrolysis Techniques in the Characterization of Chitin, 56,
21602164.
504
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(lfr)
(15)
(16)
(17)
Schulten, H.-R., U. Bahr, H. Wagner and Hermann, H. (1982). PyrolysisField Ionization Mass Spectrometry of Pharmaceutical Plant Mucilages.
Biomed. Mass Spectrom. 9, 115-118.
Schulten, H.-R. (1986). Pyrolysis-Field Ionization Mass Spectrometry - A
New Method for D irect, Rapid Characterization of Tobacco. Beitr.
Tabakforsch. Int. 13, 219-227.
Simmleit, N. and H.-R. Schulten (1986). D ifferentiation of Commercial
Tobacco Blends by Pyrolysis-Field Ionization Mass Spectrometry and
Pattern Recognition. Fresenius . Anal. Chem. 32fr, 9-12.
Haider, . and H.-R. Schulten (1985). Pyrolysis-Field Ionization Mass
Spectrometry of Lignins, Soil Humic Compounds and Whole Soil. 3. Anal.
Appi. Pyrolysis 8, 317-331.
Schulten, H.-R.~(l987). Pyrolysis and Soft Ionization Mass Spectrometry of
Aquatic/Terrestrial Humic Substances and Soils. J. Anal. Appi. Pyrolysis
_12, 1*9-186.
Post, B., R. Hempfling, H. Klamberg and H.-R. Schulten (1988). Zur
Charakterisierung von Huminstoffen. Fresenius Z. Anal. Chem. 331,
273-281.
Schulten, H.-R. (198fr). Relevance of Analytical Pyrolysis Studies to
Biomass Conversion. 3. Anal. Appi. Pyrolysis 6, 251-272.
Schulten, H.-R. (1987). Workshop on Pyrolysis as a Basic Technology for
Large Agro-Energy Projects, Commission of the European Communities,
L'Aquila, Italy, Oct. 15-16.
Schulten, H.-R., N. Simmleit and R. Mller (1987). High-Temperature,
High-Sensitivity Pyrolysis-Field Ionization Mass Spectrometry. Anal.
Chem. 59, 2903-2908.
Fengel, D . and G. Wegener 1983. Wood : Chemistry, Ultrastructure,
Reactions, W. de Gruyter, Berlin.
Schulten, H.-R. and 3. M. Halket (1989). Characterization of Wood by
Pyrolysis-Field ionization Mass Spectrometry, Proc. Int. Conf. Pyrolysis
and Gasification, Luxembourg, May 23-25, and literature cited.
Acknowledgements
This
work
was
financially
supported
by
the D eutsche
Forschungsgemeinschaft, the Bundesministerium fr Forschung und Technologie,
Bonn-Bad Godesberg, and the Umweltbundesamt, Berlin.
505
CHARACTERIZATION OF WOOD
BY PYROLYSIS - FIELD IONIZATION MASS SPECTROMETRY*
H.-R. SCHULTEN1 and 3. M. HALKET 2
Fachhochschule Fresenius, Department of Trace Analysis, Dambachtal 20
_
D-6200 Wiesbaden Federal Republic of Germany
Department of Chemical Pathology, Queen Charlotte's and Chelsea Hospital,
Goldhawk Road, London W6 OXG United Kingdom
.
Summary
Direct pyrolysis-field ionization mass spectrometry (Py-FIMS) is used for
the investigations of birch and pine woods. The thermal behaviour and
global chemical characterization of these complex biomaterials by insource thermal degradation coupled with soft ionization mass
spectrometry is demonstrated.
Comparison between the spectrum of a synthetic blend (cellulose, birch
hemicellulose and birch lignin) and an authentic birch wood sample clearly
shows that artefact formation in temperature-programmed Py-FIMS is
negligible. Curie-point pyrolysis gas chromatography/mass spectrometry
(Py-GC/MS) is further employed to investigate the identities of selected
pyrolysis products. The combined methodology should find use in
fundamental research in the thermal analysis of plant materials as well as
in applications to environmental problems such as the present tree
damage and/or in monitoring feedstocks and products in biomass
conversion.
1. INTRODUCTION
In a concomitant publication (1) the state of the art of pyrolysis-field
ionization mass spectrometry (Py-FIMS) for biomass investigations is described and
an analytical scheme is introduced, based upon this method and pyrolysis-gas
chromatography/mass spectrometry (Py-GC/MS) for the rapid profiling of biomass
and identification of plant constituents. Recent work has demonstrated the
usefulness of direct Py-FIMS in combination with Py-GC/MS in characterizing
tobacco (2), food (3), spruce needles (<0 and soils (5,6). The reproducibility of the
Py-FI mass spectra of plant materials (7,8) and plant litter in forest soils (9) has
been shown by the application of chemometric methods.
The present paper reports the application of the improved Py-FIMS
method (7) to birch and pine woods. In particular, the complementary techniques of
capillary column Curie-point Py-GC/FIMS and Curie-point Py-GC/EIMS for further
characterization of Py products are described.
2. MATERIALS and METHODS
Wood samples
The birch wood as well as the pine wood were gifts of the Federal
Research Centre for Forestry and Forest Products, Hamburg, FRG.
*
Characterization of plant materials by Py-FIMS, Part VII. For Part VI see ref. (1).
506
Pyrolysisfield ionization mass spectroscopy
For direct, temperatureprogrammed pyrolysisFIMS, approximately 100
/Ug of dried, ground wood were placed into the quartz crucible of the modified
direct introduction system of a Finnigan MAT 731 doublefocussing mass
spectrometer. The experimental parameters recently have been given in detail (1).
Curiepoint pyrolysisgas chromatography/mass spectrometry
The flash pyrolysis experiments were performed using a Fischer 0310
Curiepoint pyrolyzer (Fischer, Meckenheim, FRG). The total heating time (THT)
was 9.9 s and the final temperature 500 C. The only modification made to the
commercially available apparatus was the inclusion of a leak as previously
described (10) to enable rapid pressure release after pyrolysis and sample injection.
Approximately 1 mg of biomass sample is placed into the sample holder and flushed
with helium prior to pushing through the GC inlet septum and activation of
pyrolysis. After pyrolysis, the sample holder is removed from the GC inlet system.
Gas chromatography
A standard split/splitless injector (Labormechanik Gerstel, Mlheim/Ruhr,
FRG) was employed together with a Varian 3700 gas Chromatograph. The injector
was maintained at 250 C and operated in the splitless mode or at a split of 10
ml/min. The helium carrier gas pressure was 10 Pa.
In PyGC/EIMS experiments, a 30 m 0.32 mm i.d. fused silica column
was employed (chemically bonded DB 1, 0.25 ium film thickness, J&W Scientific,
Rancho Cordova, CA, USA). In PyGC/FIMS experiments, a 26 m 0.32 mm i.d.
fused silica column was used (CpSil5CB , film thickness 1.3 ium. Chrompack,
Middelburg, The Netherlands). The columns were maintained at 50 C for 2 min
after pyrolysis and then programmed at 20 C/min to 250 C. Connection to the
mass spectrometer ion source was via a deactivated 0.1 mm i.d. fused silica line.
Mass spectrometry
For flash PyGC/MS, a Finnigan MAT 212 mass spectrometer fitted with a
combined EI/FI/FD ion source was employed under the following conditions: Field
ionization: accelerating voltage and emitter potential, 3kV; counter electrode,
8kV; multiplier, 2.2kV; scanning speed, 1.1 s/mass decade; mass range, m/z 50
1,000. Electron ionization: accelerating voltage, 3kV; ionizing energy, 70eV;
multiplier, 2.2kV; scanning speed, 1.Is/mass decade; mass range, m/z 33500.
3. RESULTS and DISCUSSION
The results obtained by application of temperatureprogrammed PyFIMS
to birch and pine woods are given. The complementary use of flash PyGC/MS using
both EI and FI as ionization modes is illustrated by application to the volatiles
produced from wood. Further characterization of the peaks can be carried out by
high resolution mass measurement (4).
Pyrolysisfield ionization mass spectrometry
) B irch wood
The timeintegrated survey spectrum of authentic birch wood is
reproduced in Figure la together with the original output of the corresponding
thermogram (ordinate : intensity; abscissa : pyrolysis time; number of recorded
single spectra; temperature). The spectral features are swamped by peaks due to
birch wood lignin at m/z 180, 210 and ^18 (see ref. 1). Of particular interest are
the FI signals in the mass range between m/z 250 and 500 as some of these
pyrolysis products have been identified as oligomeric lignin building blocks (11).
Other peaks of interest in the highmass range are observed at m/z 595, 689, 855
507
21
60
114
211
332
B79
S
ie
il
(,^,^^,,,,^,.,,,,
48
see
m/2
see
'
60
126
154
332 358
^ l | h h38fJ4if
UJ^Jl
*ln2
108
400
f*t*p rii r<*' ti1! f
500
608
788
800
988
m/z
Fig. 1
a) Pyrolysis FI mass spectrum of birch wood;

b) Pyrolysis FI mass spectrum of a synthetic blend : 42% crystalline
cellulose, 35% birch wood hemicellulose, and 21% birch wood lignin.
and 879 which are probably due to lipid fragments. The polyose content is
practically indicated by m/z 114 only. The series of ions having m/z 60, 84, 85, 96,
98, 114, 126, 144 and 162 are, at least mainly due to the hexose constituents in
wood such as hexose sugars, hemicellulose and cellulose.
508
For analytical pyrolysis of plant materials with respect to biomass
conversion (12) and environmental problems e.g. forest decline (13,14), it is of
fundamental interest to understand the relationship between observed pyrolysate
and the chemical structure of the starting material, wood in this case. Therefore, a
synthetic birch wood was prepared by mixing the three major constituents of birch
wood,i.e. birch hemicellulose, cellulose and birch lignin. For comparison, Fig. lb
shows the survey spectrum of a synthetic blend consisting of 35% birch
hemicellulose, k2% cellulose and 21% birch lignin. The high degree of similarity is
obvious.
In order to investigate the similarity further, a difference spectrum was
obtained by subtracting the synthetic blend spectrum (Fig. lb) from that of
authentic birch wood (Fig. la). The result is given in Fig. 2. The differences in the
4000
20000
1 *
416
2
3961434
596 6 4 4 689
879
55|
I , , i ! r., il ^ V " '*

1' " ' ' " ' 'ft":'" '! ' ''
,, M V;>.,,..Mr
40
30
60
70
0
20000
' ''!
18
40000
210
Fig. 2
Difference spectrum obtained by subtracting the synthetic blend spectrum

(Fig. lb) from that of genuine birch wood (Fig. la).
two spectra are now clearly revealed. Highmass peaks above the xaxis e.g. m/z
596, 64, 689, 855 or 879 are those which are either absent in the blend or present
to a much lesser extent. These significant groups are probably due to
aliphatic/paraffinic lipid components which are, of course, not present in the blend.
Peaks below the xaxis are those present to a lesser extent in the authentic wood
spectrum e.g. m/z 180 and 210. The sensitivity of PyFIMS for these aromatic
lignin constituents, coniferyl and sinapyl alcohol, is very high as can also be derived
from Fig. 5. Thus, these constituents are overemphasized in the summed spectrum
of the synthetic mixture. However, it has to be considered that these subunits may
also be overrepresented in the lignin preparation due to the isolation procedure.
When the subtraction from the authentic wood spectrum is performed by
calculating the corresponding sensitivities of PyFIMS for cellulose, hemicellulose
and lignin, only minor intensities of signals below the xaxis are observed.
As an important result, the statement can be made that the method gives
a qualitative estimate of wood and wood constituents mixtures and that the
formation of artefacts (i.e. pyrolysis products which are not directly related to
chemical substructures in the macro molecules) is negligible.
509
b) Pine Wood
The survey FI mass spectrum obtained from pine wood is reproduced in
Fig. 3. The survey spectral pattern is highly differentiated and free of background
31
1003
80
60
29
40
85
18
20
i+\
114
98 i
ML
K AM
lj
80
60i
226
2
15
*witi
4VJL
200
230
2 8 4 3 0 328
iX,M
t
330
40
2 H
'
374
374
tllHl'<'i'if
474
"
sS 0 :2
.^,,,,
55
ll>|i(.i|.lvl|,|,4îl|lt|ilJUk|ll
500
Fig. 3
59 612 626
6
650
Pyrolysis FI mass spectrum of pine wood.
indicating once again the advantages of this ionization technique. The major
products start at the highmass end with m/z 682; a series at 598, 612 and 626 with
CH_homologues; and continues with a series at m/z 226, 270, 272, 284, 286, 300,
302and 328 which is partly due to lignin dimers. This has been confirmed by
accurate mass measurements giving, for instance, 270.0895 ( C . n H ] 4 0 A ) , 272.1048
( C 1 ( . H , 6 O j , 284.1047 ( C , 7 H , , O a ) , 286.1200 ( , , , . 300099 ( C 1 7 H . , 0 5 ) ,
302l5S (CjyHjoO,.) ancT 328.1344 (C^HjgO^f (15). In this reference fignin
monomers have afso'Deen reported from spruce wood and litter at m/z 150, 152,
178 and 180. In addition, two main groups of components are seen in the ranges m/z
300396 and m/z 420550. The large peaks at m/z 18, 31, 43, 60, 84, 96, 98, 114
(partly), 126, 144 and the weak 162 are typical of hexose sugars, mainly cellulose
(12).
Figure 4a shows the thermogram for the total ion intensity (Til, plot of
the intensity of all ions in the recorded mass range versus temperature) which
yields a maximum at 320C. In order to illustrate the usefulness of the time (and
temperature)resolution in deciding whether a peak is a released volatile or higher
temperature pyrolysis product, the FI signals for water (18.0106; HO),
methoxystilbenol (226.0994; C^H.Ô) and
tocopherol (430.3811;
C2^^-^
were chosen. The first m/z 18 is clearly released volatile water whereas the later
m/z 18 (300 to 400C and around 450C) indicate water eliminations which
originate from higher temperature Py processes. Also, the temperature frame for
the release of the volatile wood constituent methoxystilbenol (m/z 226) is
completely resolved from the thermal production of tocopherol (m/z 430).
In addition, complete thermal fractions of pyrolyzates can be displayed
which give full PyFI mass spectra as illustrated for the temperature range 50 to
250 C in Fig. 4b. As illustrated for soil samples (6), it can be assumed that this
third dimension of the pyrolysis mass spectra plus high mass resolution is an
510
500
Temperature
600
700
[*C]
226
tee-.
B0-
e-
316
20-
180
18
328
114
; 9
JUJ.
396414
n
Ji.H'l'
108
Jk-
Lt
Jll
TVU+
m/z
Fig.
a) Thermogram of pine wood showing the TIC trace together with the
single traces for m/z 18, 226 and 430 illustrating the time-resolution;
b) Pyrolysis FIMS survey spectrum of pine wood obtained by summing the
mass spectra from 50 to 250 C in Fig. 4a.
essential step for a better understanding of pyrolysis pathways and the identity
and thermal behaviour of individual chemical species.
Curie-point Py-GC/FIMS
The field ionization mass spectra contained within a whole Py-GC/FIMS
run may be summed in a similar way to give a time-integrated survey spectrum.
511
164
100
)
80
160
60:
150
I
c
Q
<
40
20
60
58
74
|61
138
97
84 112
7
'I
[ ^ . ^ i j k t)l| m
50
182
2
. . .
IUmiJUL
100
m/z
150
200
?7
1270
250
300
350
b)
12
10
4UuA*iJÂ>JyJLJlLA
IBI. A^ÎU.
I H 11 1111 11 11 U I I 11 | I l I 11 111111 11 I I A I |*H+1 I 11 I 11
100
150
200
250
300
350
400
_^
m/z 180
m/z 178
m/z 164
I 11111 I 111 I |
450
500
Scan Number
Fig. 5
a) The timeintegrated survey spectrum of pine wood after Curiepoint

pyrolysis GC/FIMS (m/z 50350);
b) Curiepoint pyrolysis GC/FIMS of a pine wood sample. Total ion
current (m/z 45 450) and single ion chromatograms (m/z 164, 178 and
180); and
c) Total ion current chromatogram obtained after Curiepoint pyrolysis
GC/EIMS of pine wood (see top next page).
512
C)
00
300
200
3.
100
I ' I ' I ' I ' I ' I I J' I I I ' I ' I ' I ' I '
2:00 4:00 6:00 8:00 11:00 12:00 U:00 16:00
Time [min]
1111 1111111111111111111111111111111 1111111111111 1111 I I I
50
100 150 200 250 300 350 400 50 500
Scan Number
The survey spectrum obtained in the pine wood analysis is reproduced in

Fig. 5a and shows strong peaks at m/z 12, 126, 138, 150, 152, 16*l, 166, 178, 180
and 182. This spectrum summarizes the whole molecular weight contents of the
GC/MS run. It is also highly differentiated and may be compared with the low
molecular weight region of the direct PyFIMS thermogram (Fig. kb). Indeed, a
relatively small group of peaks (e.g. coniferyl alcohol) is evident having a similar
profile superimposed on the weak cellulose peak at m/z 180. The thick film
capillary column used in this case has a higher sample capacity allowing more
information to be obtained from the less sensitive FI technique but discriminates
strongly against higher molecular weight or polar components.
Such a timeintegrated PyGC/FIMS spectrum can act as a rough bridge
between the direct PyFIMS masses and the fingerprintlike mass spectra obtained
after Curiepoint PyGC/EIMS (see below). As in the thermogram case, the survey
spectrum tells the analyst which are the most significant masses so that selected
ion chromatograms may be directly plotted. Normally, the choice of ions to include
in such mass chromatograms can be a very tedious process, involving examination
of the spectra corresponding to many GC peaks. An example of such a mass
chromatogram formed from the PyGC/FIMS data for the pine sample is shown in
Fig. 4b for the m/z values 180, 178 and 16f, together with the TIC chromatogram.
Curiepoint PyGC/EIMS
The same sample subjected to PyGC/EIMS gave the TIC profile shown in
Fig. 5c containing a wealth of EI spectra suitable for identification purposes. Mass
chromatograms may then be constructed in the same way as in the PyGC/FIMS
case, above, and the spectra may be compared by their GC retention indices.
Further investigation of structures :
The peaks present in the direct Py survey spectrum may be further

investigated either by high resolution mass measurement (volatile and involatile
components) and by PyGC/MS using both FI and EI modes (volatile components).
Thus, a powerful strategy emerges for the rapid characterization or identification
of survey spectrum components (Schulten et al., 1989b). This may be of particular
importance where the survey spectral peaks are found to differ significantly
513
between, for example, 'good' and 'bad' batches of feedstock for a particular
application.
Using such a strategy, the following survey spectrum peaks (at least in
part) were tentatively identified (volatiles) :
m/z 58, acetone; m/z 60, acetic acid; m/z 112, 2-hydroxy-3-methyl-2cyclopentene-1-one; m/z 124, 2-methoxyphenol and 1,2-nonadiene; m/z 138,
phenol-2-methoxy-4-methyl; m/z 150, acetophenone, 2-hydroxy-4-methyl; m/z 164,
phenol, 2-methoxy-4-(2-propenyl)- and phenol, 2-methoxy-4-(l-propenyl)- and
phenol, 2-methoxy-5-(l-propenyl); m/z 166, acetophenone, 4-hydroxy-3-methoxy
and phenol, 2-methoxy-4-propyl; m/z 180, 2-propanone, l-(4-hydroxy-3-methoxy)
and phenol, 4-(3-hydroxy-l-propenyl); m/z 182, benzeneacetic acid, 4-hydroxy-3methoxy-.
The major molecular ions found in the Py-GC/FIMS case are m/z 150, one
prominent GC peak, m/z 164, three prominent GC peaks, m/z 180, five prominent
GC peaks (plus three others, probably fragment ions owing to somewhat longer
retention times).
These results show that the Py-FIMS method is readily applicable to wood
and wood components to yield highly differentiated and interpretable mass spectra.
Also illustrated is the potential of accurate mass measurement and Curie-point Py
GC/MS for further investigation of single components. The additional possibility of
cross-correlation between the GC FI survey spectrum containing all the molecular
weight information of the GC run and the FI chromatogram containing the time
dimension and therefore retention index data, suitable as a further important
identification parameter. Thus, it is possible to rapidly obtain a more
comprehensive picture of the whole sample contents from occluded volatiles up to
the m aero molecular structure.
The GC/MS part of this work will be further improved by ready
availability of modern high capacity capillary columns allowing higher mass and
more polar Py products to be separated and identified. Cryogenic trapping followed
by derivatization for gas chromatography should present no significant difficulties
in those cases where considered desirable. In the present work, emphasis has been
placed on illustration of rapid profiling so that a fast GC temperature program has
been chosen. For research work involving a thorough attempted identification of
components, a much slower temperature program or longer GC column may be used
thereby improving the separation and information content of the chromatogram.
The potential also exists for creation of libraries of Py-FIMS spectra as
well as application of pattern recognition techniques (13,14,16) to aid further
investigation both from a fundamental research point of view and for application in
commercial biomass conversion. One of the most important aspects of this
treatment is the demonstrated power of chemometrics using the integrated
approach allowing incorporation of external parameters such as chemical, physical,
technical properties and spectroscopic data e.g. IR, NMR etc.
4. CONCLUSIONS
The results obtained from both a real wood samples and a synthetic blend
of the three major macromolecular components cellulose, hemicellulose and lignin
clearly show that a direct, characteristic relationship exists between the products
of thermal degradation monitored by Py-FIMS and the original chemical structures
of even such complex biological materials as wood. Artefact formation may occur
during pyrolysis but obviously plays only a minor role and can be excluded for the
major observed signals.
Thus, it can be expected that technical processes of biomass conversion
can be simulated qualitatively and quantitatively in the ion-source microreactor of
the mass spectrometer. If sufficient data sets are available, modeling and
prediction of biomass properties should be accessible by chemometric evaluations.
514
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
Schulten, H.R. (1989). Characterization of Wood Constituents by

PyrolysisField Ionization Mass Spectrometry, Proc. Int. Conf. Pyrolysis
and Gasification, Luxembourg, May 2325, and literature cited.
Halket, 3. M. and Schulten, H.R. (1985). Rapid Characterization of
Tobacco by Pyrolysis Field Ionization Combined PyrolysisMass
Spectrometry and PyrolysisGas Chromatography/Mass Spectrometry
Studies. 3. Anal. Appi. Pyrolysis 8, 547560.
Halket, 3. M. and H.R. Schulten (1988). Fast Profiling of Food by
Analytical Pyrolysis. Z. Lebensm. Unters. Forsch. 185, 112.
Schulten, H.R, . Simmleit, and R. Mller (1989)7 Characterization of
Plant Materials by PyrolysisField Ionization Mass Spectroscopy: High
Resolution Mass Spectrography, TimeResolved High Resolution Mass
Spectrometry and CuriePoint PyrolysisGas Chromatography/Mass
Spectrometry of Spruce Needles. Anal Chem. 61, 221227.
Hempfling, R. and Schulten, H.R. (1988). Characterization and Dynamics
of Organic Compounds in Forest Humus Studied by PyrolysisGas
Chromatography/Electron Impact Mass Spectrometry and Pyrolysis(High
Resolution) Field Ionization Mass Spectrometry. 3. Anal. Appi. Pyrolysis
_13, 319325.
Hempfling, R., W. Zech and H.R. Schulten (1988). Chemical Composition
of the Organic Matter in Forest Soils . Moder Profile. Soil. Sei. 146, 262
276.
Schulten, H.R., . Simmleit and R. Mller (1987). HighTemperature,
HighSensitivity PyrolysisField Ionization Mass Spectrometry. Anal.
Chem. 59, 29032908.
Simmleit, N. and H.R. Schulten (1989). Analytical Pyrolysis and
Environmental Research. 3. Anal. Appi. Pyrolysis 15, 328.
Schulten, H.R., R. Hempfling, W. Zech (1988). Discriminating Horizons in
a Moder Profile by Field Ionization Mass Spectrometry and Pattern
Recognition. Geoderma 41, 211222.
Halket, 3. M. and H.R. Schulten (1986). Simple Pyrolysis Chamber
Modification
for
Capillary Column CuriePoint
Pyrolysis Gas
Chromatography/Mass Spectrometry of Complex Biomaterials. J. High
Resolut. Chromatogr. Chromatogr. Commun. 9, 596597.
Kgel, I., R. Hempfling, W. Zech, P. G. Hatcher and H.R. Schulten
(1988). Chemical Composition of the Organic Matter in Forest Soils I.
Organic Chemical Composition of Forest Litter. Soil Sci. 146, 124136.
Schulten, H.R. 1984. Relevance of Analytical Pyrolysis Studies to
Biomass Conversion. J. Anal. Appi. Pyrolysis 6, 251272.
Simmleit, N. and H.R. Schulten (1989). Characterization of Biomaterials
by InSource PyrolysisMass Spectroscopy IV : Differentiation of Spruce
Needles by Integrated Field Ionization Mass Spectra and Principal
Component Analysis. Biomed. Environ. Mass Spectrom. ^8, xxxxxx.
Simmleit, N. and H.R. Schulten (1989). Characterization of Plant
Materials by PyrolysisField Ionization Mass Spectrometry V: Pattern
Recognition of Spruce Trees An Integrated, Analytical Approach to
Forest Damage. Environ. Sci. Technol., in press.
Hempfling, R. (1988). Charakterisierung verschiedener Waldhumusformen
und ihrer Dynamik durch analytische Pyrolyseverfahren. Bayreuther
Bodenkundl. Ber. 6, 1126.
Windig, W., H. L. C. Meuzelaar, F. Shafizadeh, and R. G. Kelsey 1984.
Biochemical Analysis of Wood and Wood Products by PyrolysisMass
Spectrometry and Multivariate Analysis. 3. Anal. Appi. Pyrolysis 6,
233250.
SECTION 2
PROLYSIS TECHNOLOGY
517
PYROLYSIS OF HAZARDOUS WASTE OIL

U. STEFFENSEN, J. FRANCK, R. RAHNENFHRER, and W. KAMINSKY
Institute for Technical and Macromolecular Chemistry
Summary
The recycling of waste oils which are contaminated with
organo-chlorine compounds is a problem of growing
economical and ecological importance. The combination of
the Recyclon-procees with fluidized bed pyrolysis offers
suitable method to dispose high loaded oils. In contrast
to other technologies the enormous advantages of the
described process are the low emissions, the low PCBconcentration and high quality of the yield products and
the minimal amounts of pyrolysis residue.
1. INTRODUCTION
More or less viscid liquid waste are used which are
composed of mineral oils, synthetic oils, oil containing
residues or water oil mixtures (1). The elemination of waste
oils in the Federal Republic of Germany was reorganized in
1986. Now it is part of waste ordinance according to which the
originator of the waste has to pay for its elimination.
Because of rising amounts of used lubricants with
different compositions (of polychlorinated compounds) in the
industrialized world, its recycling gets economical and
ecological importance. Especially the possibility of the
formation of highly toxic dioxines and furanes from chlorine
containing compounds by combustion or any other thermal
utilization attracts attention.
Many waste oils contain considerable concentrations of
chlorinated hydrocarbons because of the contamination of used
motor oils with used transformer oils.
The conventional utilization of waste oils gets impossible
because of the emissions of ordinary reprocessing plants. The
Recyclon process (2) offers a solution for dehalogenation of
waste oils by the reaction of a fine sodium dispersion with
chlorinated hydrocarbons to sodium chloride. After
distillation, a distillation residue of about 20% of the
feedstock is obtained. The combustion or deposition of this
viscous, salty residue is very difficult. The conversion to
chemical raw materials succeeds by fluidized bed pyrolysis.
518
FLUIDIZED BED PYROLYSIS
The core of the plant is an electrically heated reactor.
Its fluidized bed has a diameter of 80 mm and a height of 280
mm. The bed consists of quartzsand with particle sizes of 0,3
to 0,5 mm. A piston pump injects the preheated distillation
residue through a water cooled, ceramic isolated injector into
the fluidized bed, where the pyrolysis takes place (3). The
ceramic isolation inhibits an untimely decomposition of the
feedstock surely.
The inert fluidization gas conveys the gaseous or
evaporated reaction products out of the reactor through the
following cyclone to precipitate dust and fine grained coke and
sand. The porous pyrolysis residue adsorbs the melted sodium
chloride. Three cooler and an electrostatic precipitator
condense the pyrolysis oil. A membrane compressor conveys the
obtained pyrolysis gas as fluidization gas back into the
fluidized bed.Excessive gas is registrated by a gasmeter and
combusted in a torch.
The composition of the pyrolyeis products depends on the
temperature, the residence time, the feed, and the composition
of the fluidization gas. The most important parameter is the
temperature. It was variated between 590C and 750C.
As product fractions a pyrolysis gas, a pyrolysis oil,
carbon black, and pyrolysis residue, which contains coke and
the inorganic components of the distillation residue, are
obtained.
Pyrolysis o distillation residues - mass balances
Syo'C
6so"C
700'C
75"C
519
The best temperature to pyrolyse distillation residues is
700C. The yield of pyrolysis gas increases with increasing
temperature, while highboiling tars in the oil decreases.
The formation of the pyrolysis gas depends on the
pyrolysis temperature. Important components are methane, ethene
and propene.
Tab. I: Important Components of the Pyrolysis Gas in Dependence
on the Temperature (% by weight)
Temperature
590*C
650'C
700C
750C
Hydrogen
2,00
1,23
1,29
1.37
CO/CO
7,83
5,16
2,31
2,71
Methane
13,75
24,49
30,10
40,59
Ethene
17.76
22,58
32,56
31,34
Ethane
9,83
12,06
8,22
7,55
Propene
17.91
15.95
12,43
7,11
Propane
2,94
1,82
0,74
0,43
16,80
8,75
3,44
1,51
5,20
3,71
2,83
1,67
4,25
6,08
5.72
n/iso Butene
EC5-Hydrocarbons
Other Hydrocarbons
TOTAL
Gas density (kg/m 3 )
5,98
100
1,10
100
1,05
100
0,97
100
0,89
The yield of gaseous products, especially of methane and

ethane increases with the temperature. Fropene and ethane show
a maximum while the yield of compounds like propane and the C4and C5~hydrocarbons decreases with increasing temperature.
Traces of H 2 S are also obtained if the feedstock contains
sulphur components. COS can't be detected.
520
Tab. II
Important Components of the Pyrolyais Oil in Dependence of the Temperature

59o"C
6so*C
70o"C
750-C
C , Hydrocarbons
0,19
0,05
0,9
0,75
1,87
1,99
1,28
0,08
0,09
Temperature
Aliphatic Compounds
Hydrocarbons
7
C Hydrocarbons
C Hydrocarbons
9
C
Hydrocarbons
C
Hydrocarbons
0,24
0,193
o,97
0,81
0,86
0,39
1,02
0,49
0,13
0,76
0,86
0,49
0,38
0,89
0,43
0,50
0,57
0,2
0,30
0,76
12,93
16,34
Hydrocarbons
Cyclopcntaclicnc
n.d.
0,66
Aromatic Compounds
Benzene
0,42
2,44
Cyclohexadiene
0,03
0,38
1,29
o,37
Toluene
0,25
3,20
8,88
10,74
Ethylbcnzcnc
0,05
0,56
1,01
1,27
m/p-Xylcne
0,10
0,71
1.93
2,42
Styrcnc/o-Xylcnc
0,13
0,76
2,92
6,19
3.49
4,35
Mcthylstyrenc
n.d.
0,74
2,04
Indcnc
0,14
0,44
1,26
Mcthylindcnc
0,15
0,87
i,99
2,75
Naphthalene
0,15
0,38
1,44
4,58
2-Mcthylnaphthalcne
0,01
0,22
0,74
1,45
i-Methylnaphthalene
0,01
0,17
0.59
1,26
Biphenylene
0,01
0,07
0,15
0,24
Accnaphthcnc
0,01
0,12
0,30
0,35
Acenaphthylcne
0,01
0,11
0,34
0,45
Fluorene
n.d.
0,11
0,31
0,25
Phenanthrene
n.d.
0,09
0,25
0,19
Anthracene
n.d.
0,05
0,15
Other Hydrocarbons
Tar
C/H ratio of tar
0,05
8,13
16,4
30,5
14,6
85.59
64,79
25,06
25,96
I/I,74
1/1,67
1/1,01
1/0,94
521
The pyrolysis oils consists of many different compounds.
The yield of the oils increases with temperature and shows a
maximum at 700C.
The most important compounds of the oils are benzene,
toluene, xylene, tyrene, and naphthalene. The share of these
components raises with the temperature. Opposite to this the
share of the higher boiling tars decreases.
The C/H ratio of the tars grow less with higher
temperature.
Although the waste oil had been contaminated with 600
ppm' of FCBs. After the pyrolysis no PCBs, PCOOs, and PCDFs
could be detected.
REFERENCES
(1) Gesetz
(AbfG)
(2) Patent
(3) Patent
ber die Vermeidung und Entsorgung von Abfllen

(BGBl.) (waste law of FRG) I p. 1410
in FRG no. DE 2813200 C2, 1986
in FRG no. 3728871.7, 1988
522
ENERGAS
SEWAGE
SLUDGE
PYROLYSIS
H.-F. Hinrichs, H. Mller

ENERGAS, Gesellschaft zur Energiegewinnung
aus Mll und Kohle mbH
Summary
Due to the extension of the sewage sludge system in the Federal
Republik of Germany the annual amount of sewage sludge is increasing
constantly. Considering the restrictions on waste disposal, such as
composting and agricultural utilization, thermal processes are becoming more and more significant. Beside the mineralization and sterilization of sewage sludge in refuse incineration plants or flui di zed
bed reactors the ENERGAS pyrolysis process (ENERGAS KlrschlammPyrolyse = EKPy) is an interesting alternative for the treatment of
sewage sludge. The simple, compact construction of the indirectly
fired pyrolysis reactor including its measuring and regulation system
is suitable for the thermal treatment of sewage sludge. Additionally
it is possible to link noxious substances such as heavy metals, HCl,
etc. by additives.
The products obtained are gas and coke. The gas is combusted in
order to provide the energy for the degassification process and to
produce hot-water, steam and electricity with the surplus energy. Due
to its residue content of carbon the coke can be sold as a fuel or
used as activated carbon.
The process is especially suitable for catchment areas with a low
population density (100.000 EGW = calculated refuse production per
inhabitant) where the sewage sludge transport to bigger, thermal disposal plants (refuse incineration plants etc.) is economically unfavourable.
1. General - Sort, Amount and remain of the sewage sludge
Sewage sludge is a result of mechanical, biological and chemical treatment
of municipal sewage. It is a concentrate of solid substances contained in
dissolved or suspended form in untreated waste water. Its condition is not
only determined by the components of the sewage given to the purification
plant, but is essentially influenced by the purification process as well as
the sludge treatment applied in the purification plant.
In 1973 43 mill, tons of raw sludge (solid substances content 4,6 %)
or 2 mill, tons of dry matter and in 1986 50 mill, tons of raw sludge or
2,3 mill, tons of dry matter were produced.
Shown in statistics of the Umweltbundesamt for the years 1986/1987 the
sludge is disposed off as follows:
- Depositing
46,6 %
- Agricultural utilization
24,9 %
- Combustion
13,7 %
- Composting
1,3 %
- Others
13,5 %
523
However, depositing and agricultural utilization of sewage sludge is
getting increasingly difficult. This is due to generally less depositing
space available resp. the protests against such deposits. Moreover, sewage
sludge regulations on heavy metal content impose restrictions on the usage
of sewage sludge.
2. Current methods of thermal treatment of sewage sludge
The most suitable way of sanitation and decrease in volume is the combustion. Concerning the combustion the fluidized bed incineration is
especially approved for dried sewage sludge. By this process sewage
containing 25 - 30 % of dry matter can be combusted i. e. mineralized and
sterilized without special problems. The emission of noxious material,
especially of acid components, can be decreased by additon of limestone to
the fluidized bed incineration and by a succeeding flue gas cleaning.
Another way of combusting sewage sludge is to dry it as much as
possible and to blow it into the furnace of a refuse incineration plant
operating by means of grate firing. This process is also well approved. On
the other hand, it is possible to add adequately dried sewage sludge to the
refuse and to combust them together.
Although there are technical possibilities for the thermal treatment
of sewage sludge in a fluidized bed incineration as well as in a joint
combustion in refuse incineration plants, alternative thermal ways of
treatment are of high interest. That can be explained by the fact that in
the Federal Republik of Germany not even 50 refuse incineration plants are
in existence, but more than 8.800 purification plants. This means that now
as well as in the future there are not enough thermal plants for the treatment of sludge available.
Therefore, a thermal treatment process is required that can be applied
for small and medium sized purification plants at reasonable costs. An
alternative to the combustion of sewage sludge is the pyrolysis. Its
processing engineering principles are known and need not be explained in
detail. The pyrolysis reacts at the temperature range of 300 - 600 C and
does not require as high a temperature as the combustion.
3. Pyrolysis of sewage sludge - EKPy System
Basically the pyrolysis can be conducted under 2 different objectives:
- Pyrolysis for sanitation and decrease in volume with recourse recovery
at the same time
- Pyrolysis for sanitation, decrease in volume and energetic utilization
of the products obtained
Disadvantages of the pyrolysis are, however:
- The gets of the obtained products are far from covering the operating
costs.
- Experience with the pyrolysis has shown that the aromatics obtained are
too highly loaded to be sold.
In a way, at present only the energetic utilization of the sewage sludge is
favourable. Its objective is to split the sewage sludge into a usable gas
and a residue that can possibly be used as a fuel.
524
The conduction of the sewage sludge pyrolysis EKPy System proceeds as
follows:
Punctureproof or dry sewage sludge is given into the inlet device of
the stationary reactor. From there it is conveyed into the reactor by means
of a screw.
The reactor is subdivided into
stages:
- Drainage up to complete drying
- Heating up to 300 C
- Zone of pyrolysis of 300 - 500 C
The stationary reactor is heated wiht e. g. thermal oil. At the inside
transport equipment is provided. It is designed not only to convey sewage
sludge, but also to crush newly formed, bigger parts. This is achieved by
other stationary devices next to the conveyor, where bigger parts are demi ni shed. Furthermore the reactor contains a temperature probe controlling
all the individual processes.
4. Results of the sewage sludge pyrolysis by EKPy
The loss in weight depending on temperature is shown in figure 1.
The first graph shows the loss in weight dependence on temperature at air
addition (combustion conditions). The second graph shows the loss in weight
dependence on temperature in a nitrogen atmosphere ( pyrolysis conditions).
The decomposition, i. e. a noticeable output of substances, starts at
approx.
= 190 C. At higher temperatures there is still some output,
though it may be the beginning decomposition of anorganic substances.
200
Figure 1
400
600
800
1000
Temperature (Degree Celsius)
1200
: Loss in weight (%) depending on temperature

Graph 1 : Loss in weight at air addition
Graph 2 : Loss in weight in a nitrogen
atmosphere
525
According to the graph, at a temperature of 520 C the weight in loss
is 58 weight% related to the raw material. Raw material is the sewage
sludge when it is delivered to the purification plant, i. e. the organic
substance plus anorganic parts. The standardized value, the actually
determining value is 75,3 weight%. Therefore the residue of carbon
containing material of the sewage sludge input is 24,7 weight%.
Figure 2 shows the standardized loss in weight. From this graph the
loss in weight depending on temperature can be determined.
100
_.
90
80
1 70
fe
o
/
/
60
50
40
30
20
10
remperature
C
200
250
300
350
400
450
500
550
600
LO
"
200
Figure 2
Loss in weignt
weight%
6
16
31
50
62
70
75
77
70
70 t;
* ** >
400
600
800
Temperature (Degree Celsius]
1000
Loss in weight (%) standardized at

77 (%) org. sustances
sewage sludge pyrolysis < 650C
The essential pyrolysis rections happen at the temperature range of 200 and
520 550 C. At a higher temperature range turnover is neglible. The use
of higher temperatures is only suggestive to expedite the pyrolyis
reaction.
Additionally it is of high significance that at low temperature ranges
of 250 350 C only 50 % of sewage sludge input can be decomposed and
therefore considerable amounts of anorganic substances remain in the
residue.
Advisably, the pyrolysis of sewage sludge is conducted up to a final
temperature of 520/550 C. It is also possible to fix the final temperature
at 480 500 C and to prolong the time of treatment accordingly.
526
A product obtained at a temperature of 620 C was checked on carbon,
hydrogen and nitrogen. The temperature of 620 C was chosen because it
could be expected to obtain a completely degassed product. The following
data was received:
Element
Carbon
Hydrogen
nitrogen
Unit
weight-%
II
II
Actual value
34,22
0,92
2,38
Standardized value
77,77
2,09
5,41
527
COGENERATION PYROLYSIS
G. BONINO
Biomass Energies Integrated Systems
25 Strada della Viola, 10133 Turin, Italy
Summary
Exhaust gases from a wood or charcoal gasifier generating set can
provide the appropriate temperature and heat carrier to sustain a
pyrolysis process for charcoal production, as shown by tests which
have been conducted with satisfactory
results.
A commercial
application of the system is envisaged when operating gasifier
generating sets from 40-50 Kwel installed power upwards. The required
time is approximately four hours with a maximum product output of
about half a ton, within the 50-80 Kwel power range. Thus it is
possible to double the output to approximately one ton of charcoal in
the course of an eight hour working day.
This process adds new
economical flexibility to gasifier generating set utilization, with a
new and advantageous cost/benefit ratio. The pyrolysers are of simple
construction and the operational requirements are also simple.
Unloading is made easy by previously wrapping the wood during the
loading phase by means of metal nets. Cogeneration pyrolysis appears
to be most appropriate for agricultural residues which are carbonized
without wastes, an operation unlikely to be performed with traditional
kilns. The integration of systems, namely electricity and charcoal
production,
increases overall efficiency
and can add biomass
gasification for engine feeding with a new competitive profile also in
European conditions.
1. INTRODUCTION
No author on charcoal making seems to be aware that production of
commercial charcoal is also possible in an economically efficient and quick
way by using the sensible heat of engine exhaust gases out of a gasifier
generating set. Therefore, the scope of this paper is to provide more
information on this process which the writer has called 'Cogeneration
Pyrolysis' - meaning here the carbonization of biomass first started and
then sustained by means of the heat recovered (cogeneration) from the engine
thermodynamic cycle. As this process is strictly linked with producer gas
for electrical power production, it proposes mainly new flexibilities in
gasifier generating set operation, rather than aiming at competing with or
replacing other long established charcoal technologies.
In contrast to a traditional diesel fed generating set, the exhaust
gases of a gasifier generating set can directly transfer their sensible heat
to wood and/or agricultural residues, thus inducing the pyrolysis process
for their conversion into commercial charcoal.
Kilns are of simple construction, requiring an exhaust gas inlet at
the bottom centre and an outlet at the top leading to a chimney. No air has
to be allowed inside the kilns. Since they operate as engine mufflers, the
standard engine exhaust muffler becomes redundant and can be removed.
Build-up of counterpressure which reduces engine efficency is avoided by the
draught action provided by the chimney. The carbonization time span required
528
is reduced to between four and four and a half hours. Several stages of
charcoal formation are observed during this period. Although the engine
exhaust fumes have a temperature of about 380C at the beginning, the final
emission temperature at the chimney of the kilns remains constant at about
100C. The wood absorbs heat as it is dried, giving off its moisture as
water vapour. Subsequently, the temperature rises and eventually reaches the
point where exothermic decomposition of the wood starts. The temperature
stabilizes at approximately 500C.
Kilns of several cubic metres in size can cool off overnight so that
the charcoal can be removed on the following day. In order to make this
operation easy, rapid and relatively clean, nets are previously laid in the
kilns to wrap round the wood contained therein and form packages one over
the other. Thus the charcoal can be unloaded simply by hooking up the nets.
2.
This new integration of systems, namely electricity and charcoal,
should be investigated further as it can lead to additional applications.
One initial result is the opportunity for small charcoal gasifier generating
sets to produce the amount of fuel required for their own operation,
possibly from locally available agricultural residues, e.g. yellow corn
stokes. Charcoal in excess of the gasifier requirements can be used for
grill, or in developing countries, for cooking fuel. It is clear that if the
gasifier is working on wood or torrefied wood,
the total quantity of
charcoal produced is then available.
A relevant industrial application of cogeneration pyrolysis lies in
the medium to large size sawmills, especially those located in developing
countries. Sawmill wood wastes, excluding sawdust, account for 30 to 35% or
more of the original timber weight. The 300 Kwel size gas engine generating
set, on a three sets layout, can reach the one MW installed power often
required.
Charcoal conversion of wood wastes by means of cogeneration
pyrolysis can cheaply overcome the difficulty of their conversion into
useful electrical energy,
due to the high humidity content and size
differences. Once converted to charcoal, the original large sizes can be
reduced to producer gas requirements with little or no effort.
At this level of undertaking, the recovery of the energy contained in
the pyroligneous gases and vapours also becomes economically interesting and
feasible, thus abating the pollution caused by pyrolysis emissions in the
air. In fact, out of the total biomass energy content, 50% remains in the
charcoal and 50% is carried away with gases and vapours. From one thousand
kilograms of dry wood the following approximate heat quantities,
in
megajoules (MJ), are available: charcoal 9500 MJ 50%, gas 1500 MJ 8%,
condensibles 8000 MJ 42%.
The pyrolysis gas, when cleared of condensibles, has a composition
physically resembling that of producer gas inasmuch as the combustible gases
- carbon monoxide, methane and hydrogen - have approximately the same volume
in both instances. Likewise, the calorific values which average in both
cases 1100 to 1200 Kcal per cubic metre. In fact, the non reacting gas is
approximately 50% of the total volume in both cases - nitrogen for producer
gas and carbon dioxide for pyrolysis gas.
Two main total energy utilization scenarios can be envisaged:
burning the vapours and gases in order to dry the commercial wood
produced by the sawmill ;
separating gas from condensibles to use it in a dual fuel diesel
engine, the condensates to be burnt in the drying furnace.
529
Fig. 1. Wood charcoal from cogeneration pyrolysis
Fig. 2. Agricultural residues are easily converted to charcoal
530
CARBONISATION OF LARGE WOOD PIECES IN A LABORATORY RETORT

PRODUCT ANALYSIS AND ENERGY ASSESSMENT
N. SHAH &. P. GIRARD

ENERGIE Division
CTFT (Dpartement of CIRAD)
45 Bis, Avenue de la Belle Gabrielle
94736 NOGENT SUR MARNE (FRANCE)
R. CAPART
Dpartement Gnie Chimique
U.T.C.
BP 233
60206 COMPIEGNE (FRANCE)
Summary
Pyrolysis of big wood blocks (65 mm* 35 mm* 35 mm) of Oak and plaquettes (250 mm* 40 mm* 25 mm) of Assao was studied in a laboratory retort to investigate : 1. Supplementary Specific Energy required to
carbonise 1 kg of dry wood (termed hereinafter as SSE). An attempt is
also made to estimate thermicity of pyrolysis reactions and the value is verified later by isothermal calorimetrie analysis.
2. Indicators characterising the retort carbonisation such as :
a) weight & net energy efficiencies,
b) effluents produced per kg. of dry wood carbonised (condensibles and non-condensibles),
c) effluents produced as a function of carbonisation cycle time,
d) SSE consumption.
The pyrolysis retort set-up is classical (with possibilities of recuperation of all effluents generated) and uses electrical resistors to
provide heat for carbonising wood. Electrical energy utilized during
a complete cycle of carbonisation was measured by a w-hr meter to estimate the SSE. Other technical carbonisation process parameters (i.e.
initial wood moisture, final temperatures, residence time at final
temperatures and heating rates employed) were varied and chosen to approach field carbonisation at industrial scale. This paper reports
the typical results achieved with the laboratory set-up used. The results are compared with the industrial retort-kiln measures.
Amongst all the methods of thermo-chemical conversion of wood into upgraded fuels, pyrolysis/carbonisation is most well-known, commonly practised presently and is poised to play even grater role if the conversion efficiencies are further improved and when the oil based fossil-fuels become more expensive and scarce. As an evidence of trade importance France
consumed in 1985 about 115,000 tons of charcoal. The traditional methods
of charcoal making (without emissions recovery) are known to be less than
50 % energy efficient and could also cause environmental nuisance if charcoal emissions are unutilised or untreated (1).
According to (2) it was discovered that the energy demand of a charcoal process is closely related to the retort capacity, if the operation
takes pace batchwise. However, the yields of charcoal and byproducts are
very little affected by alteration of the retort capacity.
531
The objective of this research work was to characterise the batch retort pyrolysis process.
MATERIALS AND METHODS
The details about the wood used in this study are given in Table 1.
Schematics of the laboratory retort with condensate recuperator and measurement instrumentation used is shown in Fig. 1. Two wood heating rates
such as 1.5 'C/min (Tests 1, 2, 5, 6, 7 4 8) and 4,5 'C/min (Tests 3 & 4)
were used. The final temperatures reached i.e. 400-600 "C corresponds to
the field charcoal making practise and the typical heating rates employed for field carbonisation are mostly between 1-2 *C/min. The emissions of carbonisation were passed through the condensor maintained at
0 "C and additional security condensor traps assured the complete condensation before the emissions pass through a dry filter, gas meter and finally were collected in a rubber balloon.
The condensates recuperated at different temperatures were measured
for its weight and were later analysed in the laboratory to know its composition according to the procedure given in (3). The non-condensable
fraction was sampled during the cycle at different temperatures and was
analysed to know the correct composition by gas chromatography. The calorific values were calculated separately for condensables and non-condensibles and were added to give total potential energy of the effluents.
The charcoal was analysed for its humidity, volatile contents and ash
to calculate
PC
(fixed carbon) content (proximate analysis method
NF B55101). The calorific values of wood and charcoal were determined by
bomb calorimeter. The charcoal friability was measured using a classical
method of trommel adapted from coal testing procedures. The friability of
charcoal is a commercially important parameter and here it gives a relative measure of physical strength of charcoal which could indicate its resistance to handling losses.
Measurement of SSE of carbonisation and estimation of heat of pyrolysis : the effective energy used to carbonise 1 kg of dry wood was found
as below :
Em = ( E(w + r) - E(r) )/Mb
where,
Em
: energy consumption measured giving SSE in MjAg dry wood
E(w+r) : energy required to heat wood charge and retort
E(r)
: energy required to heat only retort without wood
Mb
: weight of dry wood
The following equation calculates Ec :
t^f
Ec =CMw.Cpw(100 -Ti) + Mw.Lv + Mb.Cpb(270 - Ti) +l7J Mr.CptdT]] /Mb
Simplification : Tf( Mr.CptdT = (Mb + Mc)/2).Cpt (Tf - 270)
Where,
zjo
: weight of moisture in the wood
Mw
Cpw Cpb, Cpt : specific heat of water, dry wood and residual weight
at about 270 "C (residual charge is considered as torrefied wood)
Lv
latent heat of vaporisation of water at 100 *C
Mc
weight of charcoal produced
Ti, Tf
initial and final temperature respectively
Mr
residual weight between 270 "C and Tf that changes
with temperature and is close to (Mb + Mc)/2
The Ec a
and Em values were compared. Since the measured values turned
out to be always
a
inferior to those calculated we are lead to formulate a
532
hypothesis that the differential heat comes from reaction heat which is
evidently exothermic. Thus an estimation of pyrolysis heat value (Hr) was
done as below :
Hr = Ec - Em
To verify the results obtained from the retort isothermal calorimetrie analysis was done using Calvet type calorimeter (SETARM HT 1 000).
RESULTS AND DISCUSSION
Table 1 summarises the principle characteristics of eight carbonisa
tions.
Influence of heating rate on carbonisation process :
It was observed that rapid heating (4.5 'C/min) provokes gas forma
tion and reduces charcoal yield. Higher heating rate also produced a char
coal of nonacceptable friability. Hence from the limited experimenta
tion in this study (only two heating rates employed) it could be said
that the heating rate needs to be optimised to minimize process duration
and maximize charcoal yields.
Carbonisation effluents :
From the analysis of carbonisation effluents, one could estimate the
product distribution at a given temperature of wood charge.
Following was generally observed :
Until wood reaches about 150 "C the components other than water are
not found in the effluents whereas acetic acid and furfural starts volata
lising when wood reaches about 180200 'C.
The bulk of pyrolysis reactions take place between 270400 "C du
ring which the maximum effluents are produced.
After 540 'C the effluents would contain mostly noncondensible ga
ses and practically no fraction is condensed at 0 *C.
Other technical carbonisation parameters.
Weight efficiency :
The usual fashion of calculating weight efficiency (charcoal wt./wood
wt.) does not take into account the quality of charcoal and hence in or
der to have a fair comparison of weight efficiencies of charcoal produ
ced of different qualities, an efficiency indicator (E80) is calculated
as below : E80 = Wt. eff (db)* FC (x)/80
where,
E80
: Efficiency indicator calculated considering charcoal
having FC of 80 X
Wt. eff. (db) : Weight of charcoal/weight of dry wood used
FC ()
: X FC of charcoal obtained in each test.
The E80 for this retort lies between 3340 X for carbonisation
between 400600 *C. The higher values corresponded to slow heating rate
(1. 5 'C/min). Thus while employing rapid heating rate one may gain time
at the cost of reduced charcoal yields. The tradeoffs could be determi
ned for a given technology while product qualities are matched with the
market demands.
Initial moisture content :
The initial moisture content of wood directly affects two important
parameters of the process viz. cycle duration i SSE. The energy required
for drying of initial moisture of wood represents a large fraction of SSE
requirement of carbonisation. A s seen in Table 1 to carbonise about same
quantity of dry wood at initial moisture content of 47 X (wb) required
about 1.5 times longer time than the wood at 0 X moisture to obtain near
ly same quality charcoal (PC). About 35 X reduction in SSE was obtained
when initial moisture content dropped from 47 X to 30 X (wb).
533
Fixed carbon (FC) content : FC is an important indicator of quality
of charcoal and is used as a criterion to classify charcoal for trade. As
seen from results in Table 1 higher the temperature of conversion higher
is the FC to a certain limit. The residence time at the final temperature also has a similar effect on FC.
Friability index : Higher the index value lesser is the charcoal resistance to physical shocks. The values of friability index illustrated
in Table 1 indicate that higher the heating rate lower is the resistive
quality.
Energy assessment of the process : As seen from the results in the Table 1 the charcoal making in the laboratory retort has energy conversion
efficiency between 53-57 % when heating rate employed is 1.5 "C/min. The
energy conversion efficiency could drop down to 44-49 % if heating rate
of 4.5 "C/min is used. The values of potential energy content of effluents are calculated per kg of dry wood carbonised and are represented
in Table 2. This experience of studing the effluents from a retort kiln
leads into following general conclusions :
a) GHV (gross heating value) of noncondensable gases varies according to the cycle time and the weighted average value could be taken as
13 MJ/Nm3.
b) About 65-70 % of condensibles is water and the rest has GHV of
about 25 MJ/Nm3.
c) The condensible combustibles represent about 50-60 % of the total
GHV of the effluents.
Table 3 shows the SSE of carbonisation. Fluegge (4) had reported the
SSE values of 1420 kJ/kg dry wood for a batch retort (Reichert) and put
forward the advantage gained while using continuous retort system (Sific
retort) that demanded only 71 kJ/kg dry wood (enhanced heat exchange rate in continuous retort where wood charge is moving). The average value
of reaction heat found in this study is about 435 kJ/kg dry wood which
has the same order of magnitude as reviewed by (5). It is widely understood that the pyrolysis of wood till a certain temperature (about 270280 *C) is endothermic whereafter the reactions turn to be exothermic and
if the pyrolysis is continued further till say 400-500 "C the global balance of reaction heat could be slightly exo/endo-thermic. The isothermal calorimetrie analysis on about 60 mg of wood samples in Calvet type
calorimeter gave reaction heat value of about 150 kJ/kg (endo).
It was interesting to note that 70 % reduction in SSE could be achieved as a result of emissions recovery for providing carbonisation heat.
This explains the recent interest shown by carbonisation industries in valorisation of effluents of carbonisation for optimal wood energy conversion.
REFERENCES
(1) GIRARD Ph., Atmospheric pollution from charcoal manufacture. State of
production in use, IUFRO 5. Division Conf. Sao Paulo, (May 1988).
(2) WALTER E., Handbook of charcoal making, EEC. Solar Energy R & D . Series E, vol. 7, (1985).
(3) VERGNET A.M. and VILLENEUVE F., Techniques for the analysis of pyrolysis gases and liquids from tropical biomass. Bois et Forts des Trpiques. N' 205, III quarter,( 1984), CTFT.
(4) FLUEGGE F., Chemische Technologie des Holzes (56,57), Munich FRG
(1954).
(5) WAI-CHUN, R. CAHN, M. KELBON & B. KRIEGER, Modelling and experimental verification of physical and chemical processes during pyrolysis
of a large biomass particle, Fuel, vol. 64. (Nov. 1985) pp. 1505-13.
534
I. Retort
2. Heating program renul ator 3. Temperature recorder
4.6.7.9 Refrigerant
5. Condensate collector
10. Dry filter
II. Security vase
12. Gas meter
13. Gas collector balloon
Fig. 1 : SCHEMATICS OF THE CARBONISATION RETORT & EFFLUENTS
RECUPERATION SYSTEMS
Table 1 : GLOBAL ELEMENTS CHARACTERISING CARBONISATION IN

LAB RETORT
test ' tnp of rende nei
HOD
t IM it haidit; Dry it
doriti cubo
(d)
(kr)
Cc) TI (kr) l i b
1) 14.0
550SM
2.0
2)9.0
550600
3)5.5
550600
4)5.5
550600
511.0
en
CUtCOil
Telatile FC
IA
ar
V/U
mietila
Iriibilit
I
wit CH
XA
t
irrUHTS/U drr nod

bern I n end Cndeu
Tot tol
I
U
0120 tali h 3
47
1,5
19,8
7,9
90,9
34,3
17,1
35,0
39,8
56,6
0,16
434
0,70
2,0
1,56
19,9
6,4
92,6
35,2
16,3
35,5
41,1
63,1
0,17
414
0,(1
2,5
31
1,47
19,2
4,9
94,1
31,5
31,5
21,6
33,6
44,1
0,19
426
1.72
2,5
29
1,51
19,2
5,4
93,2
34,7
34,7
21,0
32,1
41.5
0,19
399
0,(9
400475
4,1
10
2,65
20,3
16,2
11,9
32,8
32,8
34,0
34,1
53,1
0,11
450
0,(7
6)7.3
400475
1,5
10
2,65
20,3
11.4
79,9
32,5
32,5
35,3
35,3
55,3
0,12
409
0,63
7)5.5
440490
0,6
2,96
20,3
16,0
80,3
32,7
32,7
35,1
35,2
56,1
0,13
433
0,67
114.0
390410
2,49
20,3
24,4
73,2
31,0
31,0
37,8
34,6
57,7
0,10
371
0,56
535
Table 2
Test
N'
Potential Energy of Effluents

(per kg of dry wood carbonised)
Non cond. Condensibles

MJ
gases MJ
2,08
2,21
2,47
2,47
1,43
1,56
1,69
1,30
1
2
3
4
5
6
7
8
Total
MJ/Nm3
MJ
2,28
2,17
2,24
2,10
2,36
2,15
2,27
1,94
4,36
4,38
4,71
4,57
3,79
3,71
4,96
3,24
6,22
6,44
6,54
6,62
5,66
5,89
7,4
5,78
Table 3 : SSE required & heat of reaction

(per kg dry wood)
Test
N'
1
2
3
4
5
6
7
8
SSE (kJ)
Exothermicity
meas (ra calc (c) (c) - (m) (kJ)
1 370
0 (*)
900
850
400
430
170
0 (*)
2 610
210
1 460
1 360
530
530
430
300
1 240
210
560
510
130
470
260
300
(*) negligible
Table 4 : Comparative SSE requirement data
Retort
system
1. Lab retort
(well insulated)
capacity 9, 7 lit
2. M.S.T.
single retort
capacity 3 m3
3. A.C.C.
two retorts coupled
capacity 5,6 m3 each
(*) negligible
Source of
Wood X
suppl. heat humidity
SSE cons.
Mj/kg dry wood
electricity
0-47
(*) 0 - 1,37
wastewood
14 - 23
4,8 - 8,5
11,7 - 47
3,16 - 7,2
i)wastewood
. without
emissions
recovery
. with
emissions
recovery
ii) propane
11.7
0,88
11,7
1,3 - 1,54
536
MILD PYROLYSIS PROCESS IMPROVES STEAM CYCLE EFFICIENCY

P. Graversen, R.M. Hummelshj, and . Jenslev
COWIconsult, Consulting Engineers and Planners AS
45 Teknikerbyen, DK-2830 Virum, Denmark
Telephone 45 42 85 73 11, telex 37 280 cowl dk.
Summary
This paper describes a new design for combining a traditional
steam cycle power plant fueled by municipal refuse with a pyrolysis
unit for biomass e.g. straw.
The electricity gain from the traditional plant is limited by
a superheating temperature of 380-430C. Above this temperature
chlorides in the fluegas mainly from PVC in the refuse will result
in high-temperature corrosion.
In this new concept the much less corrosive pyrolysis gas is
used in a separate super-heater in order to increase the steam
temperature above this limit. Approx. 80% of the energy added to
the steam in the super-heater can be converted to electricity. The
degassed biomass is utilized in the furnace/boi1er increasing the
steamflow and hereby also increasing the electricity production
further.
The pyrolysis unit is designed as a simple duct which is heated
externally to 600C by fluegasses and through which the compressed
biomass is fed using a hydraulic piston machine.
The overall efficiency and electricity production from the
biomass resource, in this case straw, can be compared with the
best gasifier-engine based system but without the well-known
operational problems associated hereto, e.g. tar-cracking,
condensate removal, clogging and slag sintering.
1. Background
During participation and work in an adviser group for the Danish
Ministry of Energy, 15 gasification plants, mainly in industrial scale
in various countries, have been visited. The aim of the work was to
registrate state-of-the-art and to point out R&D areas of interest for
Denmark.
The biggest unexploited biomass resource for gasification and
pyrolysis purpose in Denmark is straw and municipal organic waste, but
energywise utilization of this resource is mainly seen as incineration
plants for production of district heating.
Straw is, however, abundantly available in Denmark and the northern
agricultural zones in general, and abroad there is hardly no previous
experience abroad with pyrolysis and gasification of straw. Therefore
the R&D of processes where this resource can be converted to electricity
are given a high priority in Denmark.
In the following, one of the new promising concepts is described.
537
2. Limits of traditional processes
Through the previously mentioned study of the state-of-art for many
pyrolysis and gasification methods already tested, the basic knowledge
gained was to a large extend, how not to do. Therefore, our approach is
to develop a very simple process that works and short-cuts the wellknown limits and problem areas of traditional concepts.
The limits for the traditional steamcycle concepts are:
*
*
High-temperature corrosion, slag sintering, and erosion in the

super-heater due to high content of chlorides - mainly from PVC
in the refuse - and fly-ash in the fluegas.
Low power/heat ratio due to low superheating temperature of max
380C-430C in order to reduce the speed of the above mentioned
corrosion.
Corrosion
Surface temperature
100
Fig. 1
300
500
700 C
Corrosion speed by fluegas from combustion of municipal refuse.
Experience shows that straw is not readily accepted by any of the

traditional gasification and pyrolysis processes due to associated
technical and economic problems.
The limits for earlier straw gasification concepts are:
*
*
*
*
Power and maintenance demanding pretreatment i.e. chopping of

straw
Clogging of silo and gasifier
Slag sintering and ash softening above 800C
Difficult gas cleaning in combination with engine/gen-set
(tar/condensate formation and dust removal)
3. Principle of the new concept

The pyrolysis unit is combined with a traditional steam cycle
power plant fueled by municipal refuse, see dotted line on fig. 2.
Non-chopped straw is fed through 1-3 parallel pyrolysis ducts
depending on size - using a hydraulic piston machine.
The straw is compressed to a density above 160 kg/m^.
538
The first section of the pyrolysis is perforated and acts as a
convective dryer zone using fluegas circulation.
The second section is heated externally with fluegas from a
separate super-heater, see fig 2, in order to pyrolyse the dried straw
at approx. 600C, i.e. below the ash softening temperature.
The pyrolysis process is initiated using another heat source.
The hot gas generated incl. the vapours of the tar fraction are
representing more than 50% of the energy content of the energy content
in the initial straw, and are utilized in the separate super-heater
without letting the temperature of the pyrolysis gas fall below the
tar dew point at any place.
Approx. 80% of the energy added to the steam in the super-heater
can be converted in the turbine to mechanical energy/electricity.
As the gas has a low content of chlorides and particles, the
additional superheating will not create corrosion problems, as would
be the case when increasing the superheating temperature in a
traditional concept where the superheating is performed by the
fluegasses directly from the incinerator plant.
The degassed 'straw coke' is also utilized to increase the
electricity production as it is fed into the furnace/boiler which
creates the heat necessary to evaporate the steam. The steam is
evaporated at a temperature below the limit for high-temperature
corrosion. Hereby this straw based top-up fuel raises the calorific
value of the municipal refuse basically used, which results in an
increased steamflow/electricity production.
The overall efficiency will be above 80% for the straw utilization
itself, and with a power/heat ratio of approx. 0.7 comparable with the
best gasifier genset based systems but without the well-known problems
associated hereto.
The extra capital costs of a complete pyrolysis plant for a 4 t/h
waste to energy plant based on municipal refuse incl. the necessary
modifications are below 0.7 mill ECU, which amount shall be compared
with an increase in the electricity output of 26-58%.
The advantages of the new concept can be summarized in the
following headlines:
*
*
*
*
*
*
*
*
*
*
Improvement of the electricity gain by 26-58%

Essential reduction of high-temperature corrosion
No risk for ash softening and slag sintering
No demand for gas cleaning or tar cracking
No condensate disposal demand
Low N 0 X combustion at approx. 1200C
Low demand for moisture control of biomass due to built-in
dryer section with heat recovery
Easy handling (no pretreatment, stirring devices,
adding/regeneration of catalysts or need for modification of a
gas-engine)
Due to the simple pyrolysis unit design can presumably be
modified to handle other biomass fuels, e.g. wood chips, shells,
park and garden waste or a mixture of these and straw
Low marginal cost
539
1
Seperate super-heater
4 8 5 1 66 bar
380167 bar
Pvrolvsls gas
Municipal
refuse
>
Ruegas
to filter/scrubber
Fig. 2
Fvrolvsis unit
/T\
K J\
\ry
I District
heating/
IhBatsink
\
>
/
e-
Simplified process diagram

Mech. Dower
Municipal refuse
100%
Furnace
Steam
380t
Generator
+ gear
Turbine
Condenser
Electricity
17.7%
2.0 MWe
n
56%
Heat
Waste
\ \
>6.5 MJ/s
/
4t/h
11.6 MJ/s
10440kJ/kg
Power/heait ratio = 0.31
Fig. 3
Sankey diagram for a traditional waste to energy plant

f
Ruegas
760kg/h
Straw
Pyrolysis
26%
unit
Pyrolysis gas
Turbine
[coke
Municipal waste
100%
Mech. power
superheater
Steam
485C
Bedridtv
Generator
+ gear
Condenser
Furnace
28%
i
\
70%
Heat
Waste i
4t/h
11.6MJ/S
10440kJ/Xg
Fig. 4
3.2SMW
VlMJ/s
^\^
Power/heat ratio = 0.4
Sankey diagram for a waste to energy plant improved with the

pyrolysis unit
540
4. Present Stage and Perspective
Our concept has in 1987 been awarded the first prize in a Danish
competition for utilization of non-imported fuels for decentralized
co-generation power plants, funded by the Danish power company
ELKRAFT.
Laboratory tests with the pyrolysis unit carried out by the
TECHNICAL UNIVERSITY OF DENMARK during last year have shown very
positive results.
Product development and engineering are carried out in
collaboration with the Danish manufacturer VLUND.
The straw handling and hydraulic piston feeder machines are already
developed to commercial scale in the MW size.
Patent rights have been claimed for the principle and involved
machinery.
A pyrolysis unit for 120 kW is scheduled for test during autumn
of 1989.
If the test in pilot scale also confirms the present optimistic
views, then the path is open to full size demonstration in the MW size.
It is expected that the concept has wide perspectives, especially in
countries where end-disposal of waste involves a fee, which, together
with sold electricity and in many cases district heating, will serve as
a source of income for this type of plant.
REFERENCES
(1)
(2)
(3)
COWIconsult, Vlund Energy, The Technical University of Denmark,

Laboratory for Energetics (1989), Development of a Pyrolysis Unit,
a) Main Report b) Report of Experimental Work c) Appendices (Danish
Language).
Janzen, P., The Danish Corrosion Centre (1988), Proceedings of a
conference on corrosion problems associated to biomass fueled
decentralized power plants (Danish Language).
Ministry of Energy, Energy Research Programme, Steering Committee
for Biomass, Denmark (1987). Report on biomass to energy
utilization via thermochemical conversion methods (Danish Language)
541
FLASH PYROLYSIS OF BIOMASS FOR LIQUID FUELS
S A Bridge and A V Bridgwater
Department of Chemical Engineering and Applied Chemistry
Aston University
Aston Triangle
Birmingham B4 7ET
UK
ABSTRACT
Fast or flash pyrolysis has been shown to give very high yields of liquid "bio-oil" on
laboratory scale processes of up to 70%. The principle of flash pyrolysis for liquids
production is that very high heating rates are combined with relatively low temperatures
and with rapid quenching of liquid intermediate pyrolysis products. Several techniques
have been employed including fluid beds, entrained flow reactors, cyclone and vortex
reactors; and the principles employed include gas-solid heat transfer as in entrained
flow reactors and solid-solid heat transfer as in ablative pyrolysis. This paper reviews
the reaction mechanisms, pathways and kinetics of pyrolysis by reference to the flash
pyrolysis technologies employed to date. Conceptual designs for liquid producing
pyrolysis processes are developed from specifications laid down for process
performance by evaluating known theories of reaction pathways and mechanisms, and
by examining the resultant technical requirements.
INTRODUCTION
Pyrolysis produces a solid char, liquid products (tar and pyroligneous acid) and a fuel
gas, the proportions of which are dependent on the process conditions and the nature of the
feedstock. Current interest is focussed on liquid fuels which include the crude pyrolysis liquid
or "bio-oil", upgraded products such as gasoline and diesel, char-water slurries and char-oil
slurries. The first of these, bio-oil, is of particular interest as it is a liquid that can readily
substitute for conventional hydrocarbon fuel oils, and it has been produced on laboratory scale
processes at yields of up to 70% using fast or flash pyrolysis technology.
This paper prescribes a specification for an ideal pyrolysis process. By analysis of
reaction mechanisms, reaction pathways, models of pyrolysis processes, and evaluation of
technical requirements, a conceptual process is outlined and compared to the initial
specification.
SPECIFICATION
The specifications of an ideal pyrolysis process are set out in Table 1. While clearly
these are not all possible and some are contradictory, this does identify the main features that a
successful and competitive process has to address. After consideration of the principles of
pyrolysis, these are re-examined to form the basis of a potentially successful plant.
Pyrolysis liquids approximate to the original biomass in elemental composition by the
following idealised relationship:
C6H9O4
>
C6H9O4
In practice the following reactions can be considered to occur in flash pyrolysis:
2C6H9O4
>
2C6H7O3 + 2H2O
4C6H9O4
>
16CO + 8CH4 + 2H2
2CO + 2H2O
>
2C02 + 2H2
6C6H9O4
>
2C6H7O3 + 14CO + 8CH4 + 4H2 + 2C02
542
Table 1
Ideal Pyrolysis Process Specification for Liquids Production
PROCESS
Minimum feedstock pretreatment and preparation
Maximum feedstock versatility and insensitivity to feedstock characteristics
Minimum heat input to reactor
Minimum heat losses
Minimum reaction temperature
Good separation of oil and water phases
Minimum number of product separation steps
Minimum product stabilisation and/or upgrading
Scaleability
PRODUCTS
QU
Maximum oil yield
Maximum oil HHV
Minimum char content
Minimum oxygen content
Minimum water content
Neutral pH
Easy upgradability
Low viscosity
Single phase
High stability
Char
Minimum char yield
Minimum volatiles
Gas
Minimum gas energy
As clean as possible
Water
Minimum yield
Minimum COD
Neutral pH
REACTION PATHWAYS AND MECHANISMS

Pyrolytic reactions are very complex and consist of both concurrent and consecutive
reactions which results in a variety of products. The general overall mechanism for fast
pyrolysis is dehydration, depolymerisation followed by melting and vaporisation to form
vapours and gases with minimum char formation. However different pathways may be taken
depending on the process conditions.
The most recent hypothesis on reaction pathways of fast pyrolysis has been proposed
by Evans and Milne (1) based on molecular-beam, mass-spectrometric sampling (MBMS).
They postulated that the primary vapours formed in the rapid pyrolysis of biomass under high
pressure (but in the absence of catalysts or reactive environments) appear to have the same
composition as the vapours obtained directly from low-pressure pyrolysis. Under high
pressure conditions, the direct formation of a liquid product mixture is due to the pyrolysis of
wood that has become "plastic" at the temperatures and pressures involved. This has been
confirmed by Diebold (2) and Led et al. (3) who have shown that under direct-contact fast
pyrolysis conditions, wood exhibits many properties of a "molten plastic state". At low
pressures they found that the charcoal formed, though retaining structural features of the wood,
shrinks, which could indicate a plastic state where pyrolysis products pass directly into a liquid
state before devolatilisation. The direct formation of gaseous species from primary pyrolysis
reactions, known as prompt gases, are primarily CO2, H2O and CO. These are largely
associated with the char forming reactions.
The sequential transformation of the primary products in the vapour phase is shown in
Figure 1 as passing through three stages. In the first stage at temperatures between 500-600C,
slight cracking reactions occur before substantial conversion occurs to permanent gases. The
higher molecular weight lignin products are cracked to lighter aromatics and oxygenates. The
second stage occurs from about 600-700C with the formation of secondary products
characterised by CO, light olefins and aromatics. Aromatics are also formed from the primary
products of carbohydrate degradation at this stage. The third stage above 700C, gives tertiary
products from thermal degradation which include CO, CO2, H2, CH4, low molecular weight
543
saturated and unsaturated hydrocarbons and some polynuclear aromatics. These are generally
formed only in high temperature conversion processes such as gasification and combustion,
and in low yield.
lePyrolytlt severity
Blomais
Solid
Phai
Liquid
Phis
Gat
Phas
Primary procassas
Figure 1
ISecondary processes;
< | | T e r t l s r y processes s|ts~
Reaction Pathways in Biomass Flash Pyrolysis (1)
MODELLING
Modelling implies mathematical descriptions designed to help in the analysis and
understanding of complex physical or chemical processes. The development of a mathematical
model can be theoretical using physicochemical principles, empirical based on experimental
data, statistical or any combination of the three. The need to develop models for pyrolysis may
be attributed to the following reasons:
to provide a step for establishing better reactor design techniques,
to develop a diagnostic tool for evaluating the importance of the various system
parameters such as particle size, heat of pyrolysis (reaction) and thermal properties
of the feedstock and products,
to identify system characteristics or conditions useful to researchers,
to predict devolatilisation behaviour as a function of reactor conditions like weight
loss, volatile release rate, product distribution and composition and temperature
profiles,
to be applied when experiments are too expensive to be conducted or are not
possible.
A knowledge of the system kinetics is necessary in order to satisfactorily design or
simulate the process equipment. Several models have been proposed and a few are outlined in
the section below.
Kinetic models of pyrolysis
The pyrolysis process has been shown to be very complex and is a dynamic process in
which reaction quenching is a critical part of the process for obtaining liquid products. The
pathway generally quoted for the overall pyrolysis process is
biomass > char + voltiles
and the rate of the above reaction is described in the form of a first order Arrhenius type rate
law:
dp/dt
=
kexpE/RT(ppf)
where represents the local density, pf the final density, k the preexponential (frequency)
544
factor, E, the activation energy and R, the universal gas constant.
If the sample is heated at a constant rate M, then:
dp/dt
=
-k/Mexp-E/RT(p-pf)
The kinetic parameters, E and k, are usually derived from weight loss data obtained by
either dynamic or static thermogravimetric analysis (TGA). Owing to the different
experimental conditions used to carry out these studies, considerable variations exist in the
published values of kinetic constants. This makes it very difficult to generate general pyrolysis
models due to the specificity of essential data to specific experimental conditions and
feedstocks. These models cannot be used to predict product yields. Other methods used for
predicting weight loss have modelled the activation energy as a function of the extent of
reaction (4), used constant kinetic parameters but different orders of reaction (5), and used
different kinetic parameters for different parts of the reaction (6).
The modelling of biomass pyrolysis in terms of individual products has also been
proposed (7). However kinetic parameters cannot be predicted a priori and must be estimated
from experimental data, a problem that increases as the number of reactions postulated
increases. It has been suggested that this model should be viewed as a method for correlating
data and comparing results from different biomass materials.
Rate laws based on a competitive mechanism have also been proposed to account for
the variations in product yields with temperature and heating rate. Bradbury, Shafizadeh et al.
(8) and Diebold (9) have used this technique to investigate the kinetics of cellulose pyrolysis.
Recently kinetic models for the secondary decomposition of primary pyrolysis tars have
been proposed (10,11,12). Testing of these models showed that predicted liquid yields agreed
with achieved yields within 10% for the temperature range 500-700C with residence times
of up to 1 second (13,14).
Different approaches have been used to develop kinetic models. However, most have
been developed for predicting the weight loss of biomass rather than the product yield and
distribution. One research group found that even a change of 1 kcal/mol in the activation
energy of a competitive, multi-step reaction scheme caused changes in the product yield and
distribution (15). Hence research in this area of pyrolysis requires further investigation.
For a complete model of pyrolysis the kinetic equation must be coupled with equations
describing transport phenomena.
HEAT TRANSFER
Several reactor configurations have been employed for flash pyrolysis such as fluid
beds, entrained flow reactors and cyclone reactors, and each configuration heats the feed in a
different way. In fluid beds the feed is heated indirectly by convective and radiative heat
transfer from hot solids such as sand, in entrained flow reactors heat transfer is mainly by
convection from hot gases, and in cyclones heat transfer is by intimate contact of the particles
with the hot wall surfaces. In the latter case, solid-liquid-solid heat transfer occurs which is
significantly different from the gas phase heat transfer processes in fluid bed and entrained
flow reactors, and this is known as ablative pyrolysis. Higher heat transfer coefficients are
achieved using this technique resulting in potentially higher reactor specific capacities and
smaller reactor volumes as there is no need for a heat transfer gas. Also this very high rate of
heat transfer in ablative pyrolysis results in the almost exclusive production of liquids and
gases which makes this process attractive for the conversion of biomass to liquid fuels.
Heating rate
Heating rate and final temperature both play important roles in the product distribution
and yields from pyrolysis. At low heating rates of less than lC/s and at relatively low
temperatures of less than 500C, char, gas and liquid products are produced in approximately
equal amounts. Flash and fast pyrolysis, including ablative pyrolysis, are claimed to involve
extremely high heating rates of up to lxl06C/s and very short residence times of less than 1
second in order to maximise either liquid or gas production while minimising char formation.
If the desired product is liquids, moderate temperatures of between 400C to not more than
650C and rapid quenching have to be employed so that pyrolysis vapours are condensed
before secondary reactions occur. Higher yields of gases are obtained at temperatures greater
545
than 650C. The main focus of pyrolysis research in Europe currently, is the production of
liquids either for direct use or for upgrading to give high quality hydrocarbon fuels such as
gasoline.
CONCEPTUAL DESIGN OF PYROLYSER FOR LIQUID FUELS
Theory
From the specifications outlined in Table 1 and the comparisons of the flash pyrolysis
technologies mentioned above, ablative pyrolysis appears to be the most attractive route to
employ for the production of liquid fuels. This is due to the high heat transfer rates, low
reactor volume, better temperature control, and potentially higher liquid yields resulting from
these advantages.
Fundamental research on ablative pyrolysis has been carried out by Led et al. (3). A
stainless steel disc of 7.5 cm diameter, spinning at a constant and controlled speed, was heated
to different temperatures by four gas burners underneath. Wood dowels were pressed
vertically onto the hot surface by weights on the upper part of the rod. From their experiments,
the following relationships were obtained:
(i)
V = a.p
where
V is ablation rate, m/s (speed of consumption of wood dowel)
is pressure, Pa
a is constant, m slPa1
()
h = 0.017
where
h is heat transfer coefficient, W m2K4
is pressure, Pa
(iii)
Td = 739 (466C)
where
Td is temperature of decomposition
Led believed that decomposition occurs and is completed when the temperature of
wood reaches 466C independent of the reaction conditions. This behaviour of wood was
likened to the phase change phenomenon of fusion.
Practice
Based on this work, a conceptual design study produced the specification outlined in
Table 2. The pressure between the particle and the reactor wall needs to be as high as possible
for optimum results, but there will be mechanical considerations in meeting this objective.
Other aspects that require resolution in the experimental development is the masking effect of
multiple particles on the interaction of particle and wall and volatilisation of liquid products.
The vaporised liquids require rapid removal and quenching to avoid secondary reactions.
Partial vacuum operation would avoid the need for flushing gas.
Table 2
Specification of an Ablative Pyrolyser for Liquids Production
Biomass throughput, d.a.f. kg/h

Temperature, C
Pressure (particle on reactor)
Heat input, kJ/kg
Effective area for ablation, m^
Estimated actual area, m^
Minimum relative velocity, m/s
Derived from
Experimental
Specified
5
Literature
600
Led
As high as possible
Estimated
2000
Led
3 IO"3
9 IO"3
Estimated
Led
1.2
Commercial
1700
600
As high as possible
2000
1
3
1.2
CONCLUSIONS
As a result of the above work, the main conclusions are :
Ablative pyrolysis is the most promising route to employ for the production of liquid fuels
based on the ideal pyrolysis process specifications and characteristics outlined.
Further research is required in the area of the of pyrolysis kinetics.
546
REFERENCES
"1. Evans R J and Milne A, "Characterization of the Pyrolysis of Biomass 1:
Fundamentals", Energy and Fuels, American Chemical Society Journal, 1, No 2, 1987.
2. D iebold J and Power A J, "Engineering Aspects of the Vortex Pyrolysis Reactor to
Produce Primary Pyrolysis Oil Vapours for Use in Resins and Adhesives", in Research
in Thermochemical Biomass Conversion, Phoenix, Arizona, USA, April 1988,
Bridgwater A V and Kuester J L (eds), 609, (Elsevier Applied Science Publishers,
London and New York, 1988).
3. Led J, Panagopoulos J, Li and Villermaux J, "Fast Pyrolysis of Wood: D irect
Measurement and Study of Ablation Rate", Fuel 64, Nov. 1985, 1514.
4. Tran D Q and Rai C, "A Kinetic Model for Pyrolysis of Douglas Fir Bark", Fuel 57,
1978, 293.
5. Madorsky S L, Hart V E and Straus S J, Journal of Research of the Natural Bureau of
Standards, 56, (6), 1956, 343-354.
6. Tinney E R, "Tenth Symposium (International) on Combustion". The Combustion
Institute : Pittsburgh, 1956, 925.
7. Nunn R, Howard J B, Longwell J and Peters W A, "Studies of the Rapid Pyrolysis
of Sweet Gum Hardwood", in Fundamentals of Thermochemical Biomass Conversion,
Estes Park, Colorado, Oct 1982, Overend R P, Milne A and Mudge L K (eds),
Elsevier Applied Science Publishers, New York, 1985, 293-314.
8. Bradbury A G W, Sakai Y and Shafizadeh F, Journal of Applied Polymer Science 23,
1979, 3271-3280.
9. D iebold J and Scahill J W, "Ablative Entrained-Flow Fast Pyrolysis of Biomass" in
Proceedings of the 16th Biomass Thermochemical Conversion Contractors' Meeting,
Portland, Oregon, 1984, 319.
10. D iebold J, "The Cracking Kinetics of Depolymerized Biomass Vapors in a Continuous
Tubular Reactor", MASc Thesis, Colorado School of Mines, Golden, CO, USA, 1985.
11. Liden A G, "A Kinetic and Heat Transfer Modelling Study of Wood Pyrolysis in a
Fluidized Bed", MASc Thesis, University of Waterloo, Canada, 1985.
12. Gorton C W and Knight J A, "Oil From Biomass by Entrained-Flow Pyrolysis",
Biotech, and Bioeng. Symp., No 14, 1984, 14-20.
13. Scott D S, Piskorz J, Bergougnou M A, Graham R and Overend R P, "The Role of
Temperature in the Fast Pyrolysis of Cellulose and Wood", Ind. Eng. Chem. Res., 27,
1988, 8-15.
14. Vasalos I, Stoikos T, Samolada M, Achladas C and Papamargaritis C, "Production and
Utilization of Synthetic Liquid Fuels", 'EEC Contractors' Meeting - Energy from
Biomass', Paestum, Italy, May 1988.
15. Krieger-Brockett B and Glaister D S, "Wood D evolatilization- Sensitivity to Feed
Properties and Process Variables" in Research in Thermochemical Biomass Conversion,
Phoenix, Arizona, USA, April 1988, Bridgwater A V and Kuester J L (eds), Elsevier
Applied Science Publishers, London and New York, 1988, 127.
547
GASIFICATION OF REFUSE, A PROCESS OF SFW
Dr. H. HUMMELSIEP and Dr. H. FUNK
Saarberg-Fernwarme GmbH, Sulzbachstrasse 26, D 6600 Saarbrcken, FRG
Summary
Since 1974 Saarberg-Fernwarme GmbH has been engaged in the technology
of gasifying municipal and industrial waste. The first pilot plant was
started up in 1975 at Neunkirchen/Saar. This unit was designed to
process solid waste at a rate of 100 kg per hour, and was intended to
prove the feasibility of this system.
The knowledge gained from this operation was used to establish
criteria for the design and construction of a large demonstration
plant for the treatment of industrial and municipal.solid waste at a
capacity of one ton per hour.
This project was supported by the
Ministry of Research and Development at Bonn.
Having proved the
feasibility of the system, this operation has since been terminated
after about 15 000 operating hours.
At the present time,
plans have been formulated for the
construction of a commercial waste gasification plant to treat
120 tons per day of refuse. It is contemplated to start operation of
this plant within the framework of a research and engineering project.
Once a successful operation has been established, this plant will
continue to serve as a solid waste utilization plant to process refuse
as delivered.
1. PROCESS DESCRIPTION
The process is carried out in three phases :
- preparation of solid waste;
- gasification and gas purification;
- water purification.
Solid Waste Preparation
The refuse is transferred from a pit on a conveyor, which carries the
material to a screen, where fines are discharged. The larger pieces are
dumped into a shredder and the chunks are reduced in size to smaller than
4 inches by 4 inches. Then the Fe-scrap is discharged magnetically and the
sorted material is charged to a vibrating screen, and classifier. Thus the
material is separated into three fractions. They are: the light fraction,
the heavy fraction, and the fines. The fines are composed mainly of inerts
and are discharged to a landfill. The light fraction, containing mostly
paper and plastics and the like, is shredded once more and compacted to a
kind of nodule. These nodules together with the heavy fraction are charged
to the reactor for gasification.
548
Gas Generation and Purification
The gas generating reactor is designed as a vertical cylinder at an OD
of about 3 metres and a height of 5 metres. The upper section is lined with
refractory and the lower one in the area of the reaction and ash holding
zone is furnished with a water wall. The reactor is fed from the top where
the charge passes through sliding gates preventing any escape of gas. The
material is then exposed to the following phases of treatment:
-
drying phase ;
degassing phase;
gasification and reduction phase;
combustion phase.
The bottom of the reactor is sealed with water by standing in a tray

where the ash is retained. While turning and stirring the bed of ash a
scraper disposes the ash into the tray. This churning action stirs the ash
and promotes a balanced combustion of the remaining carbon. The required
oxidizing fluid is injected into the reactor in the form of air through a
cone-shaped grate. Depending on the desired consistency of the gas to be
generated, one can inject pure oxygen or oxygen enriched air. A small part
of the material is burned in the lower reactor section in the presence of
oxygen.
The gas free of oxygen is heated to a temperature level of
950-1000C. This gas passes upwards through the reactor and the reducing
zone where carbon and hydrogen compounds are formed to compose the so-called
producer gas, after the gasification and pyrolysis phase has been completed.
The product gas is discharged overhead from the reactor and passes
through a hot multi-cyclone, designed for high temperature resistance, and
to retain fine particles and dust.
The scrubbing of gaseous, water soluble harmful components is carried
out with recycled water and lye added. After this 'cooling down phase' a
purified gas is available of medium heating value of about 7000 kj/m3 ,
provided oxygen enriched air is used as the oxidizing means. The measurements of emissions after combustion indicate that no harmful components are
detected.
It is possible to separate components such as hydrogen,
carbon
monoxide and methane, in a further processing step, if so required. Thus a
synthesis gas for the production of methanol can be prepared by employing
regenerators.
Water Purification
Solid waste generally contains moisture at a rate of 20% to 30%. After
its condensation this water has to be separated from tars and oils in a
decanter. The oils and tars in turn are recylced to the reactor, unless they
are to be utilized otherwise, while the water flows to the first basin as
part of a treatment system. There the water is purified in three steps:
- chemical treatment;
- biological purification;
- filtration through activated carbon.
The chemical treatment results in separation of iron, zinc, lead, and
other heavy metals in the form of hydroxides.
Then by adding phosphates in a reactivation unit the water is
subjected to biological treatment.
Legend
1) Screening
2) Shredding
3) Magnetic separator
4) Mechanical separator
5) Dryer
6) Shredder
7) Compactor
8) Reactor
9) Dust separator
10) H2O washer
11) Alkali washer
12) Clean gas compressor
13) Boiler
14) Separator
15) Cooler
16) Cooling tower
17) Two-stage water treatment
18) Steam generator
19) Air separator
20) Oxidant heater
Larger fraction,
1
Freshwater
Medium fractior
Air
_
Air^|
19
20
Raw gas
Fine dust
18
Tar/water
mixture
Fresh l y e
C i r c u l a t i n g water
14
Tar and o i l
Waste water .
17
Tar and o i l
(tfaste lye
Outfall.
Flow Chart - Gasification of refuse by the SFW-Funk process
4*.
^5
550
The final step of purification is accomplished in an activated carbon
filter.
Some of the data obtained from the results of these test runs are
beyond the limits of the required standards of water purification. However,
by optimizing the operating condition and the incorporation of an activated
carbon filter the required standards of purification can easily be met.
2. POTENTIAL OF APPLICATIONS
Solid waste gasification is closing a gap in various methods of
thermal decomposition where annual capacities in the range of 30 000 to
100 000 tons per year of refuse are available for utilization. Therefore it
ought to be of special interst for counties or medium sized communities. The
operating costs for utilizing solid waste compare with an incinerator
handling a capacity of about 200 000 tons per year of garbage.
The application of this process is not limited to the treatment of
household waste and similar industrial waste, since this gas generator is
capable of consuming a wide range of refuse. Waste from the woodworking
industry, agricultural waste, leather and textiles, to name only a few, can
be utilized while recovering energy and operating without causing pollution.
The purified gas basically
offers the same possibilities
of
applications and usage as natural or city gas. However, it should not be
piped into an existing grid of natural gas because of the high content of
CO, but it is useful as a fuel for direct heating in industrial projects,
for instance drying kilns or boilers, and water heating facilities (for
process heat or district heating).
Pipelines cost less to construct than piping for district heating,
hence product gas can be brought economically to the point of consumption to
be converted to heat and/or electric energy at district heating stations
with gas engines, gas turbines, or absorption heat pumps.
551
A CATALYTIC GASIFICATION PROCESS OF BIOMASS

J. Munck
Dansk Termo Industri/I. Krger AS
Summarv
The paper presents a technical concept for a biomass gasification
plant with an output of 1,2 MW supplying gas directly to the gas
engine delivering electrical power to the public grid as well as
heat to district heating. The plant will be situated in Hjreby
Municipal in Denmark.
1. INTRODUCTION
The gasification process is characterized
following well-known processes:
1. Pyrolysis of biomass
) CO
Biomass + heat
Cat
loo:600c
2. Watergas production
Carbon + H O + heat
>
)
J
)
)
by
coupling
of
the
C0
2
CH 4
H
HÔ
ashes/remaining carbon
) CO
P- ) CO
800-1000 ) H.
Methanization
C0 + C
2 + 2 - 3 5 0 ^
CH 4 + H 2 0 + heat
By using a suitable catalyst in the first process the following

benefits have been achieved:
a) production of a gas with a neglicible content of tar
b) production of gas with a high concentration of CH, compared with a
conventional technique
c) the process takes place at a temperature level lower than for a
conventional process
By the second process the remaining carbon from process No. 1 is
converted to a gas by adding of water.
In the third process the gas mixture from process No. 1 and No. 2
is converted to methan by using suitable catalyst.
The methanization process is an exothermic process and the formed
heat can be utilized in the pyrolytic process.
552
2. RESULTS
The key process in the concept is the pyrolytic process. For
nearly one year a pilot plant has been in operation with a capacity of
approx. 50 kW measured as gas production.
By using straw as a biomass at the pilot plant the following key
figures have been measured:
Production of gas:
pprox. 1 Nm'/kg dry straw
Heat value:
pprox. 12,5 MJ/Nm1
Composition:
Approx. CO
12% vol.
CO
30%
CHT 16%
H
37%
,
1%
C
2 C 7 4 %
shes:
Approx. 0,2 kg/kg dry straw
Carbon content in ashes:
50%
An energy calculation for the plant (process No. 1) has given the
following results:
Straw feeding:
100%
Gas production:
77%
Remaining carbon:
18%
Process heat:
5%
For the process No. 2 (water gas production) only a few tests have
been made, but the results have shown that the carbon is very active
and consequently more or less can easily be converted to water gas. A
more theoretic study has shown that the water gas process can eventu
ally take place in the pyrolytic reactor.
This concept will be tested within the next 6 months.
The conversion to methan (process No. 3) is regarded more or less
as a fully developed process which can be supplied from engineering
firms specializing in catalytic processes. Therefore, this process will
be added when the two other processes have been fully developed.
3. THE DESIGN
As the pyrolytic reaction is the key process, the pyrolytic
reactor will be described in more details.
The pyrolytic reactor (the pilot plant) has a diameter of 60 cm
and a total height of 100 cm.
The reactor is indirectly heated by a heat exchanger built in the
reactor.
In the top of the reactor a distributor is situated spreading the
straw all over the area of the reactor.
The catalytic layer has a height of approx. 40 cm and is placed in
the bottom of the reactor on a screen.
The catalytic pellets have a size of 515 mm. The working
principle is as follows:
The disintegrated straw is feeded into the reactor by means of a
screw and is spread over the catalyst by the distributor.
In the top of the catalytic layer the temperature is approx. 100C
and at the bottom approx. 600C.
The straw is forced through the catalyst by a vibration technique,
and during the passage of the catalyst the temperature of the straw is
increased from 100C to 600C.
553
The mixture of gas and ashes is separated
content of water is condensed and drained.
The total process is shown below:
in cyclons
and the
Catalytic Pyrolysis and Gasification of

Biomass
Straw
Electric energy
CooUn. water for
Disintegrator
and
Feeding silo
Electric gene- dlalrlcl hating

rator and
Gasengine .
Water drain
' G a a t o r h M ting of UM reactor
Aah
Catalytic
pyrolysis
reactor
Filter
Water drain
'
Ash
'
Water gas
reactor
Cyclone
Aah and carbon

Drain water
Cyclone
1
Gas
Catalytic
methailization
It is planned that the total concept of the plant should be

finished within 1989 so that the civil works can be carried out in 1990
and the production of heat of electricity could begin at the end of
1990.
4. APPLICATIONS
The concept can also be used in connection with other biomasses
than straw and should therefore have a high market potential not only
in the industrialized countries but also in the developing countries.
A few tests have been made on gasification of rice shells,
bagasse, seed wastes, chopped wood and sludge from wastewater treatment
plants.
554
AGRICULTURAL WASTES FOR ELECTRICITY GENERATION

C. ESNOOF and N. BEERAI
Centre National du lacbinisie agricole, du Gnie Rural
des Eaux et des Forts BP 121 92164 ANTONY Cedex France
Sumary
The ail of the project is power production in siali units in rural areas of developing
countries. The selected process is the gasification of charcoal obtained froi agricultural
wastes, straw, cotton stalks, grasses. The paper presents the results obtained on a pyrolyser
pilot of 100 Kg/h of straw. Straw bales are carbonized in fixed bed in continuous operation.
Long t e n stabilized operation has been obtained, with 331 charcoal yield and various
volatile content. The charcoal obtained is further aggloierated in a revolving pan and
resulting balls are gasified in a 15 Kg/h crossdraft gasifier. Experimental results show a
0.77 energy efficiency and a LCV of gas produced of 42004600 KJ/Ni3.
Preliiinary economics show that the profitability of the line greatly depends on the
operating tiie of gasifier unit.
1. INTRODUCTION
The ai of the project is power production with raw aterais other than wood (often rare) or
fossil fuels (often ported, rare and expensive). It concerns siali ans lediui sized units (550
KH) in rural areas of developing countries.
The selected process is the gasification of vegetal charcoal obtained froi agricultural wastes,
such as wheat and rice straw, cotton stalks and grasses.
A new concept of pyrolyser was developed and preliiinary results presented in (1). Nore
ampete results are given here, including gasification tests. A preliiinary econoiic estilate is
also presented.
2. NATERIEl AND NETHOD
The processing line is presented in figure 1.
The pyrolyser is a continuous fixed bed, processing bioiass in the fori of lediui density
rectangular bales (100120 Kg/i 3 ). It has been previsiouly described (1) The resulting charcoal is
crushed to I n , lixed with a binder and then aggloierated in siali bales (20 to 30 diaieter) in a
revolving pan.
The pan used is a laboratory unit producing 50 Kg/h, but this device is comercial in sizes
up to 1 ton/h. The balls characteristics are presented in table I.
Table I Charcoal balls characteristics
Coiposition : dry laterial 4Sstarch
25iash
71t charcoal
Lower calorific value (LCV) : 26 200 KJ/Kg
3
density : 325 Kg/i
volatile latter content : 201 (at 960"C)
Agricultural Wastes
Starch
Pulverulent Charcoal
100 Kg/h
Wheat and r i c e Stra
Cotton s t a l k s
300 Kg/h
100 t o 120 Kg/m3
STRAW PTOOLYSER
BKVOLVIKO PMI
'
: CONTINUOUS FIXED BED WITH
A
VOL TILES RECYCLING A ND BURNING
Ol
COOKING
Charcoal crossdraft gasifier

electricity generator
Gasifier
O
!
O
t3
C
>
(
VI
3
(
_
5
Balls
280 to 300 Kg/n3
100 Kg/h
Kffrtn
100 KW
3
>
556
The resulting balls have then been gasified in a cross draft gasifier of 15 Kg/h inputffigure
2). This gasifier has been experimented on charcoal in long tiie run (2).
Variable quantities of stea have been added to the air, so that the gasification temperature
would be lowered, in order to avoid clinker formation. The steam/charcoal ratio selected is 0.47 so
that a temperature of HOO'C and a very limited fusion of ashes are obtained.
3. RESULTS
Continuous stabilized operations of 7 hours have been
regularly obtained on the pyrolyser. The instabilities
previously observed (1) were due to irregular straw feeding
(on account of compression at the tight chamber entrance).
specific device now controls the progression of straw
inside the chamber and pilots the feeding device. The
pyrolysis temperature is around 600'C with a hot gas
attack at 750800'C and the stability is obtained after
3 hours of operation (not counting the first tvo hours of
preheating).
Charcoal yield is around 331 on dry straw and
281 on an ash free basis. The charcoal aspect is the
same as feeded biomass, straw or cotton stalks. The
volatile content of charcoal depends on temperature and
residence time, as can be seen in table II.
The energy efficiency of the pyrolyser is 0.55
(LCV charcoal/LCV straw)
or 0.87 ( LCV charcoal +
volatiles/LCV straw) if the volatile matter is valorized
elsewhere.
Figure 2
Table II Volatile content of charcoal

sample
12
15
17
17
17
20
22
23
27
temperature 450
425
420 460
525
640
480 560
530
7.8 12.7 10.4
8.1
residence
time
fc)
volatile
content
20.2 16.6 13.2 12.8 11.6
similar results were obtained with cotton stalks, only the pressure drop of gases in the bale
being much lower.
charcoal balls gasification with steam led to a gas containing 22251 CO, 1114* H 2 , so
a lower calorific value of 42004600 KJ/lfir. It represents an energy efficiency (LCV gas/LCV
charcoal) of 0.84 without water vaporisation and of 0.77, the latter taken into account.
This means a general efficiency of the process of (LCV gas/LCV biomass) 0.4 (without
valorization of volatile matter in excess).
The gas must be cleaned (filtration) before the engine as it contains around 0.16 g/m3 of
dust and 0.058 g/mJ of tar. The balls behaved perfectly during gasification, keeping their form
and solidity.
557
ELECTRICITY
OPERATING
TIME
GENERATOR
TIME:2500
OPERATING
H/YEAR
2
3
4
F U E L - O I L P R I C E IN FF/I
OPERATING
TIME
4000
H/YEAR
FUEL-OIL
8
Figure 3.
10
PRICE
12
4
IN
F F /I
14
16
18
20
F U E L - O I L P R I C E IN ECU/GJ
45
66
89
11 1
C R U O E OIL P R I C E J/bbl ( W I T H O U T
22,5
33
44.5
CRUDE OIL P R I C E S/bbl
H O OK
TRANSPORT)
56
TRANSPORT
COST)
558
4. PRELIMINARY ECOHOMICS :
Tbe coiplete line, carbonisation to electricity production, is estimated. The pyrolyser and
revolving pan are 100 Kg/h charcoal capacity and each electricity unit is 20 KW. (1520 Kg/h
charcoal). They are locally lanufactured except for the recycling fan of pyrolyser.
The capital costs break down as follows (table III) :
Tbe charcoal Manufacture capital costs break down as follows (table III).
revolving
pan
30
pickup pyrolyser
baler construction
5T/h
50
160
recycling
fan
2 15 KW
Total
140
380
Table III Capital costs in 10 3 FF

For the electricity generator, the additional cost as coipared with a fueloil engine is 65 to
85 10 3 FF.
For the gasifier unit, two operating tiie are studied : 2500 h/year for irrigation of 2 crops
per year, and 4000 h for a village or craftsian electricity production. For the pyrolyser,
1000 h/year corresponds to a pluvial rice crop giving 0.8 to 1.3 ton of straw per ha and year,
that is an area of 200350 ha ; 2000 h/year for the saie crop on an area of 400700 ha and 4000 h
for an irrigated rice crop giving 8 to 13 ton straw/ha and year, on an area of 100 to 140 ha.
Maintenance costs are increased as coipared with european standards, up to 10 of capital cost
per year.
At first the straw is given no price, except for harvest salaries.
Given a fueloil price, a laxiiui price for charcoal balls purchase is coiputed, allowing
profitability for the electricity unit. This price is coipared with the liniiui selling price
for pyrolyser profitability.
The results are presented on figure 3.
One can coipare the selling price of charcoal to those observed in Abidjan (Cte d'Ivoire),
lFF/Kg i 30t ; the prices of balls are equivalent for 2000 and 4000 h operating tiie.
Given the fact that the oil price in year 2000 are expected to be froi 20 to 35 $/bbl, it can
be seen that the profitability, essentially a function of electricity unit operating tiie, is
probable for 4000 h/year, or for 2000 h/year if the pyrolyser works 4000 h/year, i.e on irrigation
crops ; in both cases, the area lust be far froi oil refineries (100t transportation cost).
Hot that those figures dont take into account the tax part in the fueloil present selling
price, often leading to a 4 or 5 F/liter price.
5. CONCLDSIOH
The carbonisation of straw or cotton stalks bales is technically feasible in a fixed bed
continuous reactor. But the overall process seeis quite coiplex to iipleient so that profitability
of the line is only obtained when the electricity generator set is operated for a longtime,
irrigation of two crops per year or electricity production for craftsmen.
6. REFEREHCES :
(1) ESHODF. C al (1987) Mobile straw pyrolyser. Bioiass for Energy and Industry pp
10631067 Elsevier applied Science.
(2) PLANCON. M, GOOPILLOH. J.F, ESHOOF. C (1988) Automated operation of lean gas engines
Research in thenocheiical Bioiass Conversion pp 10491056 Elsevier applied Science.
559
PYR0LY5I5 PROCESS FOR RECYCLING FOREST AND AGRICULTURAL WA STES

FOR RECUPERATING BIOMA SS ENERGY
B. GROUX, R. GUIOL and Ph. POUSAZ

BIO-ALTERNATIVE S.A ., Case postale, CH-2063 ENGOLLON
BIO-ALTERNATIVE ITA LIA S.R.L., Via Caffaro 23, 1-16124 GENOVA
BIO-ALTERNATIVE S.A . ESPAGNE, Calle Felix Bois 18, E-28036 MADRID
ABSTRACT
There is a need for converting biomass wastes into charcoal, oil,
and gas which can be utilized in industrial or domestic equipment.
Low temperature pyrolysis, which favours coal and oil production
(respectively 50? and 20% of the energy contained in the biomass),
offers particularly promising means of conversion since charcoal
and oil products are storable and easily transportable.
Bio-Alternative S.A . developed an industrial process in order to
emphasize on charcoal production and optimization in qualitative
oil extraction with respect of the environment. This technology can
be used for different types of biomasses: eucalyptus wood, oak wood,
ash wood, fir wood, acacia wood, genista wood, sorghum waste,
grapes residues, pine cone, coffee residue, cocoa residue, coconut
shell, rice husk, marc of olives, corn residue, straw.
Results are given for an industrial plant treating 15'000 tons of
wood wastes per year.
1. INTRODUCTION
The convertion of organic wastes from broad origin (forest and
agricultural wastes) into a range of products that can be used as fuels,
is a good challenge. Pyrolysis is attractive because solid biomass wastes
which are difficult to burn in existing equipments can be converted into
products (charcoal, oil) with advantages in transport, storage and
combustion.
In this field of recuperating energy from biomass, environmental
requirements are the most important task for the design of pyrolysis
plants.
A technology has been developed by Bio-Alternative S.A . in order
to produce charcoal, bio-oil and bio-gas from biomass wastes.
2. TECHNICAL DEVELOPMENT
In order to study the processing of any biomass and to optimize
the quality and yield of the products obtained by the pyrolysis process,
Bio-Alternative S.A . operates a pilot unit allowing the continuous
treatment of 50-100 kg of raw material per hour.
In the fixed bed, the biomass is continuously in motion towards
the oxydation zone where the partial combustion of the pyrolysis gases
occures in order to maintain the carbonization process (see figure 1 ) .
Bio-Alternative S.A. carried out an extensive experimental program on
the pilot plant for evaluation of a wide variety of biomasses (see
following table).
560
Table 1 : Pyrolysis pilot plant; some relevant examples
INPUT
0 U U I
CHARCOAL
CAPACITY
kg/hr
Vield
kg/hr
Eucalyptus
85,0
23,
7200
Acacia
54,7
12,5
GenlBta
60,5
Beech
67,5
BIOHASS
BIO OIL
BIOGAS
yield
kg/hr
HHV
kcal/kg
51
7,7
5530
13
6,5
1040
14
6600
34
6,2
5900
15
92,1
1064
41
14,6
7550
44
4,4
3B20
107,4
B80
37
17,
7275
47
9,2
5350
18
40,5
1370
20
25
HHV
kcal/kg
Energy
balance
S
Energy balance
Yield
kg/hr
HHV
kcal/kg
Energy
balance
5
Olive stones
51,9
14,5
7400
48
6,2
5000
14
51,9
1055
Rice husk
2,0
18, 3
4500
48
',3
5520
10
29,4
1024
18
Coconut shell
93,4
24,3
7900
48
16,8
4850
20
56,1
1095
15
Cocoa waste
65,0
22,8
6000
52
2,6
6300
B5,3
560
IB
Coffee waste
70,0
24,5
6000
52
5,6
6300
13
70,0
BOO
20
Bagasse of
sorghun
5,0
14,4
6600
51
4,5
6200
15
40,5
560
13
Haize
66,5
14,9
5550
44
1,4
7800
52,3
720
25
Pine cone
0,0
27,0
7900
54
12,6
6100
19
7B,8
4D0
Beside the production of good quality charcoal, the leading points

in the BioAlternative technology are 1)optimization of the biooil
extraction and 2) meeting the highest antipollution requirements.
1) The selection of proper pyrolytic conditions and effective
extraction system allows the production of biooil with good stability
and quality, representing a high energetic density. Typically the bio
oil obtained has 20% maximum water content (determined by azeotropic
distillation) and does not give dcantation upon standing. The density
is around 1,2 and the viscosity between 50cp and 150cp depending on the
biomass. Energetic density is around 6500 kcal/dm3.
2) Regarding the environmental requirements, it must be assumed
that everything that leaves the plant must be charcoal, biooil and bio
gas. Most important is the absence of waste water contaminated with
toxic constituents. In the process, this problem is worked out by
safely burning all gaseous effluents without condensation except of the
components recovered in the biooil.
3. INDUSTRIAL UNIT PLANT
Our investigations on the pilot plant resulted in the construction
of an industrial pyrolysis plant which is located in Spain (Olivenza).
This plant is processing on wood wastes which are collected by a lorry
equiped with a grinding machine. Capacity of the plant is 2150 kg per
hour of wood chips ( 2 x 2 x 5 cm) with about 20? moisture. The operation
is running continuously and is controlled by 3 teams of 2 men each.
3.1 Products
Results of the pyrolysis process are presented in the following table:
Table 2 : Pyrolysis industrial plant; results
Material
Capacity
INPUT
Oak wood
2150 kg/hr
(20? moisture) ZXS3ZZ2ESX
OUTPUT
Charcoal
Biooil
Biogas
570 kg/hr
300 kg/hr
1755 kg/hr
Energetic balance
m i n i
, i n
1 1 1 V, I
100 %
>>?tT*
XVWSAXX
48
19
20
561
3.2 Analysis
Analysis of the products are the followings
Charcoal
high calorific value
ashes
volatiles
humidity
fixed carbon
sulfur content
7250 kcal/kg
3%
15 %
2 %
80 %
0,1 %
high calorific value

water content
sulfur content
5350 kcal/kg
15 %
0,3 %
Bio-oil
Bio-qas
high calorific value : 1000 kcal/kg
non-condensable content : 15 % CO; 13 % C02; 48 % N2; 8 % H2;
6 ro 0 2 : 3/0 CH4.
3.3 Use of the products
The pyrolysis plant of Olivenza is associated to a bricketting unit
which production is destined to the barbecue market (total capacity :
2500 kg briquettes per hour).
Presently, the charcoal production is completely supplied to
barbecue market but investigations are planned on activation process
and utilization as charcoal slurry.
The bio-oil is distributed as industrial fuel and the bio-gas is
used on site in the briquetting unit.
Our investigations are in progress to use them for electricity
production.
4. CONCLUSION
The experimental programme of Bio-Alternative S.A. on the pilot
plant permitted the realization of a "second generation" pyrolysis
industrial plant.
Our present R&D programmes are the followings :
- Use of charcoal as slurry for substitution to mineral liquid fuels.
- Use of bio-oil in turbin and diesel systems (electricity production)
- Use of bio-gas in a motor and boiler for electric and thermic production.
562
Figure 1 :
Uio-Alternative S.A.
pyrolysis process flow sheet
-&
OLL OUTLET
RAW MATERIAL
INLET
CHARCOAL OUTLET
Figure 2:
Pyrolysis industrial plant
in Olivenza (Spain)
563
PYROLYSIS OF GREEK LIGNITES
A.A. Lappas, and I.A. Vasalos
Aristotelian University of Thessaloniki
Thessaloniki, Greece
SUMMARY
Two different types of Greek lignites were evaluated using the fast
pyrolysis process in a fluidized bed reactor. The innovation of our
experimental system is that the reactor effluent is connected on
line with an FID and a TC detector for the continuous monitoring of
total hydrocarbons and total gases respectively. The total yield
distribution of the various products was obtained as a function of
pyrolysis temperature and lignite particle size. Two kinetic models
for coal decomposition were also tested for the determination of
the appropriate kinetic parameters. From this work it can be
concluded that:
i. The produced gases from the pyrolysis of Greek lignites are
dominated by oxygen compounds CO, CO. A number of hydrocarbons are
also produced (C,-Cg).
ii. The experimental results are interpreted reasonably well with
the competing reaction model.
1. INTRODUCTION
Pyrolysis, one of the most important coal conversion process, has
special importance for the Greek economy because of the big reserves of
lignite in two regions (Ptolemais and Megalopolis). It is possible the
big reserves of peat in the region of Philippus will be used in the
future to solve the energy problems of Greece.
Pyrolysis involves heating of coal at elevated temperatures in the
absence of air and it is a chain of decomposition reactions where the
linkages between aromatic clusters are broken and volatile decomposition
products are produced(l)
The objective of this investigation was the evaluation of Greek
lignites with respect to the distribution of gas and liquid products,
and the development of a kinetic model suitable for the decomposition of
Greek lignites.
2. EXPERIMENTAL
2.1 Unit description. A schematic diagram of the fluid bed reactor is
shown in Fig. 1. The heart of the unit is a stainless steel reactor
vessel. A close tube section at the top of the reactor is used to
introduce lignite sample to the fluid bed.
The unit is also equipped with a gas feed system which includes the
following gas components: N 2 , Air, H-0. In this work pyrolysis was
studied using N- as fluidizaiion gas.
The reactor effluent passes through a stainless steel coil placed
inside a cold liquid bath where the condensation of the liquids is
564
taking place. The rest of the pyrolysis products are collected in a gas
collection system (in a gas cylinder by liquid displacement).
The key to the successful testing of lignite with this sytem is the
withdrawal of two small sidestreams at a location downstream of the
reactor and the continuous monitoring of the total hydrocarbon evolution
profile with a Flame Ionization Detector (FID) and the total gas
evolution profile with a Thermal Conductivity Detector (TCD). The two
detectors are connected with a personal computer for the treatment of
data. From profiles like these, we can find the kinetic of evolution of
total HC and total gases during flash pyrolysis.
2.2 Unit Operation. A fixed amount of heat carrier (silica sand) is
introduced in the stainless steel reactor. A sample of dry lignite (2
gr) is introduced in a easily friable glass container when the bed reach
the desired temperature. The glass is dropped inside the fluidized bed
and thereby the sample is intimately mixed with the inert heat carrier.
2.3 Gas and Liquid Analysis. The gases from the collection system were
withdrawn and analyzed in a system of gas chromatographs: an FID (column
porapak QS) and a TCD (column carbospheremolecular sieve). The former
was used to detect hydrocarbons and the latter CO, CO, H, N, Oj.
The liquid products were collected from the stainless steef coil
(which is placed in the cold bath) with a mixture of methyldichloride
and methanol (1:1 v/v). The solution was removed by evaporation
approximately at 47C followed by a vacuum treatment using a rotary
evaporator.
2.4 Sample Preparation.
TABLE I: Elemental analysis
Greek lignite samples
from the Ptolemais and
Megalopolis lignite
Ptolemais 1 ignite
Megalopolis locations
% wt (MF) % wt
% wt (MF)
%wt
were selected for this
study.The preparation
20.67
29.48
16.00
C
52.35
of the samples includes:
1.39
1.83
0.99
H
3.52
crushing of raw material
1.89
0.74
1.51
0.83
production of fraction
0.43
3.40
1.86
S
1.10
with desired size homoge 0(diff.) 18.74
7.46
19.96
10.94
genization of samples,
8.80
43.82
23.88
Ash
22.20
elemental analysis(tabl .1) Moisture
60.50
45.50
and proximate analysis.

100.00
100.00
100.00
total
100.00
3. TOTAL PRODUCT YIELD CALCULATION
The flash pyrolysis of lignite produces tar, char and a range of
low molecular weight gases in various proportions and amounts depending
on the pyrolysis conditions (temperature, pressure, heating rate,
ambient gas, lignite type, particle size and experimental system).
3.1 Tar yield. The liquid yield increases as temperature decreases for
the two lignites (Fig. 2 ) . The reduction of the liquid yields with the
temperature can be attributed to the secondary reactions that take place
in high temperature.
3.2 Gas yield. The produced gases were dominated by oxygen compounds
which mainly consist of CO. The final CO yield increases with
temperature with high rate at low temperature.In contrast at high
temperature it tends assymptotically to a value of about 20% (of dry
lignite) for the Ptolemais lignite and 35% for Megalopolis lignite (Fig.
2)
The CO final yield is influenced by the temperature in a different way
than CO yield (Fig. 2 ) . CO is produced by carboxylic acids decompo
sition, a relatively low activation energy process (1). Activation
565
energies for the reactions of CO production are rather high and they
necessitate elevated temperature (1).
Regarding the yield of light hydrocarbons it should be noted that
each product exhibits different trend and behavior. The CpH. yield
increases monotonically with temperature. At elevated temperature this
increase in yield is extremely
rapid (Fig. 3 ) . Except of the
hydrocarbons included in Figure 3, many hydrocarbons (C 3 C 6 ) have been
produced and detected from pyrolysis.
TABLE II: Megalopolis lignite kinetic parameter [K (sec" ) , E(KJ/Kmole)]
= 1.8xl06exp(93453/RT) (from Chang et al.)
K b = 0.448exp(27727.8/RT)
K c = 96.65exp(38406.7/RT)
K
ob HC
01024exp(40253.4/RT)
oc HC
l546exp(26038.93/RT)
G = 1.322+5.47xl0"4(T500)+7.5655xl0"5(T500)2
A 0 = 6.8465.89xl0"3(T500)9.251xl0"6(T500)2
A
[T: C]
(% wt. dry lignite)
4. KINETIC MODELING
The kinetic model for our case must concern the production of total
gas and total HC from pyrolysis as we have the production profiles from
TCD and FID respectively.
It must be mentioned here that the non ideality of apparatus
affects the TCD and FID signals. The non ideality of the system was
revealed using tracer responce analysis tests (CH. was used as a tracer)
and obtaining the RTD curve. Many different kinetic models have been
proposed to explain the reaction scheme for the decomposition of coal
during the pyrolysis. THe nCSTR in series model describes well our
system (5).
The system effect on TCD and FID signals was taken into account using
the convolution integral (5).
The effect of heat and mass resistances on the kinetic model was
negligible because for the experiments Megalopolis lignite with small
particle size (60 m) was used (3, 4 ) .
Among the literature models we verified that the two competing
rection model described in (2) interprets better our experimental
results (Fig. 4, 5 ) . This model refers to a single coal particle and for
the total gas and total HC production takes the form:
The preexponential factors
.
and the activation energies
Aj > TAR > GAS + CHAR
of each kinetic constant of
model and the parameters A
Lignite
G (2) are presented at
Table II. It was considered

A 2 > GAS + CHAR
here that A , G are not
constants bat functions of
temperature (6).
566
K
A, >
1
h
u r ^ t o t a ! HC + CHAR
b,HC^
TA RCCCTKU <
Â
^ ^ G
total
S , 1 +. CHA R
HC + CHA R
GASi + CHA R
5. CONCLUSIONS
The investigation of Greek lignites under the process of pyrolysis,
using a fluid bed reactor resulted in the conclusion that Greek lignites
produce high gas yield while the yield of liquids were relatively low.
The produced gases were dominated by oxygen compounds which mainly
consist of CO especially at low temperature. At higher temperature the
yield of CO was also high. Other gases produced in significant amounts
were CH., C^H., , CgHg, C,H, CH,. Another result is that important
differences were not observed between the behaviour of the two type of
Greek lignites (Ptolemais and Megalopolis) and that lignite particle
size has not important influence on the total products yield.
Except from the evaluation of Greek lignites our experimental
system has the ability for kinetic modeling studies. The non ideality
of the experimental system has been found using tracer response
tests.The model of nCSTR in series simulates perfectly the system. It
was found that the two competing reaction model interprets reasonably
well the experimental data.
6. FUTURE PLANS
A system of traps has already constructed at the pyrolysis reactor
exit. With this system we can trap various samples from the produced
gases during the pyrolysis as a function of time and temperature.
These samples are analyzed in gas analyzers and so the time and
temperature distribution of each pyrolysis product can be obtained.
These profiles are very important because they can lead to the evolution
kinetic of each discrete pyrolysis product.
ACKNOWLEDGMENTS
This work was supported by the Greek General Secretariat for
Science
and Technology
and the European
Community
Contract
EN3B/B3/102/EL.
REFERENCES
(1) Bautista, J.R., Ind. Eng. Chem. Fundam., 1986, 25, pp. 536544
(2) Chang, P.W., Swamy, .D., Knell, E.W., Coal Process. Tech., 6, 20
(1980)
(3) Agarwal, P.K., Genetti, W.E., Lee, Y.Y., Fuel., 1984, vol. 63
(4) Gavalas, G.R., Wilks, K.A., AIChE J., vol. 26, 1980
(5) Wen, C.Y., Fan, L.T., "Models for Flow Systems and Chemical
Reactors", Marcel Dekker Inc., New York 1987
(6) Gavalas, G.R., "Coal pyrolysis", Coal Science and Technology 4,
Elsevier, Amsterdam 1982
567
Fig.l
Schematic diagram of f l u i d
bed pyrolysis reactor
N2OH2)^(^
' 5
Fig
UiUdr"
2 Effect of temperature on
pyrolysis yields from Megalopolis
l i g n i t e : o, C0 2 ; , CO; . R
io io o o 100 izo 140 ileo tao zoo 220 240
Fig.4
Simulation of TCD pyrolysis

response at 700C:, experimental
TCD response; , two competing
reaction model
Fig. 3
Effect of temperature on
pyrolysis yields from Megalopolis
l i g n i t e : o, CH^; , CjH^; 0 , H2
Ao 100 120 140 180 ISO 200 220 240
Fig. 5 Simulation of FID pyrolysis

response at 700C:, experimental
FID response; o, two competing
reaction model
568
DIRECT MASS SPECTROMETRIC STUDY OF PYROLYSIS BEHAVIOR OF

BIOMASS AND ITS CONSTITUENTS UNDER DIFFERENT IONIZATION
CONDITIONS. MS AND MS-MS STUDY OF THE PRIMARY PYROLYSIS
MECHANISMS.
P-L.DESBENE, M.ESSAYEGH, B.DESMAZIERES, C.LANGE

andJ-J.BASSELIER
Laboratoire de Chimie Organique Structurale,
Universit P.et M. Curie,
4, Place Jussieu 75230 Paris Cedex 05 (France)
Summary
Pyrolysis of biomass (wood) and its constituents (cellulose and lignin) has
been studied directly into the ion source. The different ionization techniques
used (NH3, N2, NH3 + N2) for the MS analysis of primary pyrolysis products
led to similar pyrograms. The total ion current (T.I.C.) from biomass
presented two peaks partially separated which can be attributed to two
separate steps. The comparison of cellulosic T.I.C, lignin T.I.C. and
fragmentograms corresponding to several ions that are representative of
these components indicated that the first biomass pyrolysis products stemmed
from lignin decomposition while the last one stemmed from cellulose
decomposition.
Introduction
Pyrolysis of biomass, which leads to gas, liquid and char, is a very complex
reaction which is difficult to study. The chemical complexity of biomass and the
number of parameters influencing pyrolysis (temperature, residence time, thermal
flux...) make difficult the "mastering" of this reaction.
However, advances in pyrolysis industrial application will take place only if
chemical transformations encountered during the process are understood. Some
studies have been published, but the problem of mechanisms and kinetics remains
unsolved. These studies can be divided in two classes :
- those using thermal analysis (thermogravimetry (1-6) or GC/MS
coupling in association with thermal analyses (7)
- those using direct analysis of pyrolysis products by mass
spectrometry (8).
This last approach is seducing because it allows to escape partly the
inconvnients of thermal analysis.
569
The approach by thermogravimetiy, which uses the lost of mass to
characterize conversion rates does not reckon with the nature of reaction products
and the factors of their formation.
The GC/MS coupling in association with thermal analysis allows a detailed
analysis of products but it is long, complex and gives a low precision. The complex
problems of vapors collection and of the extreme reactivity of some species are
difficult to solve.
Direct pyrolysis into the ion source of a mass spectrometer combines the
advantages of the two methods mentioned above and escape their limitations.
"Molecular evolution" is followed directly during the pyrolysis and the resulting
vapors are analyzed on line.
Considering the work of Milne et al. (8), we have studied direct pyrolysis into
the ion source of a mass spectrometer, using different operating conditions. We
analyzed various wood species (eucalyptus, hornbeam, beech, chesnut-tree and
birch) and their constituents (lignin and cellulose). We report here the results of this
preliminary study.
Results
The samples, either woods of various species or their constituents (lignin and
cellulose) were pyrolyzed directly into the ion source by means of a L.I.D. rod, with
the same conditions (fast temperature rise : 9C/s, between 40C and 800C, then
isothermal at 800C).
We choose chemical ionization (ionization gas : NH3 or ND3), electronic
impact giving too many fragments. Examples of pyrograms and averaged mass
spectra recorded during pyrolysis of extracted celluloses and extracted lignins are
reported respectively in figures 1 and 2. In order to allow comparison we report the
behavior of two woods under the same conditions, characterized by their pyrograms,
fragmentograms and averaged mass spectra (figure 3).
Discussion and conclusion
This series of experiments shows that :
a) in the case of extracted celluloses
- The shape of pyrograms is the same regardless of the wood
species (figure 1).
- Averaged mass spectra are also identical.
b) in the case of extracted lignins
- The pyrograms are characterized by several broad signals of
variable intensity, contrary to extracted celluloses.
- These pyrograms are different as a function of wood species
(figure 2). Moreover, extracted lignins begin to undergo
decomposition during the temperature rise, that is to say ,
at a lower temperature than in the case of extracted celluloses.
- At last, extracted lignins mass spectra averaged on pyrolysis
duration are the same regardless of the spectra analyzed.
570
100%.
100%
25%
20 %
800 C
800*0
180
132 " U 4
I Ifli
162
I ) J1I,,.,I,|L
8 0 100 120 U P 160 1 8 0
x16
222 240 264 282 306 3 2 , 4
1
1
|Ul...jifL .. n, .lbj.,|,ll
2 0 0 2 2 0 240 260 280 3 0 0 320
342
384
330 350 3 7 0 390 410
430 450 470 4 9 0 510 530 550 570
F r g u r e 1 : P y r o g r a m s ( T . I . C . ) and a v e r a g e d mass s p e c t r u m
of e x t r a c t e d celluloses F r o m d i f f e r e n t w o o d species:
A P y r o g r a m of e x t r a c t e d b i r c h c e l l u l o s e .
B P y r o g r a m of e x t r a c t e d e u c a l y p t u s c e l l u l o s e .
C Mass s p e c t r u m r e s u l t i n g f r o m p y r o l y s i s o f e x t r a c
ted b i r c h cellulose
571
100%
100
15%
800 C
eoo C
209
211222 235
"J ' V 249
, Q , 301 315
271 285 . ,
k ^ L l a . 1 u . ^ J h . . T l L . , i J . l | . ....^.Ji
80
100 120 140 160 160 200 220 240 260 280 300 320
t x16
401
42
)5
41 9 ||
387M* 5 *1
SWH^llllilitlllillHjt l l t l r t l Mii* iliiiy.lin y i K l I | il
330
350
370 3 9 0 410 430 450
470 490 510 530 550 570
F i g u r e 2: Py r o g r a m s (T.I.C. ) a n d a v e r a g e d mass spectrum

of e x t r a c t e d l i g n i n s
f r o m d i f f e r e n t wood s p e c i e s :
A P y r o g r a m o f extracted birch lignin
P y r o g r a r n of e x t r a c t e d beech l i g n r n .
C Mass s p e c t r u m r e s u l t i n g f r o m p y r o l y s i s of e x t r a c
ted b i r c h I i g n i n .
'132
'193
!x16
252
244
264 282
115
228 Li. I2701
, 0 5
J
< I l i ; ,L,. 21
'
uu
Mucuri..
|mdll|MlHi
îilLnil...,
. ij. J.yLjL^...i
160
200
240
120
320
280
,163
150 174
13
*,J
M r 193
209
333
:180
330
370
410
450
490
530
570
. I.C.
800 C
800 C
180
115 134
*t H .!
80
120
160
342
1
330
1x16
162
222
570
I
I
240
282
324
200
240
2 80
~320
450
490
530
570
384
370
410
F i g u r e 3 : P y r o l y s i s oF d i f f e r e n t
A and
wood
species:
P y r o g r a m s a n d f r a g m e n t o g r a m s of
r e s p e c t i v e l y b i r c h and beech wood.
, D a n d E : Mass s p e c t r a c o r r e s p o n d i n g r e s p e c t i v e l y
to d e c o m p o s i t i o n w a v e s of c e l l u l o s e f r o m
a b i r c h w o o d a n d oF l i g n i n s f r o m a
b i r c h w o o d and a beech w o o d
573
c) For every species of wood
Pyrograms have at least two broad signals. However, the
pyrolytic behavior varies for each species. B eech and chestnut
woods undergo decomposition during the temperature rise,
while hornbeam and beech woods pyrolysis begins only at
800C.
Fragmentograms (R.I.C.) of ions 193 and 180, respectively
specific of lignin and characteristic of cellulose do
not vary as a function of the species pyrolyzed. It appears
that the first wave of the various woods pyrograms is
characteristic of the thermal decomposition of lignin, while the
second wave can be attributed to the thermal decomposition of
cellulose.
At last, mass spectra corresponding to the decomposition of
cellulose in the raw wood are identical to those
of extracted cellulose. Then, cellulose undergoes the same
decomposition after or without extraction from the wood.
However, mass spectra of the thermal decomposition of lignin
in the raw material are different from those obtained
with extracted lignin. The thermal decomposition mass spectra
of lignin are different for each species and it seems
they can be used as an identification print.
These preliminary results are very encouraging, and we are presently
pursuing the study by MSMS spectrometry.
REFERENCES
[1] W.K.TANG and W.E.NEIL, J.Polymer.Sci, & 65,1964
[2] . and M.KASE, J.Polymer.Sci., 5, 833,1967.
[3] A.F.ROBERTS, Combust.Flam., 14,261,1970.
[4] D.FASENEAM, CanJ.Chem., 49_ 632,1971.
[5] K.MIN, Combust.Flam., 3J, 285,1977.
[61 C.VOVELLE, H.MELLOTTEE and J.L.DELFAU, Prepr.Pap.Am.Chem.Soc,
Div.Fuel Chem., 28_ 291,1983.
[ M.KOSK, I.SURINA, I.LAPCIK, I.RUCKA and V.REISER, Chem.Zvesti., 2Z
843,1983.
[8]
a) R J.EVANS and A.T.MILNE, J.Anal.Appl.Pyrol, 2,57,1985.

b) A.T.MILNE and M.N.SOLTYS, ibid., 5, 93,1983, ibid., 5, 111, 1983.
c) RJ.EVANS, A.T.MILNE and M.N.SOLTYS, ibid., & 273,1984.
574
A TWIN BED PYROLYZERCOMBUSTOR FLUID BED SYSTFM FOR THFRMAI PROCESSINO
OF URBAN WASTE
H. MASSON*, A. BUEKENS+, K. MA NIA TIS +, J. SCHOETERS 0

* Seghers Engineering
+ Free University of Brussels
0
Groep , Leuven
This paper describes the concept, the development and the operation of an
interconnected fluid bed system able to generate, autothermally, a medium BTU gas
from urban refuse.
In one fluidized cell, the raw waste is pyrolyzed by cooled, recycled pyrolysis
gas at about 700 C, leaving char as a residue.
The bed material, mainly sand, ash and remaining char, is sent through non
mechanical valves to the fluidized bed combustion chamber where the char is burned
at about 850 C in an air flux.
The flue gases pass through a gasair heat exchanger and downstream cleaning
equipment before being vented by the stack.
The hot bed material flows back from the combustion to the pyrolysis chamber,
again through non mechanical valves. This flux of hot solid provides the heat supply
needed to support the heating and the pyrolysis of the feedstock.
Experimental results on solid circulation fluxes and on pyrolysis and combustion
kinetics are reported.
1. INTRODUCTION
in 1988 the Krber prize was awarded to the team of Professors, Sinn and
Kaminsky for the demonstration of the thermochemical treatment of municipal refuse
in an environmentally acceptable way. Prof. Buekens and Dr. Dragala were appointed
as mentors to the project, with the task to advise respectively on the technical and
economic aspects and on the cleanup of the wastewater generated.
The Laureates envisaged a reactor configuration based on the fluidized bed
technology and the combination of gasification and combustion processes as the most
promising way in tackling this accute problem. The main reason was that during
relatively low temperature gasification process (about 700C) most of the heavy
metals are not vapourised and the final volume of flue gases is significantly
decreased. The char remaining after the gasification proceses can be combusted to
provide the heat necessary to sustain the gasification process so that the overall
system can operate autothermally. There are several possible configurations for
suppyling the heat from the combustion reactor to the gasification reactor but the
most reliable method seems to be the utilization of a solid heat carrier as was
successfully demonstrated in catalytic cracking processes using fluidized bed
reactors. This paper presents a conceptual design of one particules reactor
configurations to be evaluated in this project.
575
2. PROCESS DESCRIPTION
2.1 .Solid Circulation principles
The reactor configuration is based on the AVSA process comprising a combustor
and gasifier fluidized bed reactors. In the combustor solid, liquid or gaseous products
are combusted by air, at about 900C. The heat generated by the combustion process
is stored as sensible heat in the inert sand bed of the fluidized bed. This bed is used as
heat carrier and sand to the pyrolysis reactor which operates at about 700C. In the
gasifier, the sensible heat of the sand is used to provide the heat requirements of the
endothermic pyrolysis process. From the pyrolysis unit the sand carrier is circulated
back to the combustor reactor where its temperature is raised again to 900C. The
principle of solids circulation is illustrated in Figure 1.
The expansion of a fluidized bed increases with gas velocity. On the other hand,
the pressure drop balances the weight of solid per unit section.
In a communicating vessels fluidized bed system, in which the two sections are
fluidized at different velocities, the height of the two beds is different (a and b). If an
overflow is allowed, the two levels equilibrate Inducing a solid circulation (c). As
shown on figure (2) several units may be placed in series. It is then possible to
organize a solid ciurculation loop, without any gas mixing. This circulation principle
has been applied in the present pyrolyser-combustor system.
2.2. The AVSA pvrolvser-combustor principle
The reactor consits of four cells arranged as shown in figure 3. Two of the cells
operate as combustore and the other two as pyrolysers. The pyrolysis and combustion
sections are connected through immerged orifices in such a way that a double
communicating vessel system is realised. In each part, the two cells are fluidised at
different velocities, to promote solid overflow from one cell to another.
The solid carrier flows over the partition from cell 1 to 2 and from cell 3 to cell 4.
It flows through an immerged orifice from cell 2 to cell 3 and from cell 4to cell 1.
Smooth operation of the system requires a great and regular transport of heat
amongst the various cells but the heat supply to the gasifier is much more critical.
The AVSA configuration can achieve this in the following ways :
1 ) through the sensible heat of the circulating solid,
2) by conduction through the partition wall between combustor and gasifier,
3) eventually by heat exchange pipes located in part 1 and 3, as shown on figure (3).
3. SOLID CIRCULATION TESTS ON A COLD MODEL
3.1. Instrumentation
Gas flows are determined by means of using Pitot tubes situated in each of the
ducts suppling air to the four cells, of the system. Pressure drops through the
distributor and the fluid beds are measured with water manometers. The pressure
drop at the immerged orifices is also measured. Solid circulation is studied by
injecting a pulse of hot solid (200 g, 150 degrees Celsius) at the top of cell 4. The
thermal wave is detected in the several parts of the unit by small thermistors. The
solid dispersion mechanism is much more rapid than non stationary conductive heat
transfer from particle to particle.
576
The conduction process thus only affects the thermistor responses as a drift of the
basis line.
3.3. Effect of operating parameters
3.3.1 .Solid transfer mass flow
The specific mass flow is defined as :
(mass of solid In the system)

(cycling time) (communicating holes area)
and fluctuates between 200 and 1000 kg/s m2 and presents a maximum for Ho/H 0.92.
A predictive correlation has been derived from a sensitivity analysis
performed on th parameters by stepwise regression, as shown on figure 4.
3.3.2. Pressure drop through the communication orifices
In figure 5, a correlation is presented between the pressure drop at the
communication orifice and the solid mass flow rate.
A square root law describes the results quite well. This fact allows to measure,
after calibration, the solid transfer rate by a conventional differential pressure
sensor.
3.3.3 Pvrolvsis-combustlon experiments
Pyrolysis experiments have been performed with wood pellets at 700C. The gas
stream used was a mixture of steam and nitrogen and results of the experiment have
been reported elsewhere (1). It was found that pyrolysis was completed after about
100s while the elemental analysis of the char revealed that about 95% of it was fixed
carbon. Tests to combust the char residue in a fluidized bed were successful and
showed that the burnout time was in the order of 1000 s (1).
4.
Conclusions
1. A new combustor/pyrolyser system has been investigated. It is characterised
by compactness, simplicity and reliability.
2. Cold tests model have shown that mass transfer rates as high as 1000 kg/sm2
are possible between the combustor and the pyrolyser. The main operating
parameters have been identified and optimised. It has been shown that the solid
transfer rate is measurable by a simple differential pressure measurement, which is
very attractive from a viewpoint of regulation and control.
3. Pyrolysis and char combustion studies have been successfully performed.
5.
1.
References
H.A. Masson, A twin fluid bed pyrolyser combustor system, Research in
Thermochemical Biomass Conversion, ed. A.V. Bridgwater, J.L. Kuester,
Elsevier Applied Science, London, 1988.
577
Height of the layer
I
1
i
h static
/U
mf
reduced gas
velocity
U/U
mf
I
'U/Umf>l
'U/V'2
'/"mf '"/"mf'2 " W i 'u/umf>2
F i g . 1 . P r i n c i p l e s of s o l i d c i r c u l a t i o n
1!
,u
"
'S.
*%%^
C^
1
w
m
m...
il!
"
,l_
u2
2J
Fig. 2. Avoiding gas mixing in communicating fluidized bed systems
m = 0.2573 I O
FUEL FEED
= h 1
= H X L
1 34
( (A)"
p
( (4)'
17
H
ô
H
H
.69
) ) Ref96
(sin (
.42
Df
: hydraulic diameter of the communication window = 4 s / perimeter
= solid particles mean diameter

P
Re f : Reynolds number relative to window
> x U fa
1.25 10
steam
steam
aj.r
(recycled gas)
00
.75
.50
steam
(recycled gas)
air
.25
steam (recycled gas)

.50
Fig.
3 . Layout o f t h e AVSA p r o c e s s
.75
1.00
Measured flux (kg/s nr)

Fig.
4.
Solid flux
correlation
1.25 10
579
DP TRANSFER
h - .025 m
h = .037 m
h = .050 m
(mmH20)
O h = .075 m
X h = .075 m
+ h = .075 m
1 = .054 m
1 = .054 m
1 - .054 m
1 = .054 m
1 = .035 m
1 = .027 m
Ufa/Umf incr.: 2, 2.5, 3

125 m
L =
partition wall width =
H =
partition wall height - .50 m
1 = window width
h = window height
Ho = static bed height = .45 m

dp - 300
Ho/H = .9
Umf = .22 m/s
F i g . 5. C i r c u l a t i n g system - mass flow versus p r e s s u r e drop
580
PMMA PYROLYSTS
FUNDAMENTALS AND EXPERIMENTAT, INVESTIGATION
A. Buekens, F. De Wolf and J. Schoeters

Vrije Universiteit Brussel
Department CHIS
Pleinlaan 2
B-1050 BRUSSELS
BELGIUM
INTRODUCTION
This paper describes experiments performed at the Free University of Brussels (VUB),
Department of Chemical Engineering and Industrial Chemistry (CHIS).
These experiments were performed in order to improve the yield of MMA monomer
produced during PMMA waste pyrolysis.
The results of this study were used to design a fluidized bed monomer recovery system
for the Shanghai Resource Recovery & Utilization Co (Peoples Republic of China).
PYROLYSIS OF POLYMERS
Most polymers decompose according to one or more of the following schemes :
1.
Depolymeristation (also called inverse polymerization) into monomer.
Examples are polymethylmethacrylate and PTFE.
2.
Random cracking of the main chain into fragments of uneven length.
Polyethylene and polypropylene are important examples of this category.
3.
Elimination of reactive substituents or side groups, with formation of a cracking
product on one hand, a charring polymer chain on the other. Examples are
PVCandPVAc.
(CH2CHCl)n (CHCH) + H a
(CH2CH)n (CHCH)n + CH3CCOH
I
OOC3
Table 1 gives the yield of monomer during vacuum pyrolysis [1]. The yields reported
here are only indicative. Under different pyrolysis conditions (temperature, pressure,
residence time) other results will be obtained.
KIH Groep , Vuurkruisenlaan 4,3000 Leuven
581
Polyethylene for example will produce substantial amounts of monomer at higher
temperatures. Also polystyrene is capable of much higher yields under appropriate
experimental conditions [2].
Polymethylmethacrylate
Polytetrafluoroethylene
Poly (methylstyrene)
Poly (methylstyrene)
Polystyrene
Polyacrylonitrile
Polypropylene
Polyethylene
>98%
99
95
70
45
5
2
0
Table 1 : Monomer yield for different polymers [1]

THE MECHANISM OF PMMA PYROLYSIS
PMMA decomposes according to two mechanisms :
1.
2.
At low temperatures (220C) scission at the chain ends occurs;

At higher temperatures (270C) a random homolytic scission takes place.
The low temperature reaction is believed to start at the unsaturated end groups of
the PMMA molecule. During free radical polymerization about 50 % of the polylmer
chains contain unsaturated end groups with the following structure :
CH3
CH2
I
II
CH2 C CH2 C
C02CH3
OOÔ^
The double bond strengthens the bond in position and weakens the bond in
position, so that the molecule decomposes in the latter bond to yield the following
radicals:
CH3
I
CH2 C
I
2 *3
CH2
II
"CH2 - C
I
CO^CHj
The first radical then depropagates according to a free radical mechanism [3].
582
A higher temperatures the distinction between stronger and weaker bonds becomes
less pronounced so that a random homolytic scission occurs :
CH3
CH3
CH2 - C - CH2 - C -
CH3
->
CH2 ' C"
I
+
CO2CH3
OCH
I
C02CH3
C02CH3
CH3
2 "C ~
I
CO^CHj
Both radicals react further and produce monomer by unzipping of the main polymer
chain.
TECHNICAL UNITS
PMMA is used under two forms : extrusion grade and cast material. The latter has an
extremely high molecular weight, so that thermal reprocessing is no longer feasible.
Instead, the polymer may be reconverted to monomer by pyrolysis.
Because of the relative ease with which PMMA depolymerizes, some dedicated small
scale pyrolysis units have been in use.
The techniques which have been used are :
1.
Pvrolysis in a bath of molten lead [4]

The PMMA waste is fed batchwise or semi-batchwise in a vessel filled with
molten lead at a temperature of 400 to 500C. The monomer vapours are then
condensed and the monomer is recovered after a final purification step
(distillation).
The units are quite simple to construct and to operate. The main disadvantages
are the difficult temperature control resulting in a reduced monomer recovery
and the local overheating of the vessel walls which cause carbon depositions,
because of fouling the unit has to be cleaned at regular intervals (6 to 8 hours)
which is quite cumbersome.
2.
Pyrolysis in an extruder [5]

In this process a modified polymer extruder is used. The shredded PMMA
waste is molten at 250C and passes through an reaction zonde at 500 to 600C.
It is claimed that high yields (95%) are possible without excessive carbon
depositions.
3.
Pvrolvsis in a heated cauldrons

This system has been used by Shanghai Resource Recovery & Utilization Co.
PMMA waste is batch fed in a cauldron, placed in a coal-fired brick-lined
furnace. After preheating, volatiles are driven off gradually. The remaining
carbonized residue is allowed to burn out in situ, at the end of the production
cycle, which takes 8 hours (one shift).
583
FLUIDIZED BED PYROLYSIS EXPERIMENTS [6]
i.
Experimental
The test unit consists of :
a preheating system for the fluidizing gas (steam);
a fluidized bedreactorwith an internal diameter of 15 cm in the bed zone
and of 30 cm in the freeboard zone. The reactor is made of Inconel 600
alloy and is electrically heated;
a screw feeder;
a cyclone separator;
a condensor (shell and tube heat exchanger).
The unit is fluidized with steam.
Thereactionproducts are :
a liquid product containing the MMA monomer. This liquid is separated in an
organic phase and the condensed water (from the fluidizing steam), in which
some MMA is dissolved.
PMHA f e e d
Fly-Ash
Organic phase
Fluidizing
ngA
gas
Condensate
a t e r phase
Figure 1 : Fluidized bed unit

2.
Analysis
The permanent gases (H2, CH4, CO, CO2, N2) were analysed with a gas
Chromatograph equipped with two columns : a molecular sieve 13X and a
Chromosorb 106 column.
The condensate is also analyzed by gas chromatography on a OV-101 column.
Results
The results are summarized in Figures 2 and 3.
Figure 2 gives the MMA content and the yield of the organic phase that was
produced as a function of operating temperature.
Figure 3 shows the effect of temperature on the total MMA yield (in the organic
phase + dissolved in the water phase).
584
100
300
400
SOO
Temperatur (*C)
1
2
600
Figure 2 : MMA in organic phase and yield of organic phase

1 = % MMA in organic phase
2 = MMA in organic phase as % of feed
Both figures indicate a decrease in both monomer yield and purity of the liquid
phase with temperature. The minimal temperature of operation is set by the
reaction rate. At temperatures below about 380C the rate of pyrolysis is too
low and PMMA accumulates in the fluidized bed, when fed at a rate of 1
kg/hour. The total yields recorded were high : up to 98 % at the lowest
temperature.
100
>
\ B
90
B \
û
\
80
300
400
500
Temperature (*C)
600
Figure 3 : Total MMA yield as % of feed

Conclusions
On the basis of experimental work conducted in a fluidized bed bench scale
plant the operating conditions for the fluidized bed pyrolysis of PMMA were
optimized. This has allowed to design a commercial scale (300 kg/h) reactor for
use by Shanghai Resource Recovery and Utilization Company.
585
LITERATURE
1.
Cameron, G., "Patterns and problems in the pyrolysis behaviour of synthetic

addition polymers" NB S Special publication 357, "The mechanemisms of
pyrolysis, oxidation, and burning of organic materials", Proceedings of the 4th
Materials Research Symposium, Oct.2629, 1970, Gaithersburg, Md. (Issued
June 1972).
2.
Schoeters, J. and Buekens, ., "Pyrolysis of plastics in a steam fluidized bed",

International Recycling Congress, Berlin 1979.
3.
MacCallum, J., "The mechanism of initiation of random degradation", Die

makromolekulare Chemie, 99,1966.
4.
DomingoSegui, E., Cabaero Alarcon, ., French patent 1,079,107

(25.11.54), "Procd et dispositif de rgnration des monomres partir de
polymthylacrylate, et, en particulier, de polythacrylate de mthyle".
5.
Tokushige et al., Japan Steel Works Ltd., U.S. Patent 3,959,357 (May
25,1975), "Method for continuously thermally decomposing synthetic macro
molecule materials".
6.
De Wolf, F., "The pyrolysis of PMMA", (in Dutch), Engineering Thesis, Free
University of Brussels, 1988.
586
PYROLYSIS OF EXHAUSTED OLIVE HUSKS COUPLED WITH TWOSTAGES THERMAL
DECOMPOSITION OF AQUEOUS OLIVE OIL MILLS EFFLUENTS
G. DI GIACOMO, G. DEL RE
University of L'Aquila, L'Aquila, Italy
E. BONFITTO, S. IACOBONI
Regione Abruzzo, Avezzano, Italy
. BRUNETTI
E..E.., Centro Ricerche Casaccia, Roma, Italy
Summary
A twostage thermal decomposition process for the purification
of aqueous olive oil mills effluents has been studied. In the first
stage the vegetation waters concentrates are pyrolyzed along with
the corresponding amount of olive stone obtained from the exausted
olivehusks. The salts separate into the wood charcoal bed while the
organic compounds live the pyrolytic reactor as a gaseous stream to
gether with other decomposition products of olivestones. This
stream can be used directly or after a partial condensation process
as fuel for the energy requirements of the whole process. Wood char
coal is also obtained as an interesting by product of this waste mi
nimization process. Mass and energy balances are reported together
with a simplified flow sheet of the whole process.
1. INTRODUCTION
The purification of aqueous olive oil mills effluents, which are u
sually referred as Vegetation Waters ( V.W. ) , is a serious problem for
major virgin olive oil producing countries like Italy, Spain and Greece.
For example in Italy about 3,200,000 tons of olive per year are processed
in 11,000 olive oil mills, producing 600,000 tons of oil and 1,600,000
mes of V.W.. These waste waters are brownish and evil smelling and are
very polluting, being characterized by a COD ranging from 30 to 200 g/1
and a BOD5 from 30 to 100 g/1.
Disposal of V.W. by soil irrigation is no more allowed by italian
law since march 1989. Various methods have been proposed for the disposal
of V.W., but until now only incineration of V.W. concentrates is a really
efficient treatment (1,2). However the salts contained in V.W. (1.5? 2% by
weigth) at the temperatures involved in incineration process induce foul
ing of the equipments compromising the smooth running of the process. We
propose a process for thermal decomposition of V.W. which allows to over
come both the problem of energy demand and fouling caused by melting of
salts. The process is based on a two stage thermal decomposition of V.W.:
in the first stage concentrated V.W. are mixed with olivestones obtained
from exhausted olivehusks, dried and
pyrolyzed; in the second stage
both liquid and gaseous pyrolysis products are burnt. During the pyroly
sis the salts separate on the wood charcoal bed while the organic com
pounds originally contained in the V.W. are extracted as gaseous pro
ducts. The characteristics of charcoal produced by pyrolysis are not si
587
gnificantly affected by salts coming from V.W..
Usually a liquid organic phase is separated from the gaseous stream
by means of controlled condensation and used as fuel for the concentration of V.V.. The remaining part of the gaseous stream is used to fulfill
the energy requirements of the dryer situated just before the pyrolytic
reactor.
Wood charcoal is obtained as a by-product of the proposed process
and although its amount is about 30% of the olive-stones fed to the
plant, its commercial value is at least comparable or even higher than
the commercial value of the corresponding olive-stones.
2. MATERIAL AND ENERGY BALANCES
The main characteristics of V.V. coming from batch (traditional) as
well as from continuous centrifugation olive oil mills are reported in
table 1 (3,4).
Fig. 1 shows a block diagram of the proposed purification process.
The energy and mass balances are made on the basis of a 2000 Kg/hr pyrolytic reactor. The ratio at which V.W. and olive stones are fed to the
plant is the same as that one coming from olive oil mills.
V.W. coming from olive oil mills are first concentrated up to 50% of
water by a conventional two or three stage evaporator. Energy required
for concentration is supplied by pyrolytic oil. Steam coming from concentration unit can be usually discharged into municipal sewers after condensation, as it has a sufficently low BOD.
Concentrated V.W. are fed to a mixing unit together with olive stones (about 8% humidity). The solid like stream leaving the mixing unit is
fed to a dryer in order to lower humidity from about 24% to 6%. The energy requirement of the dryer is fulfilled by pyrolytic gas.
The solid stream leaving the dryer is fed to the pyrolytic reactor,
from which solid charcoal and a gaseous stream are continuously withdrawn.
The gas stream is condensed in part under controlled temperature to give
a liquid organic phase (pyrolytic oil); the uncondensed portion of gaseous stream is used to fulfill the energy requirements of the dryer.
TABLE I. Main average characteristics of V.W.
Extr. Syst
BATCH
CENTR:[F.
oil [g/kg]
2
6.5
dr:Led residue
at 110 C[g/kg]
salt cont. [g/kg]
110
80
COD [g/1]
20
6.4
146
86
TABLE II. Experimental results of olive-stones: pyrolysis test

(basis 100 kg, 8% humid:ity, heat of comb. 4300 kcal/kg)
CHARCOAL
YELD
HEAT (DF CO MB.
29 [kg]
7400 [kca:1/kg]
OilJ
12 [kg]
5000 [kca!1/kg]
GAS
80 [NmJ]
1500 [kcal/Nm3]
588
t
2U
Jt
<$>
Tl
TI
^k
&r
<>
&J
C = CO CENTR A TO*
T I = CO WC. KM, TANK

D=DRYER
M = MIXER
T 2 = PYROtVTIC OIL TA NK
S = SEPA RA TO
P=RVROLYTIC
^7
REA CTOR
Fig. 1 Simplified flow sheet of the plant.

A pyrolytic reactor of vertical moving bed type is particularly sui
table for the proposed process.
Yeld of charcoal, gas and oil from pyrolytic reactor are based on a
test of pyrolyzation of olive stones performed on a pilot plant by Bio
Alternative (NeuchatelSuisse); the results of the test are reported in
table II.
In the mass balance of the pyrolytic reactor it has been assumed
that all the organic matter in V.W. (about 10% in V.W. coming from batch
process and about 8% for V.W. coming from continuous centrifugation pro
cess) leaves the reactor with the gas stream. Then it is condensed to gi
ve pyrolytic oil.
In table III are reported the mass balances of the process both for
V.W. coming from batch and continuous centrifugation olive oil mills: the
only difference is in the concentration unit.
In table IV are reported the energy balance of the process. It has
been assumed that the concentration of V.W. requires 420 kcal/kg of vapo
rized water and that the dryer requires 900 kcal/kg of evaporated water
(taking into account the combustion efficiency of pyrolytic gas) .
As can be seen from data reported in table IV, energy available from
pyrolytic oil and gas is larger than the energy demand of the whole
process.
589
TABLE III. Mass balance.
BATCH
STREAM
1
2
3
4
5
6
7
8
9
11
12
13
V.W.
cone.V.W.
steam
cone.V.W.
oliveston.
FLOW RATE[kg/hr]
4300
4+5
steam
dried olive
stones+V.W.
charcoal
CENTRIFUGATION V.W.
V.W.
940
3360
940
1530
2470
470
2000
%H 2 0
89
50
100
50
8
24
100
6
510
1224[Nm3/hr]
gas
pyrol. oil
pyrol. oil
603
280
~"
FLOW RATE[kg/hr]
5530
940
4590
940
1530
2470
470
2000
510
1224[Nm3/hr]
603
474
%H 2 0
92
50
100
50
8
24
100
8
~*
TABLE IV. Energy balance.

ENERGY DEMAND [kcal/hr]
V.W. CONCENTRATOR
DRYER
TOTAL
BATCH
V.W
1.75*106
0.60*106
2.35*106
CENTRIFUGATION V.W.
2.37*10 6
0.60*10 6
2.97*10 6
AVAILABLE ENERGY [kcal/hr]

3.0*10b
1.8*106
4.8*106
OIL
GAS
TOTAL
3. CONCLUSION
The proposed twostage thermal decomposition process for the purifi
cation of aqueous olive oil mills effluents allows to overcome both the
problem of energy demand and fouling caused by melting of salts. Charcoal
of commercial value is produced as a byproduct thus allowing a decrease
of the operating costs.
REFERENCES
(1)
(2)
BACCIONI, L.,(1981). Riciclo delle acque e loro incenerimento: una

soluzione per la depurazione delle acque nei frantoi. La Rivista
Italiana delle Sostanze Grasse, LVIII 3437.
LANZANI, ., BONDIOLI, P., FEDELI, E., PONZETTI ., PIERALISI, G.,
(1988). Un processo per lo smaltimento integrale delle acque di ve
getazione con contemporanea valorizzazione delle sanse nella lavo
razione delle olive. La Rivista Italiana delle Sostanze Grasse, LXV
590
(3)
(4)
117-124.
DI GIOVACCHINO, L., (1985).
vegetazione delle olive-Nota
Grasse, LXII 411-417.
DI GIOVACCHINO, L., (1985).
vegetazione delle olive-Nota
Grasse, LXV 481-487.
Sulle caratteristiche delle acque di

I, La Rivista Italiana delle Sostanze
Sulle caratteristiche delle acque di
II, La Rivista Italiana delle Sostanze
SECTION 3
GASIFICATION TECHNOLOGY
593
STUDY OF BIOMASS GASIFICATION UNDER PRESSURE
CAPART, M. GELUS, M. LESGOURGUES, Z. LI

Departement of Chemical Engineering
University of Technology - B.P. 649
F - 60206 - COHPIEGNE Cedex
Abstract
In this work are presented results concerning the effect of pressure
on the gasification of wood-char by C 0 2 and steam, and on the
catalytic power of K 2 C 0 3 for gasification.
The experimental set-up is a pressurized thermobalance which enables
experiments under isothermal conditions up to 25 bar and 1000C.
The mathematical model presented here involves a kinetic law of
LANGHUIR-HINSHELWOOD
type
and
takes
into
account
the
intra-particular diffusion of the reactant gas.
1. INTRODUCTION
Biomass gasification under atmospheric pressure in order to produce
syngas as a raw material for ammonia or methanol synthesis is today
feasible. However, gasification under pressure appears to be highly
profitable because the energy cost of the methanol production is lower
and the processing of pressurized gas (rich in CO, H 2 and CH^) requires
smaller equipments and is therefore less expensive.
Whatever the method of working of a gasifier (fixed bed or fluidized
bed), the biomass is volatized in the same various stages. These are
mainly pyrolysis of virgin wood, and combustion and gasification of the
wood charcoal, by-product of the pyrolysis.
The chemical gasification step is the slowest and undoutbly it
limits the rate of the whole process.
The main reactants of gasification are carbon dioxide and steam. The
reactions can be written as :
C + C 0 2 -
2 CO
C + H 2 0 ->
CO + H 2
To obtain information and values about gasification reactions,
thermogravimetric analysis is undoutly the most effective method. The
thermobalance set in out laboratory allows such an investigation into the
kinetics of gasification with a pure gas (C0 2 , H 2 0) or with mixed gas, in
isothermal conditions up to 1000C and under pressure up to 25 bar.
2. KINETICS AND MECANISM OF GASIFICATION REACTIONS
The (C + C0 2 ) reaction is slower than the reaction (C + H 2 0 ) . It can
be twice to ten time slower according to the temperature value and the
nature of the carbon. Gadsby (1), Blackwood (2) and Turkdogan (3) have
studied this reaction for the case of coconut charcoal, carbonaceous
vegetable material. It is usually agreed that the decomposition of CO is
594
a two step process which creates an instable oxide C(0) formed from a
free active site of carbon : C
Cf + C02
C(0) + CO
C(0)
CO + C f
The second step is irreversible and decomposition of the oxide C(0)
leads to the formation of several active sites of carbon C f .
This
mechanism
is
consistent
with
a
rate expression of
LangmuirHinshelwood
type such as that proposed by Blackwood and
Ingeme (4).
k, PCO, + k = P C O *
(mole g/g/mn)
"CO,
1 + k, PCO, + k, PCO
In this equation, the term k 4 PCO of the denominator characterises
the inhibiting effect due to carbon monoxide. Gadsby (1), Ergun (5) and
Turkdogan (3) have established more simple relation without the term k^
PC0 2 2 . Beenackers and Van Smaaij (6) have considered the kinetics using a
power law rich reveals the complexity of the reaction process :
V = k PCO,003
The mecanism involved in the reaction C + H 2 0 is more complex. Some
instable chemisorbed products appear during the reaction and for most
authors, the kinetics is in accord with a LangmuirHinshelwood type rate
expression as far as the water gas shift reaction is not at equilibrium.
Blackwood and Ingeme (4) have found a rate expression whose simplified
form is the following :
k, PH,0 + k = PH0 2
H.O
1 + k.
3. EXPERIMENTAL SETUP
The reactor of the thermobalance
is a refractory steel tube of 5 cm
internal diameter, heated by a tubular
oven (4 kw). A steam generator (10 kw)
and a superheater (3 kw) are connected
to the reactor.
The thermobalance is designed to
operate in isothermal conditions. The
wood or charcoal sample is contained
in a 0 5 mm mesh basket which is
lowered quickly (5 seconds) into the
heated zone of the reactor, by an
electrical winch itself hung from the
balance plate.
The weighing system is a modified
SARTORIUS 1264 balance set in the
pressurized housing, the electronics
remaining
outside. The reactor is
swept
by the contained gas (C0 2 ,
steam) and the balance housing by, a
slight counterflow of N 2 in order to
protect the weighing systems.
+ k_ PH
595
4. CHARCOAL SAMPLES PREPARATION
Wood cubes (oak) are pyrolysed slowly In an inert atmosphere (N )
from ambient temperature to 700C for six hours and maintained at 700 C
for a further one hour. The samples of charcoal are then cut into smaller
cubes (1,5 1,5 1,5 cm) of which the mass is about 1.4 g and the
average density 0.4 0.02 g/cm3. It is of a great importance to heat the
wood pieces slowly in order to avoid bursting them and to provide
charcoal samples of homogeneous density.
5. PROCEDURE AND EXPERIMENTAL RESULTS
The velocity of the gas in the reactor is fixed at 5 cm/s whatever
the conditions of the experiments. After the stabilisation of pressure,
temperature and gas flowrate, the sample container was lowered in the
heated zone of the reactor and the massloss of the charcoal was
recorded.
Figure (2) represents the relation of the massloss with the time.
During a short period, a rapid decreasing in the mass was observed, due
to the loss of volatile products, following this the curve of mass loss
is approximately linear up to a rate of conversion of about 60 70 %.
The rate of gasification can be defined by the slope of the linear
portion, represented by the following relation :
1
dm
dX
m 0 : initial mass of sample
V

X : rate of conversion
c
m dt
dt
40
60
TIME
80
100
(minutes)
Fig.2: CHARCOAL GASIFICATION : MASS LOSS VS TIME

(T = 900C, m 0
1.5 g, u 3 cm s"1)
Fig. 3 : CHARCOAL GASIFICATION BY C0 2 : Influence

of pressure on the gasification rate
(m ^ 1,5 g u 5 cm/s).
The gasification rate increases with temperature and pressure.

shown by figure (3) the rate increases at first rapidly with pressure
to 6 7 bar and them much more slowly.
Experiments with steam have been more difficult to perform due
condensation problems. Similar results as with C 0 2 have been obtained
900C with higher rates of gasification (see figure 4 ) .
As
up
to
at
596
dm
m. dt
(mn1)
900C
5.10
5.10 2
4.10
4.IO"'
.10
LIO"*
2.
2.10''
0"
io
15
"")
C.co
2 CO
ICJCOJ
20
CHARCOAL GA SIFICA TION BY HjO : Influence of

pressure on the gasification rate
(m
l.Sg
linntiTyifil
20
PRESSURE
PRESSURE
Fig. 4
Fig. S : CHARCOAL GASIFICATION : Influence of

presaure on the catalytic effecc.
= S cm/s).
Gasification can be catalysed by alkali metal salts, among which

potassium carbonate (K 2 C0 3 ) is known as the more efficient. The rate of
gasification is approximately (see figure 5) four times higher when the
charcoal is impregnated with about 5 * in mass of CO .
6. MATHEMATICAL MODEL AND DETERMINATION OF KINETIC PARAMETERS
In order to determine the kinetic constants of the reaction certain
basic assumptions must be clearly defined :
the wood char particle is isotropic, of spherical shape with an
equivalent radius of 0.93 cm ;
the reaction is complete and no chemical equilibrium is reached ;
the external mass or heat transfer is neglected ;
no gradient of temperature and pressure exists in the particle ;
the pseudo steady state is appropriate for calculating the
concentration of the gaseous reactant within the particle.
With these assumptions, the mass balance equation relative to the
reactant gas (CO_ or H_0) can be written as follows :
d*p
dx
1 +
d
2
P ,
( )a +
dx
dp
dx
RTLa
+ V
De P
(1 + P)
with
: volumic fraction of the reactant gas
: radial coordinate
L(m) : radius of particle
P(Pa) : total pressure
R (J mole~ 1 K" 1 ) : ideal gas contanst
De (ma s _ 1 ) : mass diffusivity of the gas
1
,

V (mole m 3 s 1 ) : rate of reaction
T (K) : temperature of gasification
The mass balance equation was numerically solved by the Runge Kutta
method and the profile of the reactant gas concentration optimized by a
"shooting method" (criterion P(L) Ps).
The mass diffusivity of the reactant gas De is uncertain ; however,
from
the
GROENEVELD'S
investigations on the diffusivity of C 0 2
throughout
slices
of
wood
char (7), its value was fixed at
dp
0
dx
597
0.15 IO * m a s 1 , which seems a suitable value with respect to the
temperature and the high porosity of the woodchar.
In order to fit the experimental results of the rate of gasification
with C0 2 in the pressure range 1 2 5 bar and the temperature range
800 950C. The relation due to Blackwood is appropriate :
k, PC0 2
k 2 PC0 a
1 + k 3 PC0 2 + k A PCO
Each constant kt obeys to the Arrhnius law :
E<
exp
and a good fit is obtained by taking the
RT
values of kj and Et
k10
k
a
k3
k.
131 ( s 1 atm" 1 )
7.7 10" a ( s 1 a t m ' 2 )
2 (atm1)
1.26 1 0 a ( a t m 1 )
Influence of
Et
E2
E3
E
30000
20000
0
45500
cal
cal
cal
cal
mole1
mole1
mole1
mole1
Influence of temperature
pressure
'1
following
Fig. 6 : Profiles of intreparticular gas concentration
The aspects of the concentration profile of the reactant gas leads

to the following remarks : the gradient of reactant gas concentration
decreases when the total pressure increases and that gradient increases
with temperature. Indeed the rate of reaction is augmented by temperature
so that the rate control by internal diffusion is favored.
REFERENCES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
GA DSBY J. and al. Proc. Roy. Soc. London (1948), p. 35776.

BLA CKWOOD J.D., Coke and Gas, (1960) 22, p. 190194.
TURKD0GA N E.T., VINTERS J.V., Carbon (1970) 8, p. 3953.
BLA CKWOOD
J.D., INGEME A .J., A ustralian J. Chem. (1960) 13,
p. 194209.
ERGUN S.J., Phys. Chem. (1956) 60, p. 480485.
Fund, of
VA N DEN AARSEN
E.G.,
BEEN
A CKERS A A
. .,
A
V N SWAAIJ
Thermochem. Biomass. Conv., Estes Park, Colorado 1822 Oct. (1982).
GR0ENEVELD M.J., The cocurrent moving bed gasifier Ph. D Thesis,
Twente University (1980).
598
GASIFICATION OF CHARCOAL IN MALAYSIA
W HOI ! and A V BRIDGWATER
Forest Research Institute of Malaysia D epartment of Chemical Engineering
Kepong
Aston University
Selangor
Aston Triangle
52100 Kuala Lumpur
Birmingham B4 7ET
Malaysia
UK
Summary
The paper highlights the practical experience and potential of using residue charcoal for
small-scale power generation in rural areas. Trials conducted showed that with very
slight modifications diesel and petrol engines can be adapted to work satisfactorily on
producer-gas. The conversion efficiencies of diesel (13 kW) and petrol (45 kW)
engines working on producer gas was found to be 22% and 17% respectively. With its
simple operation and maintenance, the down-draft gasifier was found to be suitable for
providing areliableand independent source of electricity to the rural areas in Malaysia.
INTRODUCTION
Solid biomass such as wood and charcoal can be converted into useful gaseous fuel by
a process known as gasification. D uring the Second World War, producer gas from
gasification was used extensively in Northern Europe and many countries in the Asian and
Pacific region as fuel for driving buses, tractors, cars and other mechanical equipment (1).
Since wood was abundantly available at that time, wood charcoal was the main feedstock.
After the War, the availability of cheap oil led to a complete halt to the use of producer gas.
However, the sudden increases in the price of fossil fuels in the 1970s injected new interest in
this old technology. This has led to the development of new gasifiers that are safe, efficient
and economical to use (2). Today, gasifiers are not only designed to use charcoal as feedstock
but can also be adapted to utilise forestry and agricultural residues with relatively high
efficiencies compared to pre-war gasifiers.
In Malaysia, producer gas technology has a good potential in the generation of
mechanical and electrical power, especially for some cottage industries in rural areas which rely
heavily on liquid fossil fuel. Although it is still possible for rural population to make use of
conventional prime movers, it is expensive to depend entirely on liquid fossil fuel even when
subsidised. As a result, these industries are facing the problem of high operating cost because
of high fuel price.
Research and Development in charcoal gasification was initiated by the Forest Research
Institute, Malaysia in 1986. This work was partially supported financially by The Federal
Republic of Germany through the Malaysian-German Forestry Research Project (3). In this
project emphasis was placed on the development of producer gas systems that are easy to
operate, be maintained, and fabricated using locally available materials.
The main aim of this paper is to assess the performance of a 7 kW downdraft charcoal
gasifier which has been installed at the Institute for trials.
THE GASIFIER
The charcoal gasifier installed at FRIM consists of four main components (Figures 1
and 2). They are:
a)
Areactormade of stainless steel to generate the gases.
b)
A cooler to condense the tar and condensibles in the gas.
c)
A cloth filter to remove soot and ash.
d)
A diesel and petrol generating set
1 Currently FRIM Research Fellow at Aston University
599
The reactor has the following specifications:
Height of reactor
Diameter at nozzle level
Primary air supply
Height of reduction zone
Insulation of reduction zone
Gas cleaning
Gas cooling
Volume of reactor
Capacity
85 cm
20 cm
3 nozzles
24.5 cm
Refractory brick lining
Cyclone
Semi-circular air cooled tubes
0.09 m3
2.5 kg/h charcoal
The reactor is a downdraft system, cylindrical in shape and lined with a thick refractory brick
lining. On the top of the reactor is a fuel feeding lid through which charcoal can be fed. When
fully charged the reactor contains approximately 7 kg of charcoal and the gasifier can then run
for about 4 hours. However, the reactor chamber can be extended upwards if there is a need to
put in more charcoal in order to reduce the recharging rate. Air for the oxidation zone is
supplied through a valve located at the side of the reactor. In the reduction zone, an inspection
door is provided for inspection and starting the gasifier. An ash door is located at the bottom
of the reactor for periodic cleaning of the gasifier and removal of the ash. A shaker arm which
can be rotated helps to loosen the burning charcoal at the reduction zone in order to prevent
bridging.
Fuel hopper lid
Blower
Inspection gate
Gas test valve
Shaker arm
Air filter
Mixer
To engine
Gas cooler Gas cleaner
Figure 1
Safety stop
Gasifier Layout
The gas passes through the grate and then passes upwards in an annular space around
the reduction zone and leaves the gasifier near the top via the gas outlet pipe. The gas is then
passed through a simple cyclone which removes a large proportion of the dust carried with the
gas stream. The temperature of the gas at this point is about 120C. The gas is then passed
through a simple pipe cooler which cools the gas by natural convection. Moisture and wood
tar condense along the sides of the pipe and can be drained off at the bottom of the cooler. The
gas temperature after passing through the cooler is found to be between 27 - 30C.
To further remove the remainder of the dust, the gas is passed through a simple cloth
filter which is installed between the cooler and the generating set. The gas temperature at this
point is about 25C.
600
Figure 2
Gasifier
The diesel engine using a dual fuel system has the following specifications:
Type
: Two cylinder, 4 stroke direct injection
Volume
: 2 litre, bore 87.5 mm, stroke 110 mm
Compression ratio
: 17.5 :1
Power
: 13 kW at 2000 rpm
Governor
: mechanical
Cooling
: water cooled
Starter
: hand cranking
The petrol engine which is operated fully on gas has the following specifications:
Model
Toyota model 4K
Cylinder volume
1.29 litre, bore 75 mm, stroke 75 mm
Compression ratio
9:1
Maximum power
45 kW at 5600 rpm
Cooling system
water cooled
Starter
electric starter
Both the engines are coupled to a simple generator with the following specifications:
KVA
7.5
Rpm
1500
AC volt
415
AC amps
10.5
Frequency
50 Hz
601
OPERATION OF THE GASIFIER
Fuel preparation
During all the trials, the gasifier was fed exclusively with rubberwood charcoal
produced by the transportable metal kiln (4). The charcoal has a fixed carbon of 80-85%, ash
content of 3-5%, volatile content of 10-15% and moisture content of 7-10% (5).
In order to prevent bridging just above the nozzles the charcoal was broken into small
pieces. The ideal size distribution of the gasifier fuel was found to be between 0.5-10 cm. As
charcoal is very hydroscopic, it must be stored in a closed shed to minimise water absorption.
Starting procedure
Before starting, the reactor is filled with about 2 kg of charcoal. A blower with suction
operation is fitted to the flare pipe of the gasifier. The charcoal is ignited with the help of
burning material at the inspection gate. The fuel lid at this time is left open and the charcoal is
left to ignite freely. As soon as the charcoal in front of the nozzle is glowing well, the reactor
is filled with charcoal. The lid and the nozzles are then shut tighdy and the blower is then
transferred to the primary air inlet valve of the gasifier with pressure operation.
The gas produced can be tested at the flare located on top of the gas cleaner. The
quality of the gas is determined by igniting it. A certain amount of practical experience is
needed in order to assess the quality of the gas. A good gas is normally indicated by an almost
transparent flame which bums steadily without blowing out. A bright yellow flame indicates
that the gas is contaminated with tar and vapour and is unsuitable for the engine. Sparks in the
flame mean that carbon particles are present in the gas and this indicates that the filter system is
not working very well.
As soon as the gas burns consistently with a transparent flame, the engine can then be
started and the blower removed. In order for the engine to work uniformly the volume of the
gas provided by the blower must not be less than 30 m3/h.
RESULTS AND DISCUSSIONS
The producer gas has the following typical analysis: H2 : 10.2% vol; CO : 27.6% vol;
CO2 : 4.0% vol; CH4 : 1.0% vol; N2 : 55.0% vol; O2 0.2% vol. The analysis does not vary
by more than 10% under any operating conditions. Taking the heating value of the gas to be
about 4.5 MJ/m3, it has been found that the thermal efficiency of the gasifier is about 70%.
This means that conversion of the chemical energy in the charcoal into gas energy is 70%. The
loss of combustible material (such as charcoal fines) in the ash accounts for about 10% of the
energy supplied by the charcoal. The remaining energy is lost as sensible heat in the gas and
from the reactor as heat to the surrounding. The results of gasification trials using rubberwood
charcoal as feedstock can be summarised as below:
Power output
Fuel consumption
Start-up time
Gasifierrefuelliinginterval
Fuel replacement
Thermal efficiency of engine
Diesel engine
5.2 kW
1.5 kgft
15-20 mins
4h
75%
21.6% overall
Petrol engine
4.0 kW
2.0kg/h
20-30 mins
3h
100%
12% on gas
In general there have been no serious problems in converting diesel and petrol engines
to work on producer gas. Diesel engines seem to be more suitable when there are load
fluctuations. Petrol engines are, however, more suitable when a constant load is needed. It
must be remembered that engines working on gas are extremely dependent on the moisture
content of the feedstock. Wet charcoal with a moisture content of about 18% causes the output
power of the petrol engine to be between 5-10% lower and the diesel replacement of the diesel
engine to be reduced to 70%.
Charcoal with sizes larger than 3 cm has been found to be unsuitable as serious
602
bridging occurs in the region just above the air injection nozzles resulting in poor gas
production. When this occurs the fuel lid has to be opened (although it is extremely
dangerous) and a stick has to be inserted into the fuel bed in order to relieve the blockage.
The gasifier can be started easily with a battery and good gas production can be attained
within 10-15 minutes. If the moisture content and sizes of the feedstock used are correct the
gasifier system can be left to run for hours without much supervision. Refueling can be carried
out with the engine running but idling. The charcoal bed in the reducing zone, however, has to
be changed after every 20 hours of operation because the ash and fines will block the flow of
the gas and the output power will be significantly reduced. This process normally takes about
1 hour.
The cloth filter has to be changed after every 20 hours of operation. The cloth filter can
be reused after cleaning by shaking. The process of changing the filter normally takes about 1
hour. In order to maintain a constant output power, the cylinder head, valve port and valve
seating has to be cleaned after every 100 hours of operation. The time needed for this
operation is normally 1 hour. Because of high temperatures in the reactor chamber, the
asbestos gaskets in the reduction zone, fuel lid and the ash door have to be replaced after 300
hours. Failure to replace these gaskets can adversely affect the performance of the gasifier due
to leakage of air.
It has been found that the paint on the walls of the reactor will start to peel badly after
300 hours of operation. For long term protection of the gasifier it is necessary to repaint the
walls of the reactor and cyclone with heat resistant paint after every 300 hours of operation.
CONCLUSION
Studies on the gasification of rubberwood charcoal and the utilisation of producer gas
in internal combustion engines has shown that it is possible to develop small inexpensive
down-draft gasifier systems for rural applications by using locally available material. The main
constraint in the utilisation of producer gas in engines is the cleaning of the gas to that it is free
of impurities. Not much work has been carried out to develop a simple but efficient gas
cleaning for the gasifier.
The assessment of the results has shown that low power output systems fuelled by
charcoal have considerable potential for a number of rural applications including water
pumping, drying of food and shaft power production. Apart from being reliable, these
systems are easy to operate and maintain. The main problems in the utilisation of this system
lie in the inconvenience in the start up and the maintenance of the filter system by the operator.
REFERENCES
(1)
(2)
(3)
(4)
(5)
Anon, "Producer gas: another fuel for motor transport:", National Academy Press,
United States, 112pp, 1983.
Anon, "Producer gas technology", Papers presented at International Producer Gas
Conference, Bandung, Indonesia. The Beijer Institute, Sweden, 1985.
Graf, U, "Charcoal gasification at the Forest Research Institute Malaysia. "Report of
short-term expert", D eutsche Gesellschaft fur Technische Zusammenarbeit, West
Germany, 1986.
Hoi W K, Low, C , and Wong, W C, "The production of charcoal by the improved
transportable metal kiln.", Paper presented at International Conference on Rural
Technology, Kuala Lumpur, 1985.
Hoi, W K, "The production of rubberwood charcoal by the transportable metal kiln",
Paper presented at Rubber Research Institute Colloquium on Research and
Development in Rubberwood, Kuala Lumpur, 1985.
603
UPDRAFT GASIFICATION OF WASTE FUELS
P. STHLBERG, E. KURKELA, H. FILEN & . SALO
SF02150 Espoo, Finland
Bioneer Oy
SF13101 Hmeenlinna, Finland
Summary
The aim of the study was to extend use alternatives for gasification
technology by studying the suitability of updraft gasification for
gasifying waste fuels. The waste fuels studied were municipal waste,
forest residues, straw and car scrapyard waste. The present version
of the gasifier is well suited for forest residues, pieceshaped
municipal waste and car scrapyard waste. Faultless operation of the
gasifier with crushed and chopped municipal waste and straw requires
the use of a fuel mixture of larger piece size, for example, sod
peat or wood chips, or changes in the construction of the gasifier.
The flue gas emissions are fairly low, although the plant is not
equipped with flue gas purification. A
scrubber used in the
experiments reduced the particulate contents of the flue gas by 70 %
to 50 mg/m2n and the heavy metal contents in solids by 30 99 %.
The scrubber had no significant effect on gaseous emissions. As the
specific emissions of certain components of unpurified flue gas are
much lower than those from grate and fluidized bed combustion, the
flue gases can be purified further at lower investment costs. The
competitiveness of the gasification plant seems to be good in the
size class of 5 15 MW and municipal waste as the fuel. Two Bioneer
gasification plants for forest residues with 4 and 6 MW gasification
outputs have been in operation in Sweden since 1986. The first gasi
fication plant designed especially for municipal waste will be put
into operation during spring 1989 in Italy.
1.
INTRODUCTION
The use of updraft fixedbed gasification for producing district
heat was developed to a commercial level in the early 1980s in Finland.
There were a total of nine Bioneer gasification plants in operation in
1988 in Sweden and in Finland. These plants produce district and process
heat and are fueled with sod peat, wood chips and wood residues. Bioneer
gasifiers are manufactured for the output class of 1 15 MW.
In the Bioneer gasifier the fuel is gasified with air and steam in a
reactor of shaft furnace type. The process was primarily developed for
the gasification of sod peat and other pieceshaped biofuels. The flow
chart of the Bioneer gasification district heating plant is shown in
Figure 1.
The temperature of the combustion zone in the lower part of the
gasifier can be controlled by the amount of steam fed along with the
604
10
14
7. Ash ballette
1. Fuel bin
2. Fuel feed conveyor 8. Drop separator
9. Humidifier
3. Fuel feeder
10. Gasification air fan
4. Gas generator
11. Plate heat exchanger
5. Ash removers
12. Gas pipe
. Ash conveyor
Figure 1.
13. Gas burner

14. Combustion air fan
15. Gas boiler
16. Economizer
17. Rue gas fan
18. Stack
Flowchart of the Bioneer district heating plant.
gasifying air. In this way, ash melting, occurring even at low temper
atures, and problems due to it in the operation of the grate and in the
ash removal can be prevented. The steam reacts with hot carbon in the
gasification zone and forms carbonmonoxide and hydrogen.
The proportion of tar condensed in updraft gasification is as high
in the product gas that the gas cannot be used as such for example for
the fuel of gas engines or conveyed long distances in pipelines. In the
existing Bioneer plants the gas is burnt close to the gasifier.
The competitiveness of the Bioneer boiler plant compared to conven
tional solid fuel boilers is based on the following factors:
high reliability, automatic operation, high degree of utilization
high efficiency even at partload
low specific emissions, small need of flue gas purification
possibility to employ different feedstocks in the same plant.
In the last few years, the research and product development work on
updraft gasification, done in cooperation with the Laboratory of Fuel
Processing Technology of VTT and Bioneer Oy, has focused on the gasifi
cation of different waste fuels. Tests have been performed mainly at a
test station of 1 MW gasification output, where the gas is burnt in a
multiple tubular boiler. Experiments have also been carried out with
municipal waste at a district heating plant of 6 MW.
2.
TEST STATION AND TESTS

The test station constructed by VTT and Bioneer Oy for joint re
search and product development was completed in 1985. The nominal gasi
fication output of the station is 1 MW (Figure 2 ) . The test station is
equal to the commercial district heating plants, but its instrumentation
is more extensive than at the commercial plants and it is also equipped
with sampling units and data collectors required in research and product
development.
The waste fuels used in the gasification tests were municipal
waste, forest residues, straw, rubber and plastics waste from car scrap
605
Figure 2.
Test gasification plant, gasification output 1 MW.
yards, and mixtures of these, sod peat and wood chips. Properties of the
waste fuels are presented in Table I.
The gasification tests with different waste fuels took 3 1 0 days.
In the determinations, attention was paid especially to adjustments of
the plant, to tar contents of the product gases and, for municipal
waste, to flue gas emissions, in addition to fuel and process measure
ments.
Table I. Test fuels.
Fuel
Code
Sod size Moisture Ash

content
mm
%
11.8
16.8
13.6
13.5
MUNICIPAL WA STE
waste briquettes
crushed waste I
crushed waste II
chopped waste
C
D
0 35
0 20
8
29
46
42
FOREST RESIDUES
0 30
52
4.2
STRAW
barley straw
wheat straw
F
G
0 100
0 70
30
16
5.7
4.1
CAR SCRAPYARD WA STE

waste I
H
10 60
16
19.4
waste II
2 20
I
19
30.9
very unhomogeneous, largest metal pieces and glass removed
606
3.
RESULTS ftHD DISCUSSION

The composition of the dry product gas (main components) and the net
calorific value calculated on the basis of these are presented in Table
II. In addition, the product gas contains light hydrocarbons and tar,
which increase the net calorific value by 0.5 4 MJ/m3n [m3n = m3 (0
C, 1.013 bar)]. Typical compositions and heat values of the product gas
of wood chips and peat gasification are also presented as reference
values.
The dry product gas of wood chips, forest residues and sod peat con
tains 50 100 g/m3n tar. The tar content of municipal waste ranges 10
20 g/m3n, of straw 1 0 4 0 g/m3n and of car scrapyard waste 80 200
g/m3n.
The present construction of the Bioneertype gasifier is well suited
for the gasification of forest residues, municipal waste briquettes and
car scrapyard wastes. When chopped and crushed municipal waste and straw
were gasified, occasional fuel arching occurred at times. A rching re
sults in variations in the quality of the product gas and in the
gasification output. The operation of the gasifier is improved if a fuel
mixture in piece form is used.
Emissions developed in the combustion of gas produced from municipal
waste are presented in Table III. The experiments with waste types A and
were carried out at the test station of 1 MW and those with wastes C
and D at the district heating plant of 6 MW. Flue gas purification
Table II.
Composition and net calorific value of dry product gas.
Fuel and code
CH4
Moist,
cont.
CO
"2
Heat
value
Hu
MJ/m3n
14.6
14.8
18.5
13.8
16.3
14.8
2.6
1.9
2.0
1.5
1.7
2.0
11.0
13.0
12.0
12.7
12.4
12.5
4.7
4.5
5.3
4.4
4.7
4.2
C02
42
17.8
17.9
20.6
18.4
18.7
14.7
Forest residue
chips E
52
23.1
14.9
2.3
9.9
5.3
Straw F
Straw G
29
16
18.9
14.9
17.6
11.3
2.3
2.9
13.8
14.8
5.1
4.1
Scrapyard waste H
Scrapyard waste I
16
19
22.5
18.9
19.0
14.3
9.0
Sod
Sod
Sod
Sod
25
33
42
52
24.5
24.2
21.6
16.1
19.0
18.8
16.8
16.7
1.4
1.6
3.0
3.0
2.4
2.0
5.4
4.5
6.2
6.2
5.4
4.5
MSW1 A
MSW B/wood chips 2
MSW B/wood chips 3
MSW C/sod peat 4
MSW C/sod peat 5
MSW D
29/42
29/45
116/36
46/36
peat
peat
peat
peat
Small wood chips

Large wood chips
1 MSW = municipal solid
45 %, 3 r wood chips 60
10.6
10.2
10.3
12.5
14.3
29.0
6.8
15.4
1.6
5.9
30.2
10.8
2.5
7.1
5.9
waste. Dry matter contents: 2 wood chips
%, 4 sod peat 25 %, 5 sod peat 42 %
43
41
607
equipment was not used at the test station. A t the district heating
plant, the flue gases were purified with a wet scrubber.
The contents of heavy metals presented in Table III were determined
only for the solid matter, except that of mercury. The mercury contents
also include steam phase. The PA H contents include 7 compounds, chlor
benzenes 11 compounds and chlor phenols 23 compounds. 15 compounds were
determined for chlorinated dibenzofuranes and 12 compounds for chlor
inated dibenzopdioxines.
One of the greatest advantages of updraft gasification is a low
particulate content of unpurified flue gas, when further purification is
more simple and cheaper than in most combustion processes.
The emission values presented in Table II cannot be considered as
typical emissions from a plant based on the gasificationcombustion pro
cess. The values are primarily test results for dimensioning the es
sential flue gas purifiers (e.g. wet scrubber and fiber filter) and for
evaluating purification costs.
Table III. Contents of emission components in flue gases in the gasi
fication tests with municipal waste. The values are re
duced to 10 t CO2 content.
Type of municipal waste
A
Particulates
mg/m3n
350
Heavy metals:
Hg
mg/m3n
0.09
Cd
mg/m3n
0.42
Pb
mg/m3n
14
Cr
mg/m3n
Zn
mg/m3n
37
PAH
pg/m3n
12.3
PCB
pg/m3n
0.2
Chlorobenzenes pg/m3n
7.6
Chlorophenols pg/m3n
6.2
Furanes
ng/m3n
0.04
Dioxins
ng/m3n
N0 X
mg/m3n
240
SO2
mg/m3n
405
- 0 U C , 1.013 bar
< = smaller than analytical accuracy
Dry matter content: * wood chips 45 , **
4
B/wood
chips*
C/sod
peat**
330
42
60
0.03
0.06
0.02
0.02
0.05
5.0
40
11.6
1.0
8.2
6.5
<0.04
1.7
4.0
0.01
0.01
3.3
5.0
5.6
2.5
8.1
7.8
8.3
3.6
2.2
8.4
<1.0
<1.0
<1.0
<1.0
390
600
sod peat 25 %
CONCLUSIONS
The tests indicated that the updraft gasifier is well suited for the
gasification of pieceshaped waste fuels. When using chaff and fuels
with a high fines content, the use of a support fuel is required either
in the gasifier or in the combustion of gas to guarantee the faultless
operation of the gasification plant. The flow of the fuel can also be
improved by equipment technical measures. As the product gas contains an
abundance of condensing compounds, the gas should be burnt in the im
mediae vicinity of the gasifier. The need for flue gas purification is
lower in gasification than in direct combustion.
608
PEAT AMMONIA PLANT IN OULU - SYNTHESIS GAS PRODUCTION FROM PEAT BY
FLUID-BED GASIFICATION
K. SIPIL, C. WILN, E. KURKELA, A. MOILANEN & J. KOLJONEN
SF-02150 Espoo, Finland
Kemira Oy
SF-90101 Oulu, Finland
Summary
A peat ammonia factory was put into operation at the Oulu Works of
Kemira Oy in summer 1988. The factory uses about 1.2 million MWh sod
peat for producing 80 000 t/a ammonia for fertilizer production. The
total investment in replacing the old heavy-oil based plant with a
peat-based one was FIM 225 million, and it concerned peat handling,
drying and gasification and gas cleanup. The plant is the only plant
producing synthesis gas from peat in the world. Similar technology
can also be used for biomass. Sawdust has been gasified mixed with
peat. Sod peat is crushed and dried in a pressurized steam dryer,
and the dry peat is then gasified in a pressurized HTW gasifier with
oxygen and steam. The trial runs of the plant were started in May
1988, and ammonia production in August 1988. The longest uninterrupted operation time has so far been 31 days.
In the research work carried out in co-operation between Kemira Oy
and the Technical Research Centre of Finland, the main topics have
been crushing and drying of raw material, feeding into a pressurized
reactor, safety, reactivity and gas impurities in gasification, ash
behaviour, and waste waters. Research results are reviewed in this
paper.Further research will focus on peat handling and on gas impurities. A new project has been initiated on IGCC applications,
where hot gas cleanup and biomass utilization in pressurized reactors are of major interest. The work is a part of a national fuel
processing research programme JALO.
1.
RAW MATERIAL HANDLING

The feed rate of sod peat (moisture content 40 %) into the plant is
42 t/h. The sods are crushed and fed into a pneumatic back-pressure
steam dryer, and the moisture content of the product is 15 % after the
dryer. The dryer is operating at 4 bar pressure. The heat obtained from
the dryer is used for district heating. The condensate of the dryer is
led among the waste waters of the factory and combustible components to
the power plant. The flow-sheet of the plant is shown in Figure 1.
One research topic of significance in the peat ammonia project has
been peat properties, which are essential in pretreatment and feeding
devices. These include flow-technical characteristics of peat and biomass, feed into pressurized reactors, as well as self-ignition and dust
explosion characteristics. Attention has been paid especially to the
609
Sod
41 t/K moUtun 40%
Outotmhol
tcnibb*
ISOOkmolfo
t siuda
Dual ttpntion
Figure 1.
Flow-sheet of the peat ammonia plant of Kemira Oy.
significance of pressure up to 10 bar, and to the behaviour of dried

peat in the lockhoppers and feeding lines of the gasifier. The peat
leaves the lines at 1 - 4 bar pressure and at 95 C temperature.
The attritive effect of the dryer is shown in Figure 2. The particle
size distribution of sod peat crush is shown after the crusher and in
the outflow from the dryer. Dried lignite crush, which is used as the
raw material of the Berrenrath plant in the F.R.G., is presented as
reference.
The properties of various peat grades were determined by an annular
ring shear cell (Walker). The flow curve and function (FF) can be
determined by carrying out the measurements at several different
consolidations /1, 21. When the internal friction and effective internal
friction, volume weight and unconfined yield strength is known, the
minimum dimensions of the discharge opening of the bin can be calculated
on that basis that the gravitational flow of the bulk solids is able to
break the arch formed in the discharge opening. The results of the shear
tests are presented in Table I.
2.
The peat is fed with the nominal flow of 25 t dm/h into the HTW
gasifier. The gasifier has operated as expected. The large amount of
fines among the peat and the high naphtalene content of the gas have
caused malfunctions. A new parallel crusher is being installed at the
plant to improve the particle size distribution of the peat. Benzene
scrubbing has been intensified to remove naphtalene. The naphtalene
content might also be reduced by using limestone in the fluidized bed.
The typical operation values for the gasifier are as follows: bed
temperature 700 C, free-board temperature up to 900 C; gas composition: carbon monoxide 35, hydrogen 32, methane 6 - 8 , and carbon dioxide
22 vol?. The peat feed is 23 t/h, oxygen demand 290 Nm3/t peat (maf) and
steam 160 kg/t peat; synthesis gas output 925 Nm3/t peat (CO + H2). The
610
100.0
79.4
*
.
o
<
oc
u
.
X
o
iii
5
LU
63.1
60.1
39.8
31 .
25.1
20.0
16.8
12.8
10.0
>
I
7.9
.3
s
=>
S.0
4.0
3.2
2.6
.082
0.106
0.21
0.6
1.88
3.15
4.78
9.52
PARTICLE SIZE, mm
LIGNITE
Figure 2.
PEA T AFTER CRUSHER
PEA T AFTER DRYER
Attrition of sod peat crush in the MoDo steam dryer.
Table I. Results of shear tests (Annular Shear Cell (Walker)).

Material
Sod peat crush

Crush 1 (dried)
Crush 2 (dried)
Crush 3
Crush 4
Crush 5 (dried)
Crush 6 (dried)
Crush 7 (dried)
Crush 8
Particle
size
d| value
Moisture
content
Minimum
NFF
wtJ
opening
cm
vol. wt
kg/nP
355
512
470
470
512
292
311
348
10.8
17.4
0.5
12.1
11.9
30.9
27.9
14.0
14.8
14.5
21.4
9.4
8.7
29.9
14.9
22.1
14.0
18.1
46.4
25.2
29.1
Milled peat 1
Milled peat 2
<3
<3
11.0
36.9
5.9
3.2
10.4
39.8
200
300
Pellet crush
0.5
21.7
7.5
550
<0.27
16.7
24.7
31.6
653
Lignite
0.63
0.17
0.16
0.4
< 0.4
0.37
< 0.37
9.4
5.8
14.2
12.4
611
carbon conversion is 88 % and the ash is fed into the steam boiler for
total carbon utilization.
Research has focused on the reactivity of peat and the behaviour of
ash in gasification. The reaction rate of different sod peat chars has
been slightly lower than that of lignite. The attrition of peat grains
in the bed can be significant /3/. The reactivity of char is reduced by
densification.
The deposit formation of ash is in accordance with the theory of
sintering by viscous flow in peat gasification. According to this
theory, glassy particles are sticked to each other as a result of
viscous flow. The siliceous ash molten in the oxygen flame forms glass.
The peat ash is typically siliceous and hence, deposit formation with
this mechanism can be expected /4/. A laboratory method based on the
measurement of compression strength was developed for testing the
sintering tendency of ash /5, 6/ and viscosities were also measured for
different peat ashes. The compression strength of ash pellets as a
function of the B/A index is shown in Figure 3, which indicates a good
correlation at 800 C in these tests. This index describes the ratio of
alkaline and acid oxides in the ash. The viscosity of ash as a function
of temperature, measured at the Institute of Gas Technology, is
presented in Figure 4. The viscosity measured at 1 000 C also cor
relates with the B/A index well /4/.
3.
OUTLOOK FOR THE FUTURE

The plant is operating parallel with an existing oilfired gasifier,
and hence, the full capacity can be achieved either by peat or by heavy
oil. In summer 1989, accurate measurements will be carried out for gas
impurities and waste waters. A new object of research will be the
application of experience obtained from this plant for IGCC
applications. Preliminary plans have been made to lead a byflow for hot
gas cleanup experiments, in order to study by longterm tests the
durability of ceramic and metal filters in use for biofuels. On the
basis of the present experience it may be concluded that it is possible
to produce ammonia and chemicals from peat.
(3
UI
et
0.75
Figure 3 .
B/AINDEX
Compression s t r e n g t h as a function of the B /A index.
612
Wc"
8#
g
1400
TEMPERATURE [C]
+ JOUTENNEVA
KMNEV
A
O ILOMA NTSI
Figure 4. A sh v i s c o s i t y as a function of temperature.
VIIDANSUO
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
Rautalin, A. & Wiln, C. Peat handling and safety at combustion and

gasification plants. 10th Int. Conf. on Fluidized Bed Combustion,
San Francisco, CA, April 30 May 3, 1989.
Thun, R. & Rautalin, A. Technical flow problems and safety risks
connected with peat handling. Bulk Solids Handling 6(1986)5, p. 845
851.
Sipil, . Reactivity of biomass chars in fluidbed steam
gasification. Proc. Research in Thermochemical Biomass Conversion,
Phoenix, Arizona, 1 6 May, 1988. 11 p. + app. 2 p.
Moilanen, A. Ash behaviour in gasification. Proc. Symp. on LowGrade
Fuels, Helsinki, Finland, June 12 16, 1989. Espoo 1989, VTT Symp.
Series. In press.
Hupa, M., Skrifvars, B.J. & Moilanen, A. Measuring the ash
sintering tendency by a laboratory method
Proc. Engineering
Foundation Conf. on Mineral Matter and Ash in Coal, Santa Barbara,
Ca, Feb 21 26, 1988.
Moilanen, ., Hupa, M. & Skrifvars, B.J. The effect of temperature,
chemical composition and gas atmosphere on sintering of peat fly
ash. Int. Conf. on Coal Science, Tokyo, Japan, Oct. 1989.
Koljonen, J. Bulk chemicals ammonia. Proc. Int. Conf. Biomass for
Energy & Chemicals in Europe, Industry & Agriculture, London, Nov
26, 1987.
KolJonen, J. Synthesis gas and fuel gas from peat for industrial and
residential applications. Proc. 17th World Gas Conf., Washington,
DC, June 5 9 , 1988.
Fagerns, L. & Wiln, C. Steam drying process for peat and their or
ganic condensates. Proc. 8th Int. Peat Congr., Leningrad, Aug 14
20, 1988. Moscow 1988, Int. Peat Society. Vol. II, p. 261 271.
613
DEVELOPMENT OF A DOWNDRAFT MOVING BED BIOMASS
GASIFIER
R. Bilbao, J.Lana, P.Garcia, J. Arauzo
Department of Chemical Engineering. University of Zaragoza
50009 Zaragoza. SPAIN.
Summarv
Thermochemical processing of agricultural (corncob, cereal straw,
...) and forest residues (branches, chips, thinning residues, ...) is an
interesting alternative for small scale energy production. In
particular, air gasification in a downdrat moving bed gasifier
yields a LHV gas with a low tar content, which is useful for
electricity and/or heat production in isolated communities farms
and small industries (ceramics, dryers, wood processing, ...). Two
gasifiers of the type described above have been developed in order
to process agricultural and forest residues which are produced in
important amounts in the regions of Aragon and C a s t i l l a - L e n
(Spain). The first one is capable of processing 50 kg. of biomass
per hour and the second 200 kg. of biomass per hour. Both gasifiers
have a similar structure although there are
substancial
differences between them, These differences were introduced in
the design of the second gasifier in view of the experience gained
with the first one, and of the modelling studies carried out. Both
installations are described and some results obtained in them are
presented.
1. DESCRIPTION OF EXPERIMENTAL SYSTEMS

The 50 kg/h plant consists in the following elements: Gasifier,
Ash removal system, Blower, Rotameter, Biomass feeding system,
Cyclone, Heat exchanger, Venturi meter, Gas sample point, One way
valve, Torch. A scheme of the gasifier is shown in Figure 1, where the
dimensions have been indicated.
The building materials for the gasifier must withstand the high
temperatures developed in the oxidation zone (about 1200C), as well
as the corrosion caused by an enviroment where tars, H 2 and CH 4 are
present. The attrition caused by the solid which moves downwards
must also be taken into account. The gasifier wall consist of two
614
concentrici 10 mm. thick brick layers. The inner one is built with a
refractory material of a high alumina content (82-84% A l 2 0 3 , 12-14%
S i 0 2 , 1 % Fe 2 0 3 .), whereas the outermost layer is built with a thermally
insulating material in order to avoid heat losses. The external wall is
covered with a 5 mm. thick F-lll carbon steel layer, which also serves
as a support for the whole ensemble.
Under the gasifier there is a wedged compartment built on
refractory concrete, on whose sloped walls the ashes slide to a screw
conveyor, at the bottom of the cavity. This conveyor transports the
ashes to a hopper where they are stored. The compartment also
contains the exit pipe for the gases leaving the gasifier.
The biomass feeding system is connected directly to the gasifier,
in order to avoid leaks. It consists of a 700 I. hopper in which the
biomass required for a given run is loaded at one time. The feed is then
introduced in the gasifier by means of an electrically driven ram. The
whole ensemble is made of 3 mm. thick carbon steel plate.
Several thermocouples are located at different heights in the
gasifier, as shown in Figure 1. Two of them Fe-Konstantan are in the
drying-pyrolysis zone, and there are also thermocouples (Ni-Cr-Ni)
just beneath the throat in the combustion zone and also under the ashremoval grid. A portable temperature probe was also available to
pinpoint temperatures in different parts of the installation.
The 200 kg/h plant is basically similar to the plant of 50 kg/h,
the main differences being due to the higher scale employed.
Moving upwards from the bottom, the gasifier of this plant can be
described as follows: It consists of 1000 mm. i.d., 1200 mm. length
cylinder which narrows, reaching a diameter of 500 mm., 250 mm.
above the end of the straight section. A symmetric widening follows,
reaching again 1000 mm. i.d. in a distance of 250 mm. This is continued
by a second cylinder of constant, 1000 mm. i.d. and 350 mm. lenght. A
scheme with the dimensions of gasifier is shown in Figure 2.
A ceramic material with a density of 350 kg/m 3 was used to make
the body of the gasifier. This material was chosen in view of its good
insulating properties. However, its resistance against erosion was not
so good. Thus, it was internally covered with 1/8" thickness of an
erosion-resistant material with a density of 3450 kg/m 3 . Between
both layers of materials an annulus of 100 mm. thickness was filled
with ceramic wool, made of the same nature as the ceramic material
used for the outer layer. Finally as in the 50 kg/h. Plant, the external
wall of the gasifier is surrounded by a F-lll carbon steel shell.
The ashes are removed using an eccentric stainless steel rotating
grid. Its capacity for ash removal has been determined in previous
calibration measurements.
615
A new feeding system has been designed, in order to ensure plant
autonomy, independently of the size of the feeding hopper (unlike the
50 kg/h. plant). This consists in a compartment closed in both ends by
two gate valves, which ensure air tightness. Biomass is transported to
the top of the system from the floorlevel, usign a belt conveyor. The
air feeding system, is similar to that described previously, although,
given the higher diameter of the throat in this gasifier the air
distribution had to be improved somewhat.
2. EXPERIMENTAL
The experimental program which is being developed studies the
influence of the following process variables:
a)Air flow rate to the system. This variable controls the oxigen
input to the gasifier for the partial combustion of the pyrolysis
products. By this means the energy requirements of the process are
satisfied.
b)Residence time of biomass in the gasifier. In the 50 kg/h. plant,
this is inversely proportional to the percentage of reaction time in
which the grid vibrator is working. In the 200 kg./hr plant, the
residence time is inversely proportional to the rotating velocity of the
grid.
During the experiments gas samples are taken at regular intervals
from the exit pipe. These samples are collected for GC analysis. At the
end of each experiment the amount of biomass consumed is determined.
The weight of ashes and fines is also determined.
The results of previous test in the 50 Kg/h. Plant were used to
select the following ranges of operating conditions for experiments
with wood chips: Air flow rate: 40-70 Nm 3 /h., % Vibration:15-50
(which corresponds to approximately 50-80 min. of residence time in
the gasifier), Air to biomass ratio: 1.1-2 Nm 3 /kg. Table I shows the
operating conditions for two series of runs with wood chips in the 50
kg/h. plant and 29 % vibration were used as reference in these
experiments. Some of the results obtained in the 50 kg/h. plant are
shown in Table II. These correspond to the two series of experiments
mentioned above. Table III shows some results obtained whith wood
chips in the 200 kg/h. plant.
The average composition (volume percent) of the gas obtained
falls into the following ranges: N 2 : 45-60 %, CH 4 : 0.25-2.5%, H 2 : 1022%, CO: 13-25%, C0 2 : 8-19%, C2H2+C2H4: traces.
ACKNOWLEDGMENTS
The authors express their gratitude to C.A.I.C.Y.T. for providing
financial support for the building of the 50 kg/h plant and to
Consejera de Economa y Hacienda de la Junta de Castilla-Len, I.D.A.E.
616
and C.I.E.M.A.T. for providing financial support for the building of the
200 kg/h plant.
Table I. Operating conditions in experiments with wood ch

Run Air flow % Vibration Biomass Residence
(kg./h.)
Time(min)
(Nm3/h.)
53
50
50
46.1
1
69
38
35.8
50
2
44.7
55
50
29
3
22
88
28.1
50
4
25.4
97
50
16
5
6
7
8
9
40
50
60
70
31.7
44.7
39.3
44.9
29
29
29
29
79
55
62
55
Table II. Resu ts obtained in two series of runs with wood chips
LHV gas
Gas Yield
Run Gas flow rate
(kcal./ Nm3) (Nm 3 gas/kg. biomass)
(Nm3/h.)
73.2
939.7
1
1.59
2.02
72.1
2
1011.1
79.1
1006.3
1.77
3
925.7
2.64
71.7
4
1061.2
3.12
5
79.3
6
7
8
9
Table
66.0
79.1
95.4
119.1
1292.1
1006.3
1147.4
1187.7
2.08
1.77
2.42
2.44
Results obtained with wood chips in 200 kg/h plant

Gas flow
LHV gas
Air flow
Biomass
(kcal/Nm3)
(Nm3/h.)
(kg/h.)
(Nm3/h.)
1143.7
223.6
197.5
250.
1051.7
364.8
250.
223.6
375.4
1000.3
182.0
300.
617
co
CO
co
CVJ
13
co
en
o
618
STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED. EFFECT OF THE TYPE
OF FEEDSTOCK
J.CORELLA, J. HERGUIDO and J. GONZALEZ-SAIZ
Chemical Engineering Department (Faculty of Science). University of Zaragoza.
50009 Zaragoza. Spain.
Summary
Steam gasification of four different biomass (pine sawdust, pine wood chips, cereal
straw and thistles (Cynara Cardunculus ) from energetic crops) has been carried out
in a 15 cm. i.d. continuous fluidized bed gasifier. The gas, tar and char yields, the exit
gas composition and the conversion of carbon have been determined at temperatures
between 650 and 780C (923-1053 K) for each type of biomass. At the same
gasification conditions and due to the different structure and size of the particles,
important differences are observed in the product distribution depending on the
gasification temperature and on the biomass used. The differences in H2, CO and C02
in the gas product are important at low gasification temperatures. These differences
decrease on the temperature increasing up to 780C at which a gas composition
similar for all types of biomass is obtained.
1. INTRODUCTION
The type of biomass is an important factor to be considered in the gasification of
biomass in fluidized beds. A same gasifier should process the different types of biomass
produced in the surroundings at the different seasons. Therefore, we considered
necessary to know how the product distribution changes and what problems can appear
when the biomass to be processed is changed.
Scott and Piskorz, Nunn et al., Prasad and Kuester, etc... have studied the pyrolysis
and gasification in fluidized beds of maple, poplar bark, bagasse, wheat straw, etc...
Regarding this work it is important the previous one of Walawender and Fan of the
Kansas State University who studied the steam gasification in a 5 cm i.d. fluidized bed of
cotton wood (branches) (1), of pure cellulose (2), and of dried feedlot manure (3). Their
work is interesting and useful; however, in our region the most abundant types of
biomass are different from the ones they use. As well, we believed that there was still
work to be done in this specific field. Therefore, we have studied the steam gasification
of different types of biomass. This study has been carried out in a 15 cm. i.d. fluidized
bed gasifier at temperatures between 650 and 780C.
2. EQUIPMENT
The installation used in this work is shown in Figure 1. The gasifier is a 15 cm. i.d.
fluidized bed of 1.2 m. total height. The gas distributor plate was made of special
nozzles. Its good operation has really been of key importance in the good progress of this
research. The bed is silica sand (from beach), 32 cm. height at u = umf and t=0. The
biomass feeding point is at the bottom of the bed, at 5 cm. above the gas distributor, and
it is also fundamental for obtaining high throughputs and results similar to those of large
gasifiers (4). The biomass is continuously fed to the gasifier at a prefixed constant flow
rate. In principle, this operation is not easy because of the characterestics (form, size,
619
easy pyrolysis,...) of the biomass and the high temperature of the gasifier, but this
problem was solved in our installation. The gasifier was externally heated by an electric
oven. The plant has two lines in parallel for introducing the gasifying agent (steam) or
other gases (air, N2...). The gases from the gasifier pass through a cyclone for
separating the dragged fines (ash, char, sand), by a water-cooled heat eschanger in
which the steam and the tars are condensed, and by a demixter consisiting of five glassbulbs arranged in parallel and with a glasswool filling. After the continuous measurement
of the gas flow, gas samples are taken and analyzed by gas chromatography.
CYCLONE
Figure 1.- Scheme of the experimental installation.

3. OPERATING CONDITIONS
The main operation parameters are given in Table I. The bed temperature was varied
from one run to another, maintaining constant the other parameters. The effect of the
H20/biomass ratio and of the space-time (Ho/uo) for the gas were previously studied
(5,6).
4. FEEDSTOCKS
Four different types of biomass have been processed. Pine sawdust, small pine wood
chips with a small quantity of bark, cereal (wheat) straw (one of the most abundant and
available residues in Spain) and, finally, thistles from energetic crops have been
processed. In Table II the main physicochemical characteristics of these biomass are
shown. Concerning their fluidization, Aznar et al. (7,8) determined the umf, ucf,
terminal velocities, bed and particle densities and the segregation In the biomass-sand
and char-sand mixtures, for the biomass used here and with sand (and other solids) of
different sizes. In Table II it can be observed how the four types of biomass have a
similar composition (dry-ash-free). According to Prasad and Kuester (9) the
hydrogen/oxigen ratio (H/O) in the biomass is a important parameter for the composition
of the gas produced.
Product yield
The variation of the gas yield with the temperature of the gasifier is shown in Figure
2. An important increase in the gas yield with the temperature is observed. However,
important differences among some biomasses and others are observed, these differences
620
being more acute at high temperatures. Thus, for example, at 780C (1050 K) the gas
yield is of 1.2 Kg. of gas/Kg. of sawdust, whilst with thistles it is only of 0.63. This
increase of the gas production with the temperature may be due to the greater production
of gas in the initial pyrolysis (more rapid at higher temperatures) and to the endothermal
reactions of gasification of the char: on increasing the temperature the tar cracking and
steam reforming reactions are favoured with the resulting decrease of the same and the
gas yield increase.
TABLE
Gaslfler Operating Conditions
Reactor temperature range

Fluidizing gas mixture
Superficial gas velocity at inlet, (u 1
Bed height at U Oand 4 , ' ^ f
(Ho)
Total pressure in the gasifier
Steam/biomass ratio
Second or fluidizing solid
650780C (9231053 K)
90% H O 10% N2
0.25 m/s
0.32 m
1.1 atm
0.80
Silica sand from beach
( 8 kg)
dp = 300 + 200
Umf 6 cm/s
Ucf = 11 cm/s
650C
Flow rates: Biomass (kg/hr)

Steam (kg/hr)
Nitrogen (Nl/s)
Ng purge (Nl/s)
TABLE II
3.94
3.39
0.131
0.008
750C
3.71
.22
0.123
0.008
780C
3.56
3.06
0.120
0.008
3.46
2.98
0.115
0.008
Main characteristics of feedstocks

Sawdust
Particle size
700 C
dp~ 500
Straw
Wood Chips
Thistle
L > 5 mm.
1 0 x 5 X 2 mm
8.5
1.2
77.4
12.9
7.8
14.1
61.6
16.5
11.1
2.1
74.4
12.4
10.0
13.6
60.7
15.7
Elemental analysis (% daf basis)

carbon
42.5
hydrogen
6.3
nitrogen
0.2
H/O molar ratio
2.02
43.7
6.1
0.4
2.73
41.8
5.3
0.2
1.68
40.8
5.5
0.3
2.19
Low Heating Value

(Kcal/Kg daf)
3790
Inmediato analysis (% wt basis)

moisture
ash
volatiles
fixed carbon
4500
4450
: Thistle is constitued of fibers and pith in different proportions; it is very

difficult to give a medium particle size.
3860
621
M
1.
*
t
*
*
1G)
Sawdust
Straw
Wood Chips
Thistle
o.i
0.1
Straw
Wood Chips
Thistle
Sawdust
UJ
>
3
0.'
o.:
600
t
.
*
650
700
750
600
TEMPERATURE fC)
650
700
750
800
TEMPERATURE (C)
Figure 2.Gas yield vs temperature
Figure 3.Gas yield (Nm3/Kg daf) vs temp.
For comparing which is the production of gas by Kg of net biomass, the volume of
gases produced per Kg of biomass dryasffree has been calculated. This gas yield at
different temperatures is shown in Figure 3. In this Figure two groups of well
differentiated biomasses can be observed now: on the one hand sawdust and straw and
on the other chips and thistles. It is observed how the sawdust and the straw give a gas
yield quite a lot higher than that of the chips and thistles. The difference is high and it can
be attributed to the different sizes (and shapes) of the particles of each biomass used.
Thus, for the sawdust particles (spherical and of a very small size) the effectiveness
factor (h) is near the unit. In the case of the chips their surface/volume ratio is much
less and their char is gasified more slowly (h<1). Something similar happens with the
thistles. In the case of the triturated straw its particles have a laminar shape, with a
very small thickness. Then, the preferential direction of the gasification reaction is the
transversal. Therefore, their characteristic dimension respect to the gasification (its
thickness) is very small with a behaviour similar to that of the sawdust particles (h =
1). The night gas yield obtained with the straw can also be explained by a possible
catalytic effect of its ash: it is abundant in the straw and it has a high content in K20
which favours the charsteam reaction.
Char and Tar production
The char yield, referred to biomass daf, is presented in Figure 4. The sawdust and
the straw are those biomasses which produce less char. This is in agreement with the
greater gas yield they give.
50
+
40
Straw
Wood Chips
Thistle
Sawdust
30
20
10
600
650
700
750
TEMPERATURE (X)
Figure 4. Char yield vs. temperature
800
600
650
700
750
800
TEMPERATURE (C)
Figure 5. Tar yield vs. temperature
622
Besides the already known
it is observed how this value
production of tar occurs with
coming from the cracking and
decrease of the tar yield with the temperature.in Figure 5

is very similar for the different biomasses. The smaller
the sawdust, coinciding with its greater yield to gases,
reforming of the primary tars.
Gas
composition
The [H2] [C02]/[CO] [H20] ratio of the exit gas for each biomass and the curve
corresponding to the thermodinamic equilibrium constant are shown in Figure 6. These
curves are similars to those presented by
Figure 6
Influence of gasifier temperature
on the equilibrium of the water
gas shift reaction theoretical and
experimental.
600
650
700
750
800
TEMPERATURE (C)
Maniatis and Buekens (10). The direct reaction of the watergas shift reaction has a
kinetic constant greater than the inverse reaction at temperatures below 810C (1083
K). A t this temperature both constants (direct and inverse) are equal: k1/k2 = 1
(Figure 6), Prasad and Kuester (9), Walawender et al. (2). Besides, in our reactor the
partial pressure of the steam (in the denominator of the above ratio) is much greater
than that of the other components (1,5 to 3 times greater than that of the H2, which is
the component which is found in greater proportion in the dry gas). Then, on increasing
the temperature, the experimental ratio comes near the theoretical one, Figure 6. In
simple words, a progressive increase of the concentrations of H2 and C 0 2 , and a
reduction of that of CO is produced when the gasification temperature is increased. More
details about the gas composition will be given in the extended version of this work (11).
ACKNOWLEDGMENTS
The present work has been carried out within the Shared Project between the CA ICYT
(Madrid) and the CEE (DG XII), Contracts ns A G3/84 and EN 3B0103E. The authors
acknowledge the F.P.I, grant awarded to J. Herguido by the Spanish Ministry of Education
and Science.
623
REFERENCES
(1) Singh, S.K., Walawender, W.P., Fan, L T . , Wood and Fiber Science. 18 (2), 1986,
327344.
(2) Walawender, W.P., Hoveland, D.A ., Fan.L.T., Ind. Eng. Chem. Process Des. Dev.. 2
1985, 813817.
(3) Raman, K.P., Walawender, W.P., Fan, L T . , Ind. Eno. Chem. Process Des. Dev.. l ,
1980, 623629.
(4) Corella, J., Herguido, J., A lday, F.J., 'Pyrolysis and steam gasification of biomass
in fluidized bed. Influence of the type and location of the biomass feeding point on
the product distribution'. In 'Research in Termochemical Biomass Conversion',
Bridgwater, A .V. and Kuester, J.L. (eds), Elsevier A ppi. Sci. Pu. London, 1988,
384398.
(5) Corella.J., A dnez.J., GonzlezSiz.J., Herguido.J., 'Steam gasification of biomas
i fluidized bed reactor", in 'Biomass for Energy and Industry. 4th E.C.Conference'.
Grassi, Delmon, Molle and Zibetta (eds). Elsevier A ppi. Sci. Pu.,1987, 11071111.
(6) A gorreta, E., A znar, M.P., Corella, J., 'La gasificacin de serrn de pino con vapor
de agua en un pequeo de lecho en continuo; Estudio de las variables del proceso'. 11
Jornadas Biomasa. Soria (Spain), 1987, pp. 4.131/4.135.
(7) A znar, M.P., GrciaGorrfa, F.A ., Corella, J., A n. Quim. (Madrid^. 8_4_,1988a, 379
385.
(8) A znar, M.P., GrciaGorria, F.A ., Corella, J., A n. Quim. (Madrid), 8_4_,1988b, 386
394.
(9) Prasad, B.V.R.K., Kuester, J . L , Ind. Eng. Chem. Res.. 27 , 1988, 304310.
(10) Maniatis, ., Buekens, ., EPE, Vol XVII, n a 34, 1982, 3539.
(11) Corella, J., Herguido, J., GonzlezSiz, J., to be published.
624
STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED WITH A SECONDARY
CATALITIC REACTOR. I. RESULTS WITH THE SECONDARY REACTOR
EMPTY AND WITH SAND.
J. CORELLA, M. P. AZNAR, . CEBRIAN, J.I. IGLESIAS, M.P. MARTINEZ
Chemical Engineering Department. University of Zaragoza.
ajumara
We are going to improve the gas composition from a fluidized bed gasifier by using catalysts
placed in a secondary bed in series with the gasifier. Catalysts for tar cracking, methanation and steam
reforming will be used. To know their activity preliminary results in the same installation without
catalyst are needed. Then, in this part I preliminary runs have been carried out with the secondary
reactor empty and filled with silica sand. A bench scale facility based In a 6 cm. id. fluidiced bed
gasifier, a porous metallic filter and a 4 cm. id. secondary vessel have been used. Working at 750C in
the gasifier, steam/biomass ratio of 0.9-1.1, and 6-9 g. biomass/min. the tar and CH4 contents in the
exit gas are about 100 g/Nm 3 and 6-9% vol. respectively. The product distribution and gas
composition are given for several operating conditions
1. INTRODUCTION
It is well known that the gasification of biomass in fluidized beds still has technical problems or, at
least, that it could be improved. One of these problems is the quality of the gas produced. When air
is used to gasify, not much tar is produced but the gas only serves to be burnt and, sometimes, with
dificufty. When steam is used as gasifiing medium, the exit gas is composed of H2, CO, CO2, CH4,
some C2 and C3, tars and elutriated char and ashes. This gas could be used as syntesis gas
(CO+H2,H2+N2), as H2 rich gas, or to be burnt as medium heating value gas. In the first case the 510% vol CH4 content should be eliminated. In the later case the CH4 content should be increased.
And the tars should always be entirely eliminated for many and well know reasons.
There appears to be a clear necesity of reforming or modifiing the gas composition. Together
with other possible technical solutions (O2 Introduction, use of very high temperatures, etc..) the
use of catalysts could be a good or possible solution.
Thus, catalysts could be used for, at least, tar cracking, methanation or steam reforming of the
CH4. It is curious to observe how these processes or solutions have been widely used and studied
in the petroleum and coal refineries and industries but not in the thermochemical processing of
biomass. So, this and forthcoming papers will be devoted to the experimental study of the use of
catalysts in the steam gasificaton of biomass in fluidized beds.
As an starting point one had to face to, at least, three questions: 1st) Which catalysts to use?
2nd) Where to place them? 3rd) Which is the most commedable scale to investigate these
processes?
The catalysts we have used have been of three very different types: tar cracking, methanation
and steam reforming of CH4. The results with the last two will be shown in the next EC Conference
in Lisbon (September 1989). Here we will only show the preliminary results (part I) and the results
with some tar cracking catalysts (part II).
About the important question of where to place the catalyst, we think we already have defined
ideas but it is also necesary to say that each author seems to have his own opinions. At least three
different sites or emplacements can be envisaged for the catalyst: 1) impregnated in the biomass, 2)
in the same gasifier, mixed or instead of the silica sand, and 3) in a secondary reactor in series with
the gasifier. In our oppinion the methanation and the steam reforming catalysts have to be placed in
a secondary reactor for, at least, three other reasons: 1st) these commercial catalysts are made to be
used in fixed bed, not in fluidized beds (like the gasifier); 2nd) the temperature of these two
625
processes can be different from that of the gasifier; 3rd) the gasifier atmosphere can deactivate the
catalyst. About the cracking catalysts, these catalyst could be used in the same gasifier (1) or in a
secondary reactor. In part II of this work only its use in a secondary reactor will be studied and shown.
Two stage processes are know for coal gasification (2) but these processes (and even studies) for
gasification of biomass are very scarce.
We think that the scale of the research (i.e. the size of the gasifier and of the catalytic reactor) is
an important and previous decision that can influence not only further important results like the
product distribution and gas composition (see, for instance ref. 3) but also future decisions about
the technical and economical viability of the process. Between very small gasifiers (i.e. 2-3 cm i.d.)
and pilot plant gasifiers (larger than 15 cm i.d.), for the reasons exposed in (4) we have chosen here
an intermediate or bench scale installation. This installation has a continuous feeding of biomass and
a continuous reforming of real exit gas from the gasifier of biomass.
To compare results, to clearly see the effect of the catalyst and to differentiate it from the effects
(thermal cracking, for instance) of the installation, previous runs have been made: i) without the
secondary catalytic reactor; ii) with this reactor being empty and iii) with this reactor filled with inert
silica sand. Only these results will be shown in this part I.
2. INSTALLATION
A scheme of the installation can be seen in figure 1. The gasifier is a 6 cm i.d. fluidized bed, 30
cm height, externally heated by a 4 Kwatt furnace, followed by a disengaging zone 20 cm i.d., and
14 cm high. This upper zone was always thermally isolated to diminish tar condensation. The gas
distributor was a plate with 9 bubble cups of 8mm diameter with 10 holes each one of 0.8mm
diameter. At not very hight superficial velocities this plate gives small bubbles (good gas-solid
contact). Before the gas distributor plate there was an elicoidal pipe to preheat the fluidizing and
gasiting gas. This fluidizing gas was always steam.
Gas
sample
Gas
to vent
Secondary bed
Figure 1. Scheme of the experimental installation
626
The continuous feeding system of the biomass has had special importance. Althought several
improvements were made some runs had to be stopped by the plugging of this system. Main
aspects of this feeding systems are: the downpipe or standpipe has to be externally refrigerated
(with several quenching air flows). This downpipe has a 3 cm. diameter to dinimish its plugging. The
screw feeder has 3.5 cm i.d. The usual biomass flow rate was 6-10 g/min. (0.36-0.6 kg/hr). As
biomass, pine (pinus pinaster) sawdust was always used (C:40.8%wt, H: 6.3%wt, 0:52.9%). Its size
was always -630+250 mm, its humidity about 10-14% wt and its LHV 4400 kcal/kg daf.
After the gasifier there was a porous metallic filter (10 mm nominal pore size and 50 cm length).
Then, there was the catalytic bed of 4 cm i.d. and 15 cm height. At its bottom there was a bubble cup
(2 cm o.d.) as gas distributor. At the top there was another bigger zone of 8 cm i.d. and 20 cm. high.
At the exit of this catalytic reactor there is an heat exchanger, a tar and water receiver, an
effective demixter (with glass wool), a continuous flowmeter, a gas sampling device and the exit gas
pipe. About every 10 minutes a gas sample was taken which was analyzed by conventional gas
cromatography. Sometimes, in the same run, several samples of the condensed liquid were taken.
This liquid was analyzed by several methods: liquid cromatography, total organic carbon, tar
extraction with solvents, etc... All these analysis allowed us to know the evolution and deactivation
of the catalyst when it was used.
It is necessary to cite the complexity of this installation, the difficulty of carrying out the runs in
good contitions (maintaining constant the flowrates, temperatures, pressures, e t c . ) , the high number of plugs and conections which made escapes of gas highly probable, the difficulty in closing the
mass balaces, etc... The % of 'valid runs' was increasing with time, improvements, experience,...
In the gasifier there was always silica sand of -200 +125 mm (umf = 5 cm/s; Ucf = 9-2 cm/s), with
Ho = 30 cm(at t=0 and u=u m f). The superficial gas velocity at the gasifier inlet was 15,18 or 21 cm/s.
This variable is very important since it determines the segregation or not of the char in the upper part
of the bed, the gas velocity at the exit, the gas velocity at the inlet of the secondary reactor and the
space-time or mean residence time in this secondary reactor.
Char and tar were collected in different quantities (and of different types!) in the different parts of
this installation. Unless stated, char and tar yields will be refered to all the installation and for the
whole of the run.
3. RESULTS WITH THE SECONDARY REACTOR EMPTY

To stablish what results are obtained without catalyst, runs were made with the secondary
reactor empty and in the following conditions:
gasification temperature
height of sand in the gasifier
temperature in the filter chamber
steam flow rate
biomass flow rate
750C
30cm
515-520C
5-7 g/min.
6.2-6.6 g daf/min.
The product (gas, tar, char) distribution and the gas composition in different runs with different
temperatures in the secondary reactor (empty) are shown in figures 2 and 3. To compare with further
results with catalyst, two data are important and should be remenbered: the tar and the CH4
contents in the gas. The tar content is between 76-120 g/Nm 3 equivalent to tar yields of 5.9-8.1
Kg/Kg daf. The CH4 content in the gas is between 5 and 9 % vol.
Compariing these results with those previously obtained in the same rig but without fitter and
secondary vessel, less tar and more gas yield are now obtained. We think this is due to the
existence of thermal cracking in the filter and in the secondary vessel. Also, there is now more H2
and CO2 and less CO. This can be easily attibuted to the existence now of more volume at high
temperatures for the gas phase shift reaction (CO+H2O = CO2+H2).
627
= 60.
0
> 50
40.
0.
O 30
10
500
600
700
800
300
900
400
500
'
600
700
800
900
TEMPERATURE (C)
TEMPERATURE (C)
Figure 2. Effect of the temperature of the
secondary reactor (empty) on the
product d i s t r i b u t i o n
( gas; char; tar)
0.
300 400
(0 20
Figure 3. Effect of the temperature of the

secondary reactor (empty) on the
gas composition at the exit of
the installation
<H, CD, CO. CH 4 )
4. RESULTS WITH SILICA SAND IN THE SECONDARY REACTOR

With silica sand of 297+200mm (u m f = 6.0 cm/s; ucf= 110 cm/s) in the secondary reactor the
effects of the bed height and of the temperature of this bed have been studied. The effect of the
bed height is shown in figures 4 and 5 in which the gas yield and the gas composition at the exit of
the installation are shown. The temperature of the secondary reactor was 745 10C (gasifier
temperature = 750C, other conditions: the same as above). The gas yield does not change
appreciably with the use of sand or whit the height of the sand in the bed. Only the H2 content
increases a little and the CO decreases (attributed to the shift reaction in the bed)

o
0
.
vol.)
70
t 40
o.
S 30
O
U
20
<
O 10 .
0 .
5
10
HEIGHT (cm)
Figure 4. Gas yield vs. height of the
secondary bed with sand
El
5
10
HEIGHT
(cm)
'
15
'
Figure 5. Gas composition vs. height of

the secondary bed with sand
(297 + 200 Mm). T ^ secondary
bed 745 10C
628
The effect of the temperature of the secondary bed with silica sand (being the filter temperature
= 550C), for two sands and two different bed heights, is shown in figures 6 and 7. Comparing with
the results obtained in the empty reactor there is not a sensible influence of the sand, indicating this
solid is inert. The product distribution and gas composition will be used in further parts of this work as
the basis to see the effect of several catalyst placed in the secondary reactor.
IV
60
I
a.'
2
50
40
30
<
10
o
300
El
400
500
600
700
800
TEMPERATURE (C)
F i g u r e 6 . E f f e c t of t h e temperature of
t h e secondary bed with sand
of 297 + 200 um, 10 cm high
300
400
500
600
700
800
900
TEMPERATURE (C)
Figure 7. Gas composition a t t h e e x i t o f
t h e I n s t a l l a t i o n v s . temperature
of the secondary r e a c t o r with
sand of 630 + 297 , 14 cm high
(u ( g a s i f i e r ) = 15 cm/s
u (secondary bed) = 57 cm/s)
5. REFERENCES
(1) Corella.J., Herguido, J., GonzlezSiz, J., Alday, F.J., RodriguezTrujillo.J.L, in
Research in Thermochemical Biomass Conversion A .V. Bidgwater and J.L. Kuester
(eds.); Elsevier Appi. Sci., London (1988),754765.
(2) Juneja, M.N.; Mazundar, A; Biswas, D.K.; Rao, S.K. Fuel Sci. Techn. (2),
1987, 4560.
(3) Corella.J., Herguido, J., A lday.F.J. in Research in Thermochemical Biomass
Conversion A .V. Bidgwater and J.L. Kuester (eds.); Elsevier A ppi. Sa'.,
London (1988), 384398.
(4) Corella.J., A znar, M.P.,Cebn'n,N., Brana, P. in Adas XI Iberoamerican Symposium
on Catalysis Guanajuato, Mjico, May 1988. IMPMxico D.F. (ed), pp 10191027.
629
STEAM GASIFICATION OF BIOMASS IN FLUID IZED BED WITH A
SECONDARY CATALITIC BED . - II. TAR CRACKING WITH D OLOMITES IN
THE SECOND ARY REACTOR
M. P. AZNAR, J. DELGADO, J. CORELLA, J. LAHOZ

Chemical Engineering D epartment . University of Zaragoza.
Summary
The use of dolomites for the cracking of tars in gases from steam gasification of
biomass in fluidized beds has been studied. The installation was based in a bench scale
facility with a 6 cm i.d. fluidized bed gasifier operating at 750 C, a porous metalic
filter at 530C, and a 4 cm i.d. secondary bed filled with dolomite and operating
between 400 and 950C, mainly between 800 and 900 C. D olomites from Spain,
Sweden and United Kingdom have been used. Above 800-850C tar conversions higher
than 95% and tar concentrations in the gas less than 200 mg/Nm3 have been obtained.
The deactivation of the dolomite along the time-on-stream has been studied and the life
of the dolomite is given.
1. INTROD UCTION
In part I we indicated how the product distribution and the gas composition from
biomass gasifiers or pyrolyzers can and have to be improved. In particular, tar and CH4
contents in the gas obtained are far from the optimal ones. This part II will be only
devoted to the tar elimination in the exit gas by catalytic cracking . The problems that
tar gives are well known, and this tar has to be eliminated, or at least diminished to a
great extent. This tar could be eliminated by using very high temperatures or
introducing oxigen in the gasifing gas.The first solution is not easy when fluidized beds
are used as gasifiers and the use of oxigen Introduces the necesity of an auxiliary O2
production plant. So, here we are going to continue the study of another solution for tar
elimination. This solution is based in the use of cracking catalysts.
In the petroleum refineries very difficult feedstocks and heavy oil fractions (end
b.p. >600C) are easily cracked in riser reactors operating between 500 and 620C (at
the bottom) and contact times with the catalyst of 2-4 seconds. These commercial
catalysts (fesh or 'in equilibrium') could also be used in blomass gasification/pyrolysis
for tar cracking but its very low mean diameter (about 70 ) makes them easily
elutriables (terminal velocity, ut=20 cm/s). So they can be used only in riser gasifiers
or circulating systems (l)Therefore, here we are going to study another type of
cracking catalysts: dolomites.
At least, in recent years in four countries (Sweden, France, Spain and USA) studies
have been made about tar cracking with dolomites. Important and previous works have
already been made. Among others, there are the studies in Sweden of the Royal
Institute of Technology (2) and of Studsvik Energy (3), in France of Magne, D eglise and
colls. (4), in USA of Battelle-Pacific NorthWest (i.e. 5), of Longwell, Peters and colls.
(6) and of Wen and Cain (8) and in Spain our previous work on this subject (9). To make
here a comparative study of these works is imposible by the obliged length of this
communication. So we can only summarize the previous findings in two main ideas:
630
Calcined dolomites are very active for cracking of tars coming from biomass or coal
gasification or pyrolysis, and there is still a lot of work to be done to optimize the use
of dolomites in these processes.
The specific fields in which there is not much knowledge are: the deactivation rate
of the dolomite, its fluiddynamic properties and the effect of the origin or provenance
of the dolomite in its activity. This work is a step more in the study of these factors.
Associated with the cracking of oils, hidrocarbons or tars there is always coke
formation on the catalyst surface that in oil cracking deactivates the catalyst in a few
seconds. So, in tar cracking we are going to find this deactivation of the dolomite by
coking.
The catalyst (dolomite) can be placed in several places. In a previous work (10) we
placed it in the same gasifier. In this work only its use in a secondary reactor in series
with the gasifier will be studied.
The realtionship between the particle size of the dolomite and the superficial gas
velocity (u) in the cracking reactor is very important. Remember that the particles
with a terminal velocity (or chocking velocity in risers) less than u will be carried out
of the bed. Thus, for a fixed superficial gas velocity at the gasifier inlet, and given the
diameters of the gasifier (or pyroliser) and of the cracking reactor, the dolimite has to
have a given minimun particle diameter to be fluidized and not carried out from the bed.
2. INSTA LLA TION A ND OPERA TING CONDITIONS
The bench scale installation was shown in part I. It basically consists of constituted
by a 6 cm i.d. fluid bed gasifier continuously fed with biomass from the top, a porous
metallic filter and a 4 cm i.d. secondary catalytic reactor filled in this work with
dolomite.
The main operating variables were:
fluidizing or gasifiing gas
pressure
superficial gas velocity at
gasifier nlet(u0l)
biomass
gasifier bed
steam/biomass ratio
temperature of gasification
temperature of the filter
temperature of the
secondary bed of dolomite
height (at t=0) of the
bed of dolomite
spacetime () for the bed
of dolomite, defined as
(H0/U02)
spacetime (') for the bed of
dolomite, defined as kg dolomite/kg
biomass daf fed/hr
steam
atmosferic
15 cm/s
pine (pine pinaster) sawdust,
630+250
silica sand, 200 +125,
30 cm high
0.800.95
750800C
520550C
400950C, mainly 800900C
10cm
0.17 s
0.210.26 hr
Gas samples were collected each about about every 10 minutes and analysed by gas
cromatography. The condensed liquid (mainly water) at the cracking reactor exit was
631
taken about evry 10 minutes. It was analysed by liquid cromatography and its TOC
(Total Organic Carbon) content determined. The TOCvalue was converted to the
equivalente amount of tar on the assumption that the molecular weight of tar was equal
to that of phenol, like Sjstrm et al. did it (2)
3. DOLOMITES USED
We have used three different dolomites from three different countries:
1. Spanish, from 'Dolomitas del Norte' of Cantabria (North of Spain). Its size was
innitially 1000+600 \im but given that u 0 2 = 5070 cm/s and that there was some
carry over it was increased to 2.0+1.0 mm.
2. Swedish Sala Dolomite kindly given by the R.I.T. of Stockholm. It was of the
same origen as that used in ref. 2.
3. English, the 'stone' used in the John Brown/Wellman gasifier. It had a size of
2.5+0.6mm and it was really a calcite.
Their detailed characterization is more than length of this paper. We ca only
say that they were calcinated at 900C first in a furnace and afterwards in the same
cracking vessel previous to its use and that this variable, for instance, had some
importance.
4. SOME RESULTS
The gas yield obtained with the Spanish dolomite at different temperatures of the
dolomite bed is shown in figure 1. A bove 700C a gas yield increase is observed due to
the tar cracking as will be shown bellow.
's
Figure 1. Gas yield at different

temperatures of the bed with
dolomite.
100
*:
80
s-
6 0
>
40
<
(3
>
400
600
800
1000
TEMP. OF THE SECONDARY BED (C)
The most impresive and spectacular effect of the dolomite is in the conversion or
cracking of tars. In figure 2 the tar conversion with the Spanish dolomite at different
temperatures is shown. A bove 800850C tar conversions (cracking) higher than 95%
are obtained. The tar concentration in the exit gas at different bed temperatures is
shown in fig. 3.
632
100
600
700
800
900
600
700
800
900
Figure 2. - Tar conversion (average for

1 hr) vs. temperature of the bed of
dolomite.
Figure 3.- Tar concentration in the exit

gas (average for the 1 hr length run).
There is a very clear diminution of the tar content in the exit gas when dolomite is
used at temperatures above 800C aprox. But these results are the average for each
run of 1 hr. length and of 0.17 seconds or ' of 0.21-0.26 hr, like in ref.(2). Let us see
what happens in the first minutes of reaction.
In figure 4 the tar conversion in the secondary bed and at two temperatures (of the
cracking bed), 780 and 840C, is shown at different times-on-stream of the (Spanish)
dolomite. The tar concentration in the exit gas from the dolomitic bed at different
times-on-stream is shown in figure 5. Several clear and important effects can be seen
in these figures .For instance: the deactivation of the dolomite affects the tar
conversion or the tar content in the gas. The deactivation occurs in several minutes.
The temperature is an important factor. With the space-time used, at 840C a tar
conversion of 99% and a tar content in the gas of less than 200 mg/Nm3 can be
achieved, but this only in the first 40 minutes (of using the dolomite).
m
E
LU
o
o
cr
<
20
40
60
80 100
TIME ON STREAM (min.)
Figure 4.- Tar conversion in the bed
of dolomite vs. time on stream.
-20
40
60
80
Figure 5.- Tar concentration in the

exit gas from the bed of dolomite vs
time on stream.
The deactivation by coking of the dolomite also influences the gas composition which
varies with time-on-stream of the dolomite, as can be seen in figure 7. At t>60
minutes, the gas composition is the same as those obtained when sand was used in the
secondary bed.
633
O
t
co
O
Figure 6. Gas compos,

at the exit of the bed of
dolomite.
8
(
780 C
840 C
20
1 *

30
40
50
70
Intimated asociated with 840C curve in figures 5 and 6 are the cromatograms
(liquid cromatography) shown in figure 7. They correspond to the condensed water at
the exit of the bed of the Spanish dolomite (at 840C). In the first three samples the
dolomite was still active and there are few components and in small quiantity in the
condensed water. A fter about 40 minutes (see also figs 5 and 6) the bed begins to be
deactivated and the cromatogram now shows more componentes and in more quantity
which corresponds to a lower tar conversion in the bed of dolomite.
REFERENCES
(1) Corella.J.; Herguido, J.; RodrfguezTrujillo, J.L.;
Paper to be presented in the
5th EC Conference on Biomass for Energy and Industry. Lisbon, September 1989
(2) Sjstrm, K.; Taralas, G.; Liinanki, L. in Thermochemical
Processing
of
Biomass .V. Bridgwater and J.L. Kuester L(eds), Elsevier A ppi. Sci., London, 1988,
974986.
(3) A ldn, .; Espens, B.G.; Rensfelt, E. in Thermochemical
Processing
of
Biomass. A .V. Bidgwater and J.L. Kuester (eds.); Elsevier A ppi. Sci., London 1988,
9871001.
(4) Donnot, .; Reningovolo, J.; Magne, P.; Deglise, X., J. Anal. Appi. Pyrolysis.
1985, 8_, 401414.
(5) Elliot.D.C; Baker, E.G., Biomass, 1986, , 195203.
(6) Yeboah, Y.D.; Longwell, J.P.; Howard, J.B.; Peters, W.A . Ind. Eng. Chem.
Process Des. Dev. 1980, l i , 646653.
(7) Eilig, D.L.; Lal.C.L.; Mead, D.W.; Longwell.J.P.; Peters, W.A . Ind. Eng. Chem.
Process Des. Dev. 1985, 2 4 , 10801087.
(8) Wen, W.Y.; Cain, E. Ind. Eng. Chem. Process Des. Dev, 1984, 23, 623637.
(9) Corella, J . ; Herguido, J . ; GonzlezSiz, J . ; A lday, F.J.; RodrlguezTrujillo,
J . L , in Thermochemical Processing of Biomass A .V. Bidgwater and J.L. Kuester (eds.);
Elsevier A ppi. Sci., London 1988, 754766.
ON
W
--
Figure 7.- Liquid cromatograms of the condensed water collected at the exit of the
secondary bed of dolomite, at different intervals of time-on-stream.
635
Fixed bed gasification of lignocellulosic

biomass the CEMAGREF process
Summary
S.GAUDEMARD and JJ.BECKER

Centre d'Etudes du Hachinisiie Agricole
du Gnie Rural des Eaux et des Forts
Parc de Tourvoie ANTONY 92 FRANCE
The use of biomass as an energy carrier could solve some of the main energy problems especially
in developing countries,and gasification of lignocellulosic material in order to produce lean
gas suitable to fuel an engine seems to be one of the most promising techniques.
Nevertheless,among t h e different technologies available (fixed bed,updraft o r
downdraft,fluidized bed...) none appears able to face properly the major problem related to
the presence of tars in the gas produced.CEMAGREF developped a new technology which enables the
elinination of the tars produced during pyrolysis i n an internal burner in order to obtain a
clean gas.An automation of the wood feeding system and the internal running of the gasifier was
carried out to ensure a good gas quality even in non stationary operating o f t h e system.Tests
results obtained o n a pilot unit developed in CENAGREF showed l o w t a r content a n d good
gasification efficiency in the range o f 5 0 t o 2 0 0 kg/H o f d r y wood chips.
Therefore a generating set including a POYAUD g a s engine of 120 kW was implemented at the end
of t h e line,and t h e power is c o n s m e d i n a flexible resistance.Long r u n tests will be
conducted in order to prove the industrial feasibility of the process.
l.INTRODUCTION
Among the various energy from biomass lines CEMAGREF identified the gasification technique as
one of the most promising especially in Developing Countries.
The aim of the research described here is indeed to produce a tar free lean gas,from high or
medium grain size lignocellulosic biomass. Moreover,the thermal engine fueled with lean gas mustbe
as flexible and reliable as with an oil derived fuel.It is therefore necessary to automate the part
of the line upstream from the engine (biomass feeding,control of the inner operating parameters of
the gasifier according to the power level required by the engine).
2.0PERATING PRINCIPLE OF THE CENAGREF GASIFIER
The pyrolysis of bioiass produces charcoal and volatile matters,both products supplying
approxiiately half the energy available.Although the gasification of charcoal (action of C02 and
H20) is widespread,the required elimination of the heavy components of volatile Batters is no easy
task and very few analytical data are available.Nevertheless,we noticed that this problem could be
solved by treating them at high temperature and by using the catalytic effect of charcoal.
The horizontal positioning of the gasifier and the use of a high teiperature recycling fan (300
to 5O0*C)in tbe CENAGREF process enable to solve the above-ientioned probiere:
- horizontal position for a better distribution of coibustion gases through the bioiass bed.
- high teiperature recycling in order to boost heat transfers as soon as the load enters the
reactor (thermal shock at 400 C instead of 80*C for the DELACOTTE gasifier)and to control the
temperature range in the combustion chamber from 1000' to llOO'C even in case of complete
gasification of the charcoal.
The Bachine obtained is shown on diagram l.It is a fixed bed process and therefore the feed
Bust be large grain sized bioiass (woodchips,coconutshells,...)
636
3.TECHNICAL DESOJIPTIOH OF THE PILOT QUIT
The pilot unit at HT0NY described here is smal (annua vood iiput of about 200 kg/h) and
easy to operate ; the aim of this operation was threefold :
- defining the autoiiated and control systems required for an industrial unit
- determining all the elements necessary for an accurate dimensioning of the unit for a given
pover.
- carrying out long-run tests proving the industrial feasibility of the process
This unit includes the folioving equipment (diagrai 2) :
a) an agricultural moving floor trailer driven by an electric otor and containing the vood chips
used as raw aterial for the gasifier,
b) a belt conveyor
c) a recycling gasifier,CEMAGREF process,
d) a vet filtration unit
e) a Lov BTU gas burner,CEKAGKEF process
f) an air heating systei operating on fuel oil in order to obtain air tempratures around 400'c.
On the industrial scale,a lean gas/air exchanger is to be used instead of the systei operating on
fuel oil
g)a 120 kv generating set including a six cylinder gas engine and an alternator yielding the
produced current in a flexible resistance.
The analysis of the lean gas produced ,Boreover the composition into non condensable elements
by gas chromatography, includes the content of condensable elements (vater and tars) and particles
with a device designed for the purpose.
4.PRINCIPLE OF AUTOMATION OF THE LIME
The objective of this operation is to obtain an automatic setting of the value of the process
parameters in order to provide the power level required by the engine.
The automation of the vood feeding system is a standard operation vhich is not vorth
describing here.
On the opposite,the automation of the gasifier by it self has to be considered in detail.
The system includes four control parameters :
a) three gas flovs (air,lean gas and recycling gas).
b) the vood input.
The following constraints must be taken into consideration in order to ensure an adequate
running of the system :
a) the lean gas outflow released by the gasifier must contain the amount of energy required by the
engine
b) the pressure in the gasifier must remain close to that of atmosphere (in fact,a little
depression is set to avoid the exhaust of pyrolysis gases through the vood feeding system).
c) wood residence time in the reactor must be long enough to ensure a complete pyrolysis of the
wood when leaving the pyrolysis grate and a complete gasification before falling into the ash box.
d) the temperature in the combustion chamber must be high enough to enable a complete cracking of
the tars.
e) the temperature of the recycling gas must be high enough to avoid tar condensation in the
recycling circuit.
Whatever the output of the gasifier the geometry of the vood is maintained by controlling its
height at the end of the gasification grate.
Thus the automation carried out includes tvo control levels:
-firstly:a subsequent change in the pover level required by the engine leads immediatly to a
resetting of the three control parameters(air flov,recycling flov,piston speed (according to the
values provided by the model and confirmed by experiments.
- secondly:the regulation around the setted values during a steady state is obtained by measuring
and treating continuously the following parameters :
- pressure level inside the gasifier controlling the air flov.
- height of the charcoal bed controlling the speed of the biomass piston.
- combustion and recycling temperatures controlling the recycling flov.
637
5.EXPERIMENTAL RESOUS
A first set of experiuents aimed at obtaining a steady-state operating of the line at
different lean gas outflow levels.Table 3 gives some results obtained during twenty hours of
autonatic operating.As long as the engine was not functioned at the end of the line,the variation
in gasifier loading was obtained by changing Manually the position of the exhaust gas valve.This
operation was not perfectly representative of the actual control by an engine as it did not take
into account a possible change in the heating value of the lean gas occuring during the transient
phases.A quick switch of the lean gas production fro 600 Ni3/h (200 kg/h of dried wood chips) to
300 Hi3/h and vice versa could be realized while Maintaining the adequate temperature levels and
the geometry of the biomass bed,the change in operating paraneters being done autonatically.Moreover
no unexpected production of tars was collected in the gas analysis system.
6.FUTURE DEVELOPMENTS
The good results obtained so far encourage us to carry on with the project.Two aspects will be
worth developping in the future.
It would also be interesting to use the experiiiental data obtained on the prototype at ANTONY
and copleientary analyti caldata (ainly obtained with a big sized thermobalance developed at
CEMAGREF) to develop a odel for the optinal diiiensioning of the gasifier for a given power
level,depending on the biomass (especially its grain size) to be processed.
Long-run tests(around 1000 hours)should highlight the feasiblity of the line on an industrial
scale.But,these tests are significant only when the lean gas produced fuels the engine which is the
weak point of such a power line.
Moreover,it could be checked if the response time of the gasifier to a variation of the load
has the saee agnitude as the response tiae of the engine,in order to obtain the sate flexibility as
with diesel oil.
Therefore a 120 kW POYAUD spark engine is implemented at the end of the line.The engine runs
an alternator and the power is consuied in a flexible resistance.
7.ECONOMIC ANALYSIS
With the relative coeplexity of the CEMAGREF process and the cost of the autonation,the
comercial size of the gasifier will be in the range of 500 to 5000 kg/h of dry wood.
An economic calculation related to an unit of 1000 kg/h of dry wood was carried out and the results
are shown in diagram 4.
Two raw laterial scenarios were considered :
-wood as a by product in an agroindustrial complex(palm or
hevea plantations...)at a cost of 15$/ODT(collecting cost only),
-wood produced in energy plantations at a cost of 35$/0DT (Eucalyptus in Brasil or Congo...)
It caie out that even if wood has to be produced in energy plantations,it lakes sense to
iipleient the gasification technology in areas of Developing Countries far from the coast (because
of the high transportation cost by road or railway of the diesel oil).
8.REFERENCES
(1) BECKER,J.J,Fixed bed gasification of lignocellulosic bioiass the CEMAGREF process
Conference "Research in TermochemicalBioiass Conversion",Hay 1988,Phoenix,USA
(2)BECKER,J.J and GAUDEMARD ,S.,Dvelopprent d'une ligne de production d'lectricit partir
de biomasse.Socit franaise des thermiciens,journe d'tudes "Les loteurs biogaz",
Noveiber 1988,Paris,FRANCE
638
DIAGRAM 1
CEMAGREF Fixed bpd Gasifipr
wood
I
air_
, recycling gas
(from recycling fan)
gas exhaust
recycling gas
(towards recycling fan)
pyrolysis area
Q(bed of wood)
gasification area
(bed of charcoal only)
DIAGRAM 2
Schematic of the pilot unit in ANTONY
Wood feeding system
Engin
639
TABLE 3
EXPERIMENTAL RESULTS
210 Dry gas position (1)
Feed rate (kg/h)
H2
45/52
200/600
00
18/21
Moisture content of the feed ({)
15
C02
12/13
Heating value of dry gas (HJ/Hr3)
4.9
H2
Hater content (KG/Ni3 dry gas)
0.076
CE4
Tars (g/Hi3 dry gas) (1)
0.025
02/Ar
1.3
Gas flow rate (N3/h dry gas)
Particulates (g/Hi dry gas)(l)
78
Energy balance (\) (2)
(1) Before filtration

(2) LHV of lean gas over LLHV of wood
(one assmes that gasification air is heated by means of
an exchanger operating with lean gas outflow)
DIAGRAM 4
C o m p e t i t i v i t y of Low B TU gas
l o c a t i o n : a f r i k a n coast
2 on equipment F r a n c e b a s i s )
l e a n gas
30
^ oil price
/bbl
location : continental Afrika

(x2 on diesel oil ; 1,6 on equipment France
.
basis)
y' diesel oil
$/MBtu
"* oil price

/bbl
basis : gasification unit of 1 ODT/h biomass
(cost A00 000 $ France basis),
running 60O0h/year, amortized in 10 years at
8 X
16/20
640
STUDY ON MARKED PRODUCTS OF WOOD GASIFICATION MECHANISMS
WITH THE AIM OF PRODUCING CLEAN GASES
S. CASTILLO, S. BENNINI, G. GAS*, J.P. TRAVERSE
Laboratoire de Recherche sur l'Energie,
*U.A. CNRS No 241, Centre de Physiologie Vegetale,
Universit Paul Sabatier, 31400 Toulouse, France
Summary
This work concerns research into the thermochemical upgrading of
lignocellulose materials. It describes a method which was developed
for analysing the rupture mechanisms of the macromolecules of wood
under the effect of intense thermal flow.
A knowledge of these
mechanisms is necessary for understanding the process of gasification
and determining the respective proportions of the three phases
produced (solid, liquid and gaseous) and in particular for preventing
the formation of tars during gasification of wood.
This method uses * 4 C for the specific marking of the lignin
fraction of lignocelluloses. A study of the distribution of the marked
atoms in the different phases obtained after pyrolysis - in particular
the gaseous phase - gives information on the mechanisms of rupture
under the effect of thermal shock.
1. PRESENTATION OF THE METHOD AND ASSOCIATED TECHNIQUES

1.1
Preparation of Marked Lignocelluloses
Lignocelluloses are made by the association of polysaccharides

(cellulose, hemicelluloses) and lignin. We used the fact that it was
possible to mark the lignin fraction of the wood specifically by exposing
poplar branches to ^C-marked metabolites which are precursors of the
phenyl-propane groups constituting lignin. When one of the four precursors
represented is incorporated (Table I) we obtain lignocelluloses which are
marked only on the lignin fraction.
When a solution containing the marked precursor has been absorbed the
poplar branches are transferred to a vessel containing distilled water, in a
ventilated room at a temperature of 22C with 5W/m2 lighting so that the
precursor can metabolize.
The branches are then stripped of their leaves and bark, fixed in
liquid nitrogen and lyophylized.
They are then comminuted and screened
(250 y m ) .
The lignocelluloses are extracted successively by aqueous and
organic solvents (1) . The residue is rinsed in absolute alcohol and dried
under vacuum. The specific radioactivity of these lignocelluloses (Table II)
is obtained by measuring the radioactivity of the ^ 4 C02 obtained by
combustion of a known quantity of powder in the oxidizer. The l^COo i s
absorbed in a suitable solution and its radioactivity measured by liquid
scintillation.
641
TABLE I . L i g n i n p r e c u r s o r s
and monomers
Monomer p r e c u r s o r s
of l i g n i n
Monomers o f l i g n i n
H=CHCH2OH
*H=*CHCH 2 OH
HJHCOOH
*NH,
Phenylalanine
OH
14
H = CHCH 2 OH
H=CHCOOH
n i
Cinnamic a c i d
(cycle
^ÔCH
OH
C)
H = CHCH 2 OH
CH=CHCOOH
OCH,
OCH,
OH
H = CHCH 2 OH
*CH=CHCOOH
(f
il
Cinnamic a c i d
, 14 .
( C)
OH
: coumaryl a l c o h o l
R. = , R = OCH
: c o n i f e r y l a l c o h o l ) main p o p l a r
R, = R, = OCH
: sinapyl alcohol
TABLE II. Specific radioactivity of the various
Lignocellulose
Precursor
Phenylalanine
14
(U C)
Cinnamic acid
14
(cycle
C)
Ferulic acid
Cinnamic acid
14.
C lignocelluloses
Specific
Radioactivity
(Bq/mg)
642 000
14
(0 CH )
(alpha
) monomers
1 128 000
618 000
14
C)
1 526 000
642
1.2
Thermal Treatment Conditions
The samples undergoing pyrolysis are made up of a mass of lignocelluloses weighing approximately 0.2 g. The sample is moulded in a press at
140 kg/cm2 to produce a disk about 12 mm in diameter and approximately 1 mm
thick. The disk is placed in an image furnace powered by a Xenon lamp, the
rays of which are concentrated by a system of mirrors. The sample is
pyrolysed under a quartz bell with nitrogen flushing which removes the gases
generated by pyrolysis from the bell. We decided on 4 Kw for the power of
the lamp and 0.55 1/min for the nitrogen flow.
These conditions give
complete pyrolysis of the sample in less than one minute and a volume of gas
suitable for the analysis technique can be recovered.
2. ANALYSIS OF PRODUCTS OBTAINED
After pyrolysis, a solid residue is obtained consisting exclusively of
carbon, a liquid tar phase deposited on the base, and a gaseous phase which
is recovered - for analysis - in a spherical container.
2.1
The Gaseous Phase
The pyrolysis gas (approximately 0.5 L.N/g of material) is analyzed by

gas chromatography. H2, CH4 and CO are separated in a molecular sieve column
(60/80 mesh; vector gas: argon); CO2, C2 H 4' C'j/ft, C2H2 are separated in a
column of Porapak (80/100; vector gas: helium). The quantitative analysis
of the mixture is deduced by comparing the chromatogram obtained with the
chromatogram of a standard mixture containing the various constituents of
the pyrolysis gas in known proportions.
The radioactivity of the six carbonaceous gases which can be marked is
determined by coupling a proportional counter to the Chromatograph in the
gaseous phase. A fter separation on the Chromatograph columns the gases pass
in turn into the counter where they are completely oxidized at 600C on the
copper oxide, so that the radioactivity of the resultant carbonic gas can be
measured.
2.2
The Solid Phase
The solid residue is weighed and its radioactivity determined by

measuring the radioactivity of the carbonic gas produced by complete
combustion.
2.3
The Liquid Phase
It is difficult to recover the tars completely because they

dispersed on the plate and in the gas-collecting circuit. To present
results, the radioactivity of the liquid phase was estimated by taking
difference between the initial radioactivity of the sample and
radioactivity of the gaseous and solid phases.
are
our
the
the

Table III gives the distribution of carbon atoms in the different
pyrolysis products. It is deduced from the initial carbon content of the
lignocelluloses used (46.7%) and from chromatographic analysis for the
gaseous phase and weighing the pyrolysis residue for the solid phase. The
carbon content of the liquid phases is determined by taking the difference.
643
TABLE III. Distribution of carbon in the different phases resulting from the
pyrolysis (as a percentage of the number of moles of initial
carbon) and marked carbons in the same phases (as a percentage of
the initial radioactivity)
LIGNOCELLULOSES
Products of pyrolysis
a
C%
33
36
32
33
R%
15
34
31
C%
25
40
34
44
R%
25
40
34
44
C%
42
24
34
23
R%
50
37
45
21
Gas phase
Solid phase
Liquid phase
The gaseous phase contains approximately one third of the carbon atoms
of the starting material. A nalysis of the radioactivity of the gaseous and
solid
phases
shows
significant
differences
depending
on
how
the
lignocelluloses are marked. With lignocelluloses synthesized from uniformly
marked phenylalanine (a) , the radioactivity of the whole gaseous phase
represents less than 6% of the initial radioactivity,
while the solid
residue and the tars represent 44% and 50% respectively. This shows the low
contribution of the lignin to the formation of pyrolysis gas, as already
noted for the lignins extracted (2, 3 ) . In the cases where a single carbon
atom is marked (c, d) , the total radioactivity of the gas represents a
significant fraction of the initial radioactivity (34% and 41% respect
ively) : in this case the atoms marked have been for the most part
incorporated into the gaseous phase.
The results of a more precise study of the radioactivity of the
various constituents of the gaseous phase are given in Table IV. For each
gas the expression of the results is based on a comparison of the following
ratios :
Number of moles of carbon in the gas
C %
Number of moles of carbon in the gaseous phase
Radioactivity of gas i
and
R% =
Total radioactivity in the gaseous phase
The most abundant constituents are carbon monoxide and hydrogen. The
latter represents approximately 45% of the volume of the gas obtained but is
not mentioned in this study, which is concerned with determining the origin
of the carbonaceous gases from the macromolecules marked with 1 4 C .
644
TABLE IV.
Distribution of carbon (in brackets ) and marked carbon in the

various constituents of the gaseous phase for a given test. The
average value of the carbon content of the gases produced by the
different lignocelluloses is also given in the Table.
Average carbon content
Radioactivity of gases
LIGNOCELLULOSES
b
CO
(59)
78.6 (61)
co2
(21)
8.5 (17)
CH
(11)
6.6
2H6
(0.8)
2H4
2H2
76
c
(57)
41
(59)
67
(59)
10.8 (22)
5.7 (21)
22.2 (24)
(12)
6.3 (11)
43.5 (12)
6.3 (9)
(1)
(0.5)
3.7 (0.5)
(5.2)
3.4 (6)
(5)
3.3 (5)
4.5 (5)
(3)
2.7 (4)
2.8 (4)
(3)
(1)
(2)
The marked atoms are present in all the gases (the small quantities of
CjHg detected preclude a significant measurement). This fact is observed
even in the two cases where only one type of atom is marked (c and d) ,
showing that flash pyrolysis causes ruptures of links which cause the
formation and subsequent recombination of marked atomic entities. In all
these cases, the radioactivity measured for a gas is not proportional to its
carbon content (see in particular CO and CH^ for the lignocelluloses a,b,d
and CO and CO2 for lignocelluloses a,b,c). These results show that under the
conditions of flash pyrolysis lignin degrades mainly into CO and to a lesser
degree into CH4 and CO2, and hydrocarbons into C2.
In cases where the lignin is marked on the extracyclic methoxyl group
(c), the radioactivity of C H 4 is equivalent to that of CO. The result shows
that the OCH 3 group forms CH. and CO in equal quantities. It confirms the
theory that the origin of the methane produced by the degradation of the
lignins is the methoxyl group (4).
With the
C lignin lignocelluloses,
of which the precursor is
cinnamic acid marked on the carbon of the lateral chain, the high radioactivity of the
CO2 suggests a large proportion of the
x; in the
formation of the CO_.
CONCLUSIONS
14.
The marking with

C means that we can study specific sites in the
vegetable macromolecules. Marked lignocelluloses, extracted in almost their
natural state, are very representative of the wood used for gasification in
industrial processes.
The thermal processing,
carried out in a concentrated radiation
furnace, involves the application of an anisotropic thermal flow to a small
sample in the form of a disk of solid material studied in isolation. The
general thermal conditions reasonably approximate those in the industrial
gasification process, even though the experiment is conducted on a much
smaller scale.
645
We have shown the predominant role of lignin in the formation of tars.
The contribution of this constituent of wood to the formation of pyrolysis
gas has also been partly elucidated: the lignin forms mainly carbon monoxide
and methane, most of the latter coming from the extra-cyclic methoxy groups
(5).
All the results constitute a theoretical basis for the monitoring and
direction of gasification reactions with a view to generating clean gas free
of tar.
ACKNOWLEDGEMENT
This work was carried
Franaise pour la Matrise
Midi-Pyrenees.
out with financial support from the Agence

de l'Energie and the Conseil Regional de
REFERENCES
(1)
(2)
(3)
(4)
(5)
G. ALIBERT and A.M. BOUDET, Physiol. V e g . , 1979, 1 7 , 6 7 .

S. CAUBET, P. C O R T E , C. FAHIM and J.P. TRAVERSE, Solar Energy, 1 9 8 2 ,
2 9 ( 6 ) , 565.
J. DOAT and X. DEGLISE, Bois et Forets des Tropiques, 1982, 198, 59.
E. A V N I , R.W. COUGHLIN, P.R. SOLOMON and HSIANG HUI KING, Fuel, 1985,
6 4 , 1495.
S. CASTILLO, S. CENNINI, G. GAS and J.P. TRAVERSE, Fuel,
1989, 6 8 ,
174.
646
REDUCTION ZONE HEIGHT DETERMINATION IN SOLID WASTE GASIFICATION PROCESS
IN A SHAFT FURNACE
J. WANDRASZ and K. WALECZEK
The Chair of Thermal Apparatus and Waste Disposal
Mechanical and Power Engineering Faculty
The Silesian Technical University, Poland
Summary
The paper deals with computing of the reduction zone height in a shaft
furnace used for gasification of waste wood by means of experimental
research on the kinetics of reduction reactions (charcoal reacting
with CO2 and H2O) . The problem has been narrowed to the analysis of
the process carried on the average temperature where ash is drained
from the combustion zone in a solid state. The research results show
that in a temperature range of 700-1100 C the reactions go in a
kinetic-diffusive area and the charcoal particle diameter has no
effect on the rate constant. Coefficients in Arrhenius equation are
evaluated. Two alternative mathematical models of the reduction zone
have been worked out: one for air-flue gas blast and another one for
air-steam blast. It has been confirmed that at the analysed temperatures in the combustion zone reduction reactions cease before a state
of equilibrium is reached in the system.
1. INTRODUCTION
Gasification processes can be divided according to the temperature in
the combustion zone into mean temperature processes
(at temperatures
1000-1200C) and high temperature ones (1400-1650C). In the first case the
solid residue is ashes, in the second one granulated product of melted slag.
In practice all large units for waste gasification work in the high temperature range. Mean temperature processes are applied in the smaller units in
an industrial plant where constructional simplicity, readiness to start and
stop the process is required. Processes with a combustion temperature up to
1100C do not require a water jacket, mobile rotary grid and water bowl,
which facilitates the design of the furnace.
Furnaces with the double receipt of gas, where part of the hot
comparatively pure combustible gas is carried away from above the reduction
zone, seem to be better. Designing such a system requires parameters of the
reduction zone to be defined including its height. In the mean temperature
process it can be easily done by determining parameters of reduction
reaction kinetics if the reaction rate constant depends on the temperature
of the process only. High temperature processes are not discussed in this
paper.
2. DESCRIPTION OF REDUCTION ZONE IN A SHAFT FURNACE IN WOOD WASTES
In the reduction zone in gas generators there are five main reactions
defining the process :
647
C + CO
= 2 CO
(5)
CO + H 2 0 = C 0 2 + H 2
(8)
C + 2 H 2 0 = C 0 2 + 2H 2
(6)
C + 2H 2 = CH 4
(9)
C + H 2 0 = CO + H 2
(7)
Reaction of methane formation (9) is important mainly in pressure

processes. When pressure equals atmospheric pressure the reaction is so slow
that it can be omitted in the description of the process. Reactions (5),
(6) , (7) and (8) are dependable and two of them are sufficient for the
description of the process. Reaction (8) in contact with coal is carried on
by means of a solid phase and thus has, like reactions (5), (6), (7), a
heterogeneous character. During research on the kinetics of the reduction
process in gas generators it is simplified and reactions of coal with CO2
and H2O are of the first order. In the kinetics equation the difference of
gas content to equilibrium content has to be taken into consideration. The
rate of reaction of a given component refers to the mass of a solid material
(coal) assuming that it is proportional to the material surface.
Therefore:
-(1/m) (dnoo /dr) = koo. (Coo
- Coo.R)
kmolAg s
(10)
-(1/m) (dnH20/dr) = kH 0 (CH 0 - CH 0 R)
kmolAg s
(11)
Reaction rate constant k depends on temperature according

equation :
k
A e-E/(MR)T (
3/kg
to Arrhenius
(12)
After some tests two reactions describing the whole process (e.g.
reactions (5), (6) or (7), (8)) should be chosen. The combustion zone
influences the reduction zone. To lower its temperature to 1000-1200C,
steam or flue gases should be added to air blast. Apart from carbon dioxide
and steam, the gases leaving the combustion zone consist also of some
amounts of carbon monoxide and hydrogen oxide which are difficult to define.
The content and temperature of the gas leaving the combustion zone give some
details necessary for reduction zone analysis.
3. SOME RESEARCH ON THE REDUCTION REACTION KINETICS
The research has been carried out mainly on charcoal being a gasification product of oak wood which belongs to a group of waste materials with
high volatile content. A flow power reactor has been used, where CO2, H2O,
mixture CO2-N2, H2O-N2, C0 2 -H20-N 2 were passed through a sample of charcoal,
within the temperature range of 700-1100C. After having analysed the gas
content downstream before and after the sample, constant reaction speeds
have been defined as koo2 and kH20 in different temperatures, and then the
value of coefficients A and E have been computed in equation (12).
It seems to be interesting that experiments carried on for different
charcoal granulation proved there is no influence of particles granulation
on values kcc>2 and kH2. Introductory measurements proved that the flow rate
as well as content of entering gas influence the value of ko02 and kH2.
Therefore the research has been carried on when flow rate and content of
entering gas are similar to those occurring in industrial gas generators. An
analysis of the results showed that CO as well as CO, are formed as a result
of coal reaction. For a model description of a simultaneous reaction of
648
100
2,5
H,
MJl_
<,S
^~~~
__
HOP
MO
kmol
Hop
SO
\AU.
"LHK_
M>t_
60
1000
10 BO
00
t,,
'C
1100
50
2.
H,
m
Hx^
1,5
i
Mhfa
Hg_
0,5
0,003
0,004
0.003
, <""'
' m1 a
0,007
' o.l
n t , fr"g' [oy
2,5
ifOO
MV
H,
MWH,
MJ
.moi
80
10
H
0,5
SO
100
f,
JUL.
HO
ao
fO
S,
_
m
,50
2,5
H,
m
\
.
<5
Hgp
MA/rf
. . *
<*
Fig. 1. Dependence of reduction zone height Hop and H90 and calorific
value of the gained gas MWd on temperature in the combustion
zone ts, blast stream ns, solid phase density and heat
losses Qs (for Ot = )
a : airflue gas blast, b airsteam blast
649
charcoal with H2O and CO2,
reaction systems (5) ,
applicable. The following results have been gained:
Reaction
C + CO
A , m3 Ag s,
= 2 CO
1007600
C + C 0 2 = 2 CO
C + 2 H O = CO
+ 2H
(6) are
the
most
E, J/kmol
184650000
25230655
212650000
2946990
188278000
The values of constant reaction speed koo obtained in the research

seem to be lower in the case of charcoal reaction with CO2 than in
simultaneous reaction of charcoal and CO and H O . It is caused by reaction
(7) omitted in the model description.
4. MATHEMATICAL MODEL OF REDUCTION ZONE AND RESULTS OBTAINED
A mathematical model of the reduction zone for gasification of
charcoal wastes has been designed according to the method of elementary
energy balances dividing reduction zone into differential elements. This
model has been designed in two versions :
for airflue gas blast, assuming that there is no H O in the blast,
for airsteam blast.
Computation of reduction reaction kinetics has been done using the
experimentally obtained values given above. The most problematic is the
description of heat exchange between the gas and solid phases in the
reduction zone. Therefore, computations have been repeated several times
with variable volumetric coefficient of heat penetration a,
W/m3 in the
range 0100000. The influence of such parameters as temperature in the
combustion zone, blast stream, density of solid phase and heat losses up to
the height of the reduction zone, calorific value and temperature of the gas
obtained have been tested.
It has been established that at analysed
temperatures in the combustion zone below 1200"C, reactions in the reduction
zone cease long before a state of equilibrium is reached in the system. In
higher parts of the reduction zone temperature is lowered mainly because of
heat losses. It has been established that there is an optimal height of the
reduction zone, Hop, above which total physical and chemical enthalpy of the
gas is lowered. This height is in practice the top limit border of the
reduction zone.
To define the phenomena better the height of 90% CO2
conversion (or CO2 and H 2 0 in the airsteam blast) has been calculated. In
Figure 1 this height has been denoted as H90.
The following proportions of the components in the gases leaving the
combustion zone have been assumed: CO2/CO = 1, H2O/H2 = 2. It has been shown
that any change of the assumed values influences the calorific values of the
reduction gas but not the height of the reduction zone. A similar conclusion
concerns changeability of volume heat penetration coefficient Ct between the
solid and gas phases (Figure 2 ) . It has been computed that calorific value
of the reduction gas MWd depends mainly on temperature in the combustion
zone ts, less on apparent density of charcoal and heat losses Qs. There is
no dependence on blast stream viz s. Optimal height of the reduction zone
Hop and height Hso depend on heat losses Qs and blast stream viz ns. The
influence of other parameters is negligible (Figure 1 ) .
Definitely higher calorific value of reduction gas has been obtained
in airsteam blast than in airflue gas blast.
650
Figure 3 shows an example of temperature distribution and concen
tration of the gas components in the reduction zone for airflue gas blast.
iOODOO
Fig. 2. Dependence of reduction zone height Hop and calorific value of

the gained gas MWd on volume heat penetration coefficient in
reduction zone in airflue gas blast
1Z0O
0,3
fJ
t,
c
[]
0,25
1100
0,2
1000
Hjo
H
900
0,1S
^t
0,1
BOO
fcj
D,0S
roo
]&__
600
1,5
H, m
Fig. 3. Distribution of gas components concentration and temperature of

solid phase in the reduction zone in airflue gas blast
(a = 20000 W/m 3 K, = 100 kg/m 3 , ts = 1100C, CO2 content in the
blast 7.8%), R state of equilibrium
651
COMPUTER MODELLING OF FLUIDISED BED GASIFICATION
J M DOUBLE, E L SMITH and A V BRIDGWATER
Department of Chemical Engineering and Applied Chemistry
Aston University, Birmingham, B4 7ET, England
Summary
The objective of this study has been to provide a greater understanding of
the biomass gasification process through the development and use of
computer models. A new theoretical equilibrium model of gasification is
described, based on the operating condition called the adiabatic carbon
boundary. This represents an ideal gasifier working at maximum efficiency the point where the carbon in the feedstock is completely gasified. It is used
as a "target" against which to compare the results of real gasifiers. A second
model has been developed which uses a stagewise approach in order to
model fluid bed gasification, and the results have indicated that pyrolysis
and the reactions of pyrolysis products play an important part in fluid bed
gasification. Results from both models are presented.
1. INTRODUCTION
The work described in this paper was undertaken in order to obtain a better
understanding of the chemical processes which occur in a biomass gasifier. The
first stage of the work was to construct an idealised model of gasification against
which the performance of real gasifiers can be measured. Some results of this
work have been presented elsewhere [1]. The second stage was to construct a
more sophisticated model of fluid bed gasification which uses a stagewise
approach. Both models described here are relatively simple, and both are
designed to predict the steady-state performance of a gasifier in terms of the
compositions and flowrates of its input and output streams. A representation of
this is shown in Figure 1. The models are not kinetic models, and they cannot be
used to size gasifiers or predict the spatial variation of reaction conditions within
the reactor.
Biomass
Gasifying
agent
Temperature
Flo wr ate
Composition:
C. H, O, Ash, H20
Temperature
Flo wr ate
Composition:
0 2 , N2, H20
Gasifier
Temperature |
Pressure
|
Temperature
\
Flowrate
Composition: H2, CO,
C02, CH4.C2S, N2. H20.
Temperature
Flowrate
Composition:
Ash, Char
| Heat losses |
Figure 1
Product
gas
Variables in the Models of Gasification
Solid
residues
652
2. EQUILIBRIUM MODELLING
The basis of any model of gasification is the material and energy balances
over the gasifier, but these balances are not sufficient on their own to calculate
the values of the unknown variables. The relationships of chemical equilibrium
have frequently been used as well [eg 2,3]. In addition to the mass and energy
balances and equilibrium relationships, other assumptions are needed, and the
number of assumptions used determines the number of degrees of freedom in the
system. Some of the variables in the system will be determined by
circumstances, for example the feedstock composition, flowrate and temperature.
Others will be chosen by the designer, typically the gasifying agent temperature
and composition and the pressure of the gasifier. If it is assumed that the reactor
is well mixed, as might be the case for a fluid bed gasifier, the outlet temperatures
will be equal to the reaction temperature. This leaves only one additional
variable to be specified, which can be either the gasifying agent flowrate or the
reaction temperature.
There are two cases of chemical equilibrium, the first when there is excess
carbon present in the system and char appears in the solid residue, and the
second where all the carbon is gasified in an excess of gasifying agent. There is
a third special case at the point between these two cases where the carbon is
completely gasified without an excess of gasifying agent. This point is known as
the carbon boundary. Previous work has enabled models of gasification to be
constructed for the cases either side of the carbon boundary, but in the current
work it was decided to concentrate on the carbon boundary itself, as explained
below. In the case of a carbon boundary equilibrium model with the assumptions
and design variables as described above both the temperature and gasifying
agent flowrate are fixed by the material and energy balances. Thus, for a given
feedstock, gasifying agent composition and operating pressure the carbon
boundary condition is achieved at a unique set of operating conditions.
In an ideal gasifier, the carbon boundary condition will give the maximum
chemical energy in the product gas. In the case where there is excess carbon in
the system, the char residue will contain chemical energy, allowing less chemical
energy in the gas phase. However, excess gasifying agent would reduce the
amount of chemical energy in the system by boosting the temperature of the
system and converting energy to sensible heat of the product gases. Thus, the
equilibrium carbon boundary model represents an ideal gasifier working at
optimum operating conditions for a particular feedstock and gasifying agent, and
can be used as a theoretical optimum against which the performance of real
gasifiers can be compared.
The results of a sensitivity analysis performed using the carbon boundary
model have already been published [1]. Figure 2 is an example of the output
obtained: it shows the effect of biomass moisture content on performance for an
oxygen gasifier. The sensitivity analysis predicted that the parameters which
have the most effect on gasification were biomass moisture content and gasifying
agent composition.
The reaction temperatures predicted by the model are lower than are
achieved in real gasifiers. The equilibrium model takes no account of reaction
rates and in real gasifiers higher temperatures must be used in order to achieve
reasonable gasification rates. If an equilibrium model is to be used for predicting
the performance of a real gasifier rather than providing an idealised target, a fixed
temperature model should be used operating with an excess of gasifying agent
over the carbon boundary case, with the equilibrium temperature being based on
actual values.
653
1073
o
Key
*
-*-
H2
CO
C02
CH4
M H20
Temperature
o.
E
8to
ro
O
20
40
60
80
Biomass moisture, % dry basis

Figure 2
Typical Results of the Carbon Boundary Equilibrium Model
Whilst equilibrium models are useful in presenting an idealised picture of

gasification, they do not always accurately predict the results from real gasifiers.
A comparison between the carbon boundary equilibrium model and real gasifier
results has already been published [1]. One reason for the differences between
real and ideal gasifiers is that some of the volatile and gaseous products of
pyrolysis may pass through the reactor without attaining equilibrium. A more
accurate model may be produced by adopting a stagewise approach with
separate submodels of pyrolysis and gasification.
3. STA GEWISE MODELLING OF FLUID BED GA SIFICA TION
A stagewise model is one in which a process is subdivided into steps or
stages. In the case of gasification, the steps are drying, pyrolysis, tar cracking,
and char gasification. In a fixed bed gasifier, the stages would take place in
different parts of the bed, but in a well mixed fluid bed reactor each reaction stage
would take place throughout the bed. A stagewise model of fixed bed gasification
can include both material and energy balances for each stage, whereas in a fluid
bed only an overall energy balance can be used in conjunction with the material
balances for each stage. A generalised stagewise model of a fluid bed reactor is
shown as Figure 3.
It is easy to model the char gasification step using equilibrium methods, but
pyrolysis is a very complex process which is sensitive to reaction conditions and
cannot yet be modelled theoretically. A n empirical model of pyrolysis must
therefore be used, based on data obtained under the same reaction conditions as
occur in a fluid bed gasifier (although an inert atmosphere must be used to avoid
gasification). Such pyrolysis data is rare. There are also little or no quantitative
data available on tar cracking within fluid bed gasifiers.
For the model described here it was decided to reduce the complexity of the
stagewise model by considering only two stages: a first stage incorporating the
drying, pyrolysis and tar cracking, and a second stage of gasification, modelled
using an equilibrium method assuming an excess of gasifying agent. Volatile
and gaseous material from the first stage might either pass directly to the outlet
stream or might be involved in the gasification stage. A number of possibilities
were tested, and the results which gave the closest fit to real data were obtained
654
when the hydrocarbons and tars from pyrolysis passed to the product gas, whilst
all of the other pyrolysis products passed to the char gasification stage. This is a
model of the case where there is good mixing within the reactor, but reaction
rates prevent the decomposition of the hydrocarbon products of pyrolysis. A
conceptual diagram of this model is presented in Figure 4.
Product gas
Biomass {
Drying /Pyrolysisp
VGasifier';
Figure 3
A Generalised Stagewlse M odel of a Fluid Bed Gasifier

Product gas
=^_
>
Drying, pyrolysis
and tar cracking
Gasifier
Figure 4
The Simplified Stagewlse M odel of Fluid Bed Gasification
The model has only been tested over a limited range of reaction conditions,
because of the lack of pyrolysis data. The pyrolysis data used are from Belleville
and Capart [4], and were obtained under reaction conditions similar to those
found in a fluid bed gasifier.
Table I shows a comparison with published results from two fluid bed
gasifiers. The results were obtained using the same operating conditions in the
model as were reported with the actual gasifier results. No experimental
parameters have been used to fit the results of the model to gasifier results.
There is good agreement with the results of the Lurgi Circulating Fluid Bed
gasifier, but poor agreement with the results of the Mino gasifier. This is probably
because the Lurgi CFB has good mixing within the reactor, as assumed in the the
computer model, whereas in the Mino gasifier there may be poor mixing. There is
also the possibility that the pyrolysis data used in the model are not applicable to
the feedstock used in the Mino gasifier.
655
Table I
Model
Lurgi CFB
Mino
Comparison of Model and Real Gasifier Results

Gas yield
Nm 3 /kg feed
1.37
1.36
Dry
H2
33.0
33.5
18.7
gas composition, mol %

CO C 0 2 C H 4 HCs
1.3
35.0 24.7
6.0
1.3
33.6 26.7
4.9
1.8
35.5 30.3 10.0
Ref.
[5]
[6]
[7]
Note : Compositions adjusted to a nitrogen-free basis. Gas yield is expressed as Nm 3 dry gas per
kg dry, ash free feedstock. Feedstock is wood, gasifying agent is oxygen/steam and
reaction temperature is 780C.
The stagewise model does not provide the information required for sizing a
gasification reactor. Models for calculating the char gasification rate are well
established [eg 8]: this is the rate determining step in gasification [9].
4.
CONCLUSIONS
The equilibrium carbon boundary model of gasification represents an
idealised gasifier and may be used as a target against which to compare the
results of practical gasifiers. Equilibrium models do not predict accurately the
results of fluid bed gasifiers because of the effects of pyrolysis, but stagewise
models which use equilibrium for char gasification calculations and empirical
pyrolysis models can predict the results of well-mixed fluid bed gasifiers.
5.
ACKNOWLEDGEMENT
The authors are grateful to the Science and Engineering Research Council
for their support of J M Double.
REFERENCES
1 D ouble J M, Bridgwater A V, "Sensitivity of Theoretical Gasifier Performance to System
Parameters", in Palz W, Coombs J, Hall DO (eds), "Energy from Biomass: 3rd EC Conference",
Elsevier Applied Science, 1985.
2 Gumz W, "Gas Producers and Blast Furnaces: Theory and Methods of Calculation", J Wiley and
Sons Inc, New York, 1950.
3 D esrosiers R, Thermodynamics of Gas-Char Reactions", in Reed (ed), "A Survey of
Biomass Gasification", Solar Energy Research Institute, Colorado, USA, 1979.
4 Belleville P, Capart R, "A Model for Predicting Outlet Gas Concentrations from a Wood Gasifier",
in Bridgwater A V (ed), Thermochemical Processing of Biomass", Butterworths, London, 1984.
5 D ouble J M, "The D esign, Evaluation and Costing of Biomass Gasifiers", PhD thesis, Aston
University, Birmingham, England, 1988.
6 Mehrling P, Reimert R, "Synthetic Fuel from Wood via Gasification in the Circulating Fluid Bed",
in Beenackers AACM (ed), "Advanced Gasification, Methanol Production from Wood - Results
of the EEC Pilot Plant Programme", D Reidel Publishing Company, Dordrecht, 1986.
7 Hall D O, Overend R P (eds), "Biomass: Regenerate Energy", Wiley, New York, 1987, p248.
8 Buekens A G, Schoeters J G, "Modelling of Biomass Gasification", in Overend R et al (eds),
"Fundamentals of Thermochemical Biomass Conversion" Elsevier Applied Science, Barking
England, 1985.
9 Smith E L, Shand R N, "Design and Evaluation of Biomass Gasification Systems", in Grassi G et
al (eds), "Biomass for Energy and Industry, 4th EC conference", Elsevier Applied Science,
1987.
656
THREE-PHASE WOOD GASIFIER SYSTEM EASIMODR

H. MICHEL-KIM
Efeu GmbH
Research and Development for Energy and Environment
D-5830 Schwelm
1. THREE-PHASE WOOD GASIFIER WITH LOW POLLUTION VALUES

EASIMODK SYSTEM MICHEL-KIM
Many of the attempts to develop wood gasifiers to a stage where they could
be put on the market, however, failed due to the fact that most one-phase
processes could not prevent the formation of tar and phenol or waste products.
The technical advantage of the Michel Kim/EFEU process is based on a
systematic breaking down of the various process phases of gasification and an
optimization of the individual stages providing for all necessary interventions in
the process parameters.
Traditional gasification processes were primarily one phase only, whereby the
internal gasification process with its complex transitions in the areas of material
transport and heat was left largely to coincidence. Tar and phenol formations
occurred continually, along with bridge and channel formations as well as slag
formation. Users of traditional gasifiers often had to put up with large and
unwieldy apparatus, effluent pollution and unpleasant odors, as well as high
maintenance costs.
2. ADVANTAGES OF THE EFEU PROCESS
The EFEU process of coordinated, multiphase gasification offers the
following advantages:
Overcoming of previous technical difficulties by a thorough development
of the gasification technology; avoidance of feared tar and phenol
wastes;
A wide variety of fuels, also with high moisture levels, can be converted
into gas in a manner friendly to the environment;
Gasification efficiency and load flexibility are considerably better than
in previous gasification systems as well as in all known methods of
firing.
3. SPECIAL FEATURES OF THE EASIMODR GAS GENERATOR
The working principal of the Michel-Kim EASIMODR-gas generating
system has become known during recent years, and, most recently, in a project
actually tested in Schwelm with a gas output of 2500 kW. The following
drawings, fig. 1 - 3, help to illustrate the characteristics of the latest stage of
development.
Figure 1) illustrates the dosing silo, the bottom loaded primary reactor with
level control, the intermediate gasification with flue charcoal circulation,
activated charcoal remover and coke reactor with integrated air heater.
657
The dosing silo has a reliable air buffer delivery system. Fuel is fed continually
from the silo into the bottom of the primary reactor, whereby the rate of fuel
feeding is controlled automatically depending on the various process parameters.
A portion of the fuel is fed into a circumjacent primary chamber and ignited
with preheated air. The combustion in the primary chamber stabilizes
gasification in the primary reactor and allows the removal of stones at this
stage.
During the intermediate gasification, gas conversion takes place at approx.
900 C in a rotating Venturi-burner; whereby gas and flue charcoal are
circulated. The conversion temperature is regulated with a secondary air supply.
Tar and phenols are hereby practically fully converted.
Depending on the direction of rotation of the Venturi-burner during the
intermediate gasification, flue charcoal (wood charcoal) from the primary
reactor can be either refed to the Venturi-burner or extracted via an integrated
worm gear. Depending on how long the charcoal remains in the intermediate
gasification (a regulable timespan) a high level of activation can be achieved so
that the use of wood charcoal as activated charcoal is possible.
The coke reactor also prevents tar and phenols from escaping from the primary
reactor and stabilizes the heating value of the generator gas at a high level.
Coke cosumption lies at around 1 % of the primary fuel quantity. (The coke
reactor is equipped with a stepped grate into which the air heater is integrated.
The primary air is pre-warmed up to approx. 520 C, the generator gas cooled
down to approx. 330 C.)
Dosing-silo
1.
2.
3.
Dosing-silo
Air bag
Screw conveyor
Underfed primaryreactor
4. Vertical conveyor
5. Agitator
6.
7.
8.
9.
Guide blades
Rotating grate
Venturi-burner
Worm gear
for charcoal
extraction
Coke-reactor
10. Air-heater
11. Step grate
V'
Figure 1)
,< ,',','.<
,t ,i ,< ,
658
Figure 2) illustrates the pre-drying and excess heat utilization. The drier has an
outer jacket of gill plate and a rotating cone made from perforated plate which
carries a progressive spiral conveyer. The fuel is in a ring channel around the
spiral cone. The rotation of the cone is such that the fuel is loosened and
carried upwards. Extraction of the fuel takes place at the bottom. The drying
air flows radially from the outside to the inside of the drier in the bottom area,
then upwards through the interior of the rotating cone and finally in a radial
direction from inside to outside through the fuel bed. The drying air is prewarmed up to over 100 C by using the hot generator gas and hot water in the
gas scrubber.
Pre-drying and excess heat utilization

1
Rotating cone
Gill plate
Water/Air heat exchanger
Progressive spiral conveyor
Water/Air heat exchanger
Perforated plate
Gas/Air heat exchanger
659
Figure 3) illustrates the 4-stage gas scrubber (2 jet scrubbers and 2 packing
scrubbers) with subsequent cooling tower, gas blower and burn off. During the
first three scrubbing stages the level of condensate is regulated and, in contraflow to the gas, enriched with ammonium. The removal of the ammoniumconcentrate takes place dependent on the level of concentration in the first
scrubbing stage. Condensation of the water contained in the cooled gas takes
place principally in the fourth scrubber. The condensate has only traces of
ammonium at this stage.
Figure 3)
4-stage Gas scrubber

1
Jet scrubber
Jet scrubber
Gas blower
Packing scrubber
Gas torch
Packing scrubber
Cooling tower
660
4. STATE OF DEVELOPMENT AND MARKET INTRODUCTION
The EASIMODK technology is currently being introduced to the market.
The European Licence rights were bought by Schwelm Anlagen + Apparate
GmbH, Schwelm, who put the first industrial gas generator into operation with
a gas output of about 2500 kW in march 1989.
Following the first test weeks, it can be assumed that the initial problems have
been solved and the market introduction phase can begin.
Schwelm Anlagen + Apparate GmbH will subject the existing 2500 kW gas
generator to a long term test and use this test period to make final adjustments
before beginning small series production. It is plannend to introduce 3 standard
sizes to the market for the generation of 500 kW (el), 1000 kW (el) and
2000 kW (el).
A large number of inquiries for the technology have been registered up to date.
The first EASIMODR gasgenerator for the generation-size of 1000 kW (el) will
be delivered in 1990.
L I S T OF PARTICIPANTS
663
ANTONELLI, L.
Vice President
KINETICS TECHNOLOGY INTERNATIONAL
S.P.A.
Via Monte Carmelo 5
I - 00166 ROME
ARAUZO, J.
Professor
UNIVERSITY OF ZARAGOZA
Facultad de Ciencias
Ciudad Universitaria
E - 5009 ZARAGOZA
AZNAR, M.-P.
Ass. Prof. Chem. Eng.
Dept. Chem. Eng.
E - 50009 ZARAGOZA
BABU, S.P.
Director, Process Research
INSTITUTE OF GAS TECHNOLOGY
3424 South State Street
USA - CHICAGO, IL. 60616
BEENACKERS, A.A.CM.
Prof. Chemical Engineering
GRONINGEN UNIVERSITY
Mijenborgh 16
NL - 9747 AG GRONINGEN
BELLMANN, U.
UNIVERSITT HAMBURG
Institut fr Technische und
Makromolekulare Chemie
Bundesstrae 45
D - 2000 HAMBURG 13
BETTENS, B.
Chef de Travaux
U.L.B.
50, Avenue Fr. Roosevelt
B - 1050 BRUXELLES
BILBAO, R.
Professor
Dpt. de Ingenieria Quimica
UNIVERSIDAD DE ZARAGOZA
E - 50009 ZARAGOZA
BALDELLI, C.
Engineer
ITABIA
Via Archimede, 161
I - 00127 ROMA
BILITEWSKI, B.
INTECUS
Krefelderstrae 20
B - 1000 BERLIN 21
BARTON, J.R.
Civil Servant
WARREN SPRING LABORATORY (WSL)
Gunners Wood Road
Stevenage
UK - HERTS SGI 2BX
BLASIAK, W.
Assistant Professor
THE ROYAL INSTITUTE OF TECHNOLOGY
Department of Heat & Furnance
Technology
S - 10044 STOCKHOLM
BAYER, E.
Professor
Institut fr Organische Chemie
UNIVERSITT TUBINGEN
Auf der Morgenstelle 18
D - 7400 TUBINGEN 1
BONFITTO, E.
Technical Officer - Engineer
REGIONE ABRUZZO - E.R.S.A.
Piazza Torlonia 91
I - 67051 AVEZZANO (AQ)
664
BONINO, G.
Engineer
BIOMASS ENERGIES
25, Strada della Viola
I 10133 TURIN
CAMP, J.P.
S.E.M. PAG VAPEUR
1, rue du Four
F 38190 CROUES
BONSANG, R.
Ingenieur Civil
INIEX
200, rue des Chra
4000 LIGE
CAPART, R.
Enseignant, chercheur
UNIVERSITY OF TECHNOLOGY OF
COMPIGNE
10, Square Sutterlin
F 60200 COMPIGNE
BOUGARD, J.
Director
BOUGARD ENGINEERING S.A.
33, Chausse de Mons
1400 NIVELLES
CARLSSON, K.B.
Project manager
Dept. FUM
FLKT IP
S 35187 VXJ
BRENNDRFER, M.
Dipl.Ing.
KURATORIUM FUR TECHNIK UD BAUWESEN
IN DER LANDWIRTSCHAFT e.V. (KTBL)
Bartningstrae 49
D 6100 DARMSTADT
CARRE. J.
Administrateur
ASCAB
27, rue Louis Vicat
F 75015 PARIS
BRIDGE, S.A.
Research Student
ASTON UNIVERSITY
Dpt. Chemical Engineering
Aston Triangle
UK BIRMINGHAM B4 7ET
CARVANI, L.
Researcher
ENIRICERCHE
26, Via Maritano
I 20097 S. DONATO MILANESE
(MILANO)
BRIDGWATER, .
Reader in Chemical Engineering
UNIVERSITY OF ASTON
Aston Triangle
BRUNETTI, .
Project leader in thermochemical
biomass conversion
ENEA
Dpt. Fare
CRECASACCIA
C.P. 2400
I 00100 ROMA
BUEKENS, A.
Professor
VRIJE UNIVERSITEIT BRUSSEL
Pleinlaan 2
1050 BRUSSELS
CASTILLO, S.
Teaching and Research
Laboratoire de Recherche sur
l'Energie
UNIVERSIT PAUL SABATIER
F 31062 TOULOUSE Cedex
CHURIN, E.
Researcher
UNIVERSITE CATHOLIQUE DE LOUVAIN
Unit CATA
1, Place Croix du Sud
1348 LOUVAINLANEUVE
CORELLA, J.
Prof. Chem. Eng.
Dept. Chem. Eng.
E 50009 ZARAGOZA
665
CORTE', P.
COMMISSION OF THE EUROPEAN
COMMUNITIES
200, rue de la Loi
1049 BRUSSELS
CRANSVELD, J.
TPR (TECHNOLOGIES POUR DES PRODUITS
RESIDUAIRES)
190 Quai du Halage
4131 AWIRS
CYPRES, R.
ULB
Chimie gnerale et Carbochimie
CP 165
1050 Bruxelles
DABORN, G.R.
Department of Trade & Industry
WARREN SPRING LABORATORY, DTI
Gunnels Wood Road
UK STEVENAGE HERTFORDSHIRE SGI 2BX
DARIF, M.
Thesard
LABORATOIRE DE CHIMIE ORGANIQUE
Facult des Sciences
Ile du Sauley
F 57000 METZ
DEARMAN, C R .
V E C U S ENERGY SYSTEMS Ltd
Longmace House
Mill Lane Arundel
UK WEST SUSSEX BN18 9AH
DE BOER, F.
HEINEKEN BREWERIES
P.O. Box 510
NL 2380 BD ZOETERWOUDE
DEHAYE, J.
AQUITAINERGIE
14, rue FranoisdeSourdis
F 33077 BORDEAUX Cedex
DEJAK, C.
ENEA
Viale Regina Margherita 125
I 00198 ROMA
DELMON, .
Professeur
UNIVERSIT CATHOLIQUE DE LOUVAIN
Unit CATA
1, Place Croix du Sud
1348 LOUVAINLANEUVE
DELRE, G.
Professor
UNIVERSITY OF L'AQUILA
Dpt. Chimica Ing. Chim. e Materiali
I 67040 MONTELUCO DI ROIO
(L'AQUILA)
DENIS, E.
Research & Development Engineer
CHI (Cockerill Mechanical Industries
Seraing) et C.R.l.G. (Centre de
Recherches de l'Institut Gramme)
25, rue de la Sablonnire
4900 ANGLEUR
DERBYSHIRE, F.
Research and Development Director
SUTCLIFFE SPEAKMAN CARBONS LTD
Guest Street
Leigh
UK LANCASHIRE WN7 2HE
DESMAZIERES, .
Research Engineer
UNIVERSITY PARIS VI
Laboratoire de Chimie Organique
Structurale
Btiment F
4 Place Jussien
F 75005 PARIS
DEVAL, M.
Administrateur de Socit
S.H. DEIRA
21, Square Larouse
1060 BRUXELLES
DE WILDE, J.P.
Research Assistant
DELFT UNIVERSITY OF TECHNOLOGY
Faculty of Aerospace Engineering
P.O. Box 5058
NL 2600 GB DELFT
666
DHEE, .
Grant
CADET INTERNA TIONA L
43, rue Paton
F 59800 LILLE
DIEBOLD, J.
Engineer
SOLAR ENERGY RESEARCH INSTITUTE
Cole Blud
USA Co 80401 GOLDEN
DIRVEN, P.
Energy Program Manager
SCK (BELGIAN NUCLEAR RESEARCH
CENTRE)
Boeretang 200
B 2400 MOL
DOEHRER, K.
Forstdirektor
VERSUCHS UND LEHRBETRIEB
FORSTTECHNIK/ HOLZHOF WALDECK/
HESS. FORSTAMT
Postfach 1108
D 3549 DIEMELSTADT
DOS SANTOS, A.M.
Associate Professor
Dept. of Heat and Furnace Technology
S 100 44 STOCKHOLM
DOUBLE, J.
Chemical Engineer
UNIVERSITY OF ASTON
Aston Triangle
DUPR, F.
Geschftsfhrer
C.DUPR GmbH & Co KG
FranzKirrmeierStrae 17
D 6720 SPEYER
EARP, D.M.
Research A ssistant
Dpt. of Chemical Engineering &
Applied Chemistry
ASTON UNIVERSITY
Aston Triangle
EBBAGGI, C.
TECHNICONSULT
595/C, Via Cassia
I 00189 ROMA
EKSTRM, G.G.V.
Process Engineer
STUDSVIK ENERGY (A division of
STUDSVIK AB)
Dpt. Applied Technology
Studsvik Energy
S 61182 NYKPING
ELAMIN, A.
Etudiant
UNIVERSITY OF COMPIGNE
Appt. 239
3, Square Blaise Pascal
F 60200 COMPIGNE
ENGELBRECHT, A.D.
Research Engineer
DIVISION ENERGY TECHNOLOGY, CSIR
P.O. Box 217
SOUTH AFRICA PRETORIA 0001
ESNOUF, C.
Research Engineer
C.E.M.A.G.R.E.F.
Bte 121
F 92164 ANTONY Cedex
FABRY, R.
Expert
COMMUNITIES
200, rue de la Loi
B 1049 BRUSSELS
FARGIONE, P.
Engineer
UNIVERSITY OF ROME
244, Corso Vittorio Emanuele II
I 00186 ROME
FENZL, W.
Projektmanager
VOESTALPINE
INDUSTRIEANLAGENBAU GES.m.b.H.
Turmstrae 44
A 4031 LINZ
667
FERRER, G.L.
COMMUNITIES
200, rue de la Loi
1049 BRUSSELS
FONT, R.
Professor of Chemical Engineering
UNIVERSITY OF ALICANTE
R. Font. Divisin de Ingeniera
Qumica
Apartado 99
E ALICANTE
FONZI, F.
Gen. Manager
ITALENERGIE SPA
39, Via Repubblica
I 67039 SULMONA (A Q)
FRANCAVILLA, G.
AERIMPIANTI S.P.A.
21, Via Bergamo
I 20135 MILANO
FRANCK, J.
UNIVERSITT HAMBURG
Bundesstrae 45
D 2000 HAMBURG 13
FRANCOIS, 0.
Ingnieur
UNIVERSIT DE TECHNOLOGIE DE
COMPIGNE
BP 649
F 60206 COMPIEGNE Cedex
FRISCHKORN, C.
Chemist
KFA JLICH GmbH
Kernforschungsanlage E
D 5170 JLICH
FRITZSCHE, A.
Diplom Ingenieur
FLEUS
UNIVERSITT BREMEN
Kutsteinerstrae NWl
D 2800 BREMEN 33
FROMENT, L.
R&D Chemical Engineer
Dept. Environment & Chemical Procese
Studies
S.C.. / C.E.N.
200 Boeretang
2400 MOL
GALLASTEGUI, S.
BEAZ S.A .
Alameda Recalde, 18
E 48009 BILBAO
GAMBINO, G.
Membro Commissione A mministratrice
FIORENTINAMBIENTE AZIENDA SERVIZI
NETTEZZA URBANA
52, Via Baccio da Montelupo
I 50142 FIRENZE
GARCIA, P.
Investigator
Dpt. de Ingenieria Qumica
UNIVERSIDAD DE ZARAGOZA
E 50009 ZA RA GOZA
GAUTIER, E.
Technical Director
S.E.S. SOFT ENERGY SYSTEMS
S.P.A.
64, Via Marino Ghetaldi
I 00143 ROMA
GAVR0, S.
Bachelor of Mechanical Engineering
ENERGOINVESTWO
Institute for Thermal Technique and
Nuclear Technique
Tvornicka br. 3
YU 71000 SARAJEVO
GIL, I.
BEAZ S.A .
Alameda Recalde, 18
E 48009 BILBAO
GIRARD, P.
Ingnieur de Recherche
CENTRE TECHNIQUE FORESTIER TROPICAL
45 bis, Avenue de la Belle Gabrielle
F 94736 N0GENY/MARNE
668
GRABIK, V.
Deputy Director
UNITED NATIONS INSDUSTRIAL
DEVELOPMENT ORGANIZATION (UNIDON)
Loewenstrae 1
CH 8001 ZURICH
HAYES, R.D.
Chief Bioenergy R&D
ENERGY MINES & RESOURCES CANADA
460 O'Connor Street
CANADA OTTAWA K15 5H3
GRASSI, G.
COMMUNITIES
Directorate General for Science,
Research and Development
200, rue de la Loi
1049 BRUSSELS
HECKA, C.
VEBA OEL AG
Alexandervon HumboldtStrae
Postfach 20 10 45
D 4650 GELSENKIRCHEN
GRGUREVIC, S.
M. A. Econ. Research Associate
INSTITUTE FOR INDUSTRIAL ECONOMICS
Marsala Tita 16/11
P.O. Box 317
YU 11000 BEOGRAD
GRIMM, H.P.
W.I.P. MNCHEN
Sylvensteinstrae 2
D 8000 MNCHEN 90
GUIGON, P.
Professeur
UNIVERSITE DE COMPIEGNE
U.T.C.
Dpt. de Genie Chimique
BP 649
F 60206 COMPIEGNE
GUIOL, R.
Technical Managerr
BIOALTERNATIVE S.A.
CH 2063 ENGOLLONNEUCHTEL
GULYURTLU, I.
Principal Research Engineer
LABORATORIO NACIONAL DE ENGENHARIA E
TECNOLOGIA INDUSTRIAL
Departamento de Energias
Convenctonaie
Edificio J.
Azinhaga Dos Lameiros
1699 LISBOA Codex
HAANAPPEL, V.A.C.
Research Engineer
BIG BIOMASS TECHNOLOGY GROUP B.V.
P.O. Box 217
NL 7500 AE ENSCHEDE
HEERAH, M.
Ph.D. Student
CEMAGREF
Parc de Tourvoie
BP 121
F 92164 ANTONY Cedex
HEESINK, A.B.M.
Dpt. of Combustion Technology
TNO Division of Technology for
Society
(MTTNO)
P.O. Box 342
NL 7300 AH APELDOORN
HENIUS, U.M.
Engineer
THE TECNOLOGICAL INSTITUTE
Gregersenevej
DK 2630 TSTRUP
HERBOLD, 0.
HERBOLDENGINEERING GmbH
SUdetenstrae 2
D 6920 SINSHEIM
HINGER, K.J
Ingenieur
WERNER & PFLEIDERER GmbH
Theodorstrae 10
D 7000 STUTTGART 30
HOCHHEIM , F.W.
General Manager
BIOMATERIAL INTERNATIONAL TECHNOLOGY
S.A.
Grossheide 323
D 4050 MOENCHENGLADBACH 1
669
HUMMELSHOEJ, R.M.
Project Engineer
COWIconsulC, Consulting Engineers
and Planners A.S.
45, Teknikerbyen
DK - 2830 VIRUM
HUMMELSIEP, H.
Abteilungsleiter
SAARBERG-FERNWRME GmbH
Sulzbachstrae 26
D - 6600 SAARBRCKEN
IACOBONI, S.
Head Department
FACHHOCHSCHULE PRESENIUS
Department of Trace Analysis
Dambachtal 20
D - 6200 WIESBADEN
JACCARD, L.
Administrateur
ENS0F0R S.A.
CH - 6985 CURIO
JACKSON, D.
Consultant to DG XII El
11 Orchard Crescent
STEVENAGE
UK - HERTS SGI 3EN
JRGENSEN, L.
Engineer
DANSK TERMO INDUSTRI A/S
Induetrivaenget 27
DK - 3400 HILLERD
KAMBALE, K.
Ingenieur Forestier
Centre d'adaptation des techniques
de l'energie bois - "CATEB"
MINISTRE DE L'ENVIRONNEMENT
BP 11596
ZAIRE - KIN I
KAMINSKY, W.
Prof. Dr.
Institut fUr Technische u.
UNIVERSITT HAMBURG
Bundesstrae 45, 2
D - HAMBURG 13
KITTELMANN, J.-F.
Engineer
VLUND FORSKNINGSCENTER
Centervej 2
DK - 6000 KOLDING
KNIGHT, J.A.
Consultant
KNIGHT CONSULTANTS, Inc.
2117 Kodiak Dr. NE
USA - ATLANTA GA 30345
KOULLAS, D.
Chemical Engineer, Researcher NTU A
NATIONAL TECHNICAL UNIVERSITY OF
ATHENS
Department of Chemical Engineeerlng,
Div. IV
42, Patision street
GR - 10682 ATHENS
KROMSBEIN, G.
Process Engineer
UHDE GmbH
Friedrich-Uhde-Strae 15P.O. Box
105062
D - 4600 DORTMUND 1
KRISTENSEN, 0.
Engineer
Centervej 2
DK - 6000 KOLDING
KURKELA, E.
Research Scientist
TECHNICAL RESEARCH CENTRE OF FINLAND
Biologinkuja 5
SF - 02150 ESPOO
KUTUBUDDIN, M.
Chemist
Institut flir Organische Chemie
UNIVERSITT TUBINGEN
Auf der Morgenstelle 18
D - 7400 TUBINGEN 1
LACROSSE, L.
Gasification Coordinator
CENTER FOR AGRONOMICAL RESEARCHES
23, Avenue Marchal Juin
B - 5800 GEMBLOUX
670
LAPPAS, .
Graduate Studene
CHEMICAL PROCESS ENGINEERING
RESEARCH INSTITUTE
PO Box 19517
GR 54006 UNIVERSITY CITY
THESSALONIKI
LAURIDSEN, T.L.
Manager
Dpt. R & D
AALBORG BOILERS A/S
P.O. Box 209
DK 9100 AALBORG
LUENGO, C A .
Physicist
UNIVERSITY OF CAMPINAS
Applied Physics Dept.
CXP 6165
BRASIL 13081 CAMPINAS
LYNGE JAKOBSEN, J.H.

M.Sc.
CARL BRO AS
Granskoven 8
DK 2600 GLOSTRUP
MALY, V.
Engineer
KFA PBE
Postfach 1913
D 5170 JLICH
MANIATIS, .
Expert to the Commission of European
Communities
V.U.B.; CHIS,
Pleinlaan 2
1050 BRUSSELS
MARITANO, M.
Manager
CASTAGNETII S.P.A. (FIAT Group)
Via Acqui 86
I 10090 CASCINE VICARIVOLI
(Torino)
MARSCHEIDER, F.
Dipi. Chem.
UNIVERSITT HA MBURG
Bundesstrae 45
D 2000 HAMBURG 13
MARTINMARTINEZ, J.M.
Ph.D. Chemistry
INESCOP
Instituto Espafiol del Calzado
Polig. Ind. campo Alto
PO Box 253
E 03600 ELDA (A licante)
MARTINEZSANCHEZ, M.A.
Ph.D. Chemistry
INESCOP
Instituto Espafiol del Calzado
Polig. Ind. campo Alto
PO Box 253
E 03600 ELDA (A licante)
MARURI, J.
BABCOCK WILCOX ESPAOLA S.A .
6, Centre International Rogier
Bte 442
1210 BRUXELLES
MASS0N, H.
R & D Manager
N.V. SEGHERS ENGINEERING
Molenweg 107
2660 WILLEBROEK
MAUND, J.K.
Lecturer
Dpt. of Chemical Engineering &
Applied Chemistry
ASTON UNIVERSITY
Aston Triangle
MEIER, D.
Research Scientist
INSTITUTE FOR WOOD CHEMISTRY
Leuschnerstrae 91
D 2050 HAMBURG 80
MELAN, C.
Directeur adjoint
PAUL WURTH S.A .
.P. 2233
L 1022 LUXEMBOURG
MENDIS, M.S.
Economist Engineer
THE WORLD BA NK
1818 Street NW
USA WASHINGTON DC 20433
671
MEZERETTE, C.
Ingnieur Chimiste
CT.F.T. / C.I.R.A.D.
45 bis, Avenue de la belle Gabrielle
F 94736 NOGENTSURMA RNE
NOVAK, M.
Manager
ENERGAS
GottliebDunkelStrae 21
D 1000 BERLIN 42
MICHELKIM, H.
GeschfsfUhrer
EFEU
Loher Strae 1
D 5830 SCHWELM
0ASMAA, A.
Research Scientist
Laboratory of Fuel Processing
Technology
Biologinkuja 35
SF 02150 ESP00
MININNI, G.
Senior Scientist
CNR Instituto di Ricerca Sulle
Acque
1, Via Reno
I 00198 ROMA
MOLINA, L.
Engineer R&D
AERIMPIANTI S.P.A.
21, Via Bergamo
I 20135 MILANO
MLLER MADSEN, S.
M.Sc. Engineering
I KRUGER A/S
Gladsaxevej 363
DK 2860 SOEBORG
MUNCK, J.
Chemical Engineer
I. KRUGER AS
Gladsaxevej 363
DK 2860 SBORG
NELS, C.
Beamter
UMWELTBUNDESAMT
Postfach
D 1000 BERLIN 33
NICOLAY, D.
COMMUNITIES
DirectorateGeneral
Telecommunications, Information,
Industries and Innovation
L 2920 LUXEMBOURG
OLSEN, G.
Chemical Engineer
LABORATORY OF ENERGETICS, TECHNICAL
UNIVERSITY OF DENMARK
DTH Building 403
DK 2800 LYNGBY
0'NEIL, D.J.
Research Director
GEORGIA TECH RESEARCH INSTITUTE
USA ATLANTA GA 30332
PARK, D.
Research Scientist
KOREA ADVANCED INSTITUTE OF SCIENCE
& TECHNOLOGY (KA IST)
P.O. Box 131
Cheongryang
KOREA SEOUL
PASSANO, E.
AERIMPIANTI S.P.A.
21, Via Bergamo
I 20135 MILANO
PEREIRA, F.J.
Professor
UNIVERSIDADE DE AVEIRO
Departamento de Ambiente
3800 AVEIRO
PETERSEN, .
Engineer, Managing Director
INNOSYS
Heimdalsgade 14
DK 2200 COPENHAGEN
672
PETERSEN, E.
Manager of research cenere
Centervej 2
DK 6000 KOLDING
PISKORZ, J.
Research Engineer
UNIVERSITY OF WATERLOO
DepC. of chemical Engineering
WATERLOO
CANADA ONTARIO N2L3GI
POHLMANN, K.
Dipl. Chem.
UNIVERSITT HAMBURG
Institue fUr Technische und
Bundesstrae 45
D 2000 HAMBURG 13
POOS, .
COMMUNITIES
DirectorateGeneral Personnel and
Administration
L 2920 LUXEMBOURG
POUSAZ.P.
Ingnieur en chimie
BIOALTERNATIVE S.A.
CH 2063 E N G O L L O N N E U C H A T E L
RAHNENFUHRER, R.
UNIVERSITT HAMBURG
Institut fUr Technische und
Bundesstrae 45
D 2000 HAMBURG 13
RENSFELT, E.
Area Manager
STUDSVIK ENERGY
S 61182 NYKPING
RICK, F.
Dipl.Ing.
TUV RHEINLAND E.V.
Postfach 10 17 50
D 5000 KLON
RITAPAL, K.
Editor
ERD0L & KOHLE ERDGAS PETROCHEMIE/
HYDROCARBON TECHNOLOGY
Postfach 100 252
D 7022 LEINFELDENECHTD.
RODRIGUEZ JIMENEZ, J.J.

Professor
Dpto. Ingenieria Qumica
UNIVERSIDAD DE MALAGA
Campus Universitario de Teatinoe,
S/N
E 29071 MALAGA
RODRIGUEZ MIRASOL, J.
Research Felo
Dpto. Ingenieria Quimica
UNIVERSIDAD DE MALAGA
Campus Universitario de Teatinoe,
S/N
E 29071 MALAGA
ROSSI, C.
ENEL THERMAL AND NUCLEAR RESEARCH
CENTRE
CR.T.N.
Via A. Pisano
I 56100 PISA
RAMPLING, T.W.A.
Scientist
WARREN SPRING LABORATORY, DTI
Gunnel8 Wood Road
UK STEVENAGE HERTFORDSHIRE SGI 2BX
RSSLER, H.
UNIVERSITT HAMBURG
Bundesstrae 45
D 2000 HAMBURG 13
RAYMOND, G.A.
Ingnieur
PYROPNEU
31, rue Sompr
B 4120 IVOZRAMET
ROY, C.
Associate Professor
Dpt. of Chemical Engineering
UNIVERSIT LAVAL
CANADA SAINTEFOY (Qubec) GIK 7P4
673
SALO, .
R&D Manager
A. AHLSTROM OSAKEYHTIO
BIONEER OY
PL 537
SF 13111 HXMEENLINNA
SCHDEL, S.
UNIVERSITT HA MBURG
Bundesstrae 45
D 2000 HAMBURG 13
SCHIEBER, A.
FRA GmbH
Postfach 1645
D 7080 AALEN
SCHNEIDER, T.
CivilEngineer
KOINSTITUT e.V.
Bliro Darmstadt
PrinzChristiansWeg 7
D 6100 DARMSTADT
SCHULTEN, H.R.
Head Department
FACHHOCHSCHULE PRESENIUS
Department of Trace Analysis
Dambachtal 20
D 6200 WIESBADEN
SHAH, N.
Research Engineer
C.T.F.T. / C.I.R.A.D.
45 bis, Avenue de la belle Gabrielle
F 94736 NOGENTSURMA RNE
SIB0N0, A.
BIO ALTERNATIVE ITA LIA Sri
1, Via Caffaro
I 16124 GENOVA
SIPIL, .
Director of Laboratory
TECHNICAL RESEARCH CENTRE OF FINLA ND
Technology
Biologinkuja 35
SF 02150 ESPOO
SOLANTAUSTA, Y.
Research Scientist
Biologinkuja 5
SF 02150 ESPOO
SORACE, G.
Managing Director
FIORENTINAMBIENTE AZIENDA SERVIZI
NETTEZZA URBANA
52, Via Baccio Da Montelupo
I 50142 FIRENZE
SPINOSA, L.
Senior Scientist
CNR Instituto di Ricerca Sulle
Acque
5, via F. de Biasio
I 70123 BARI
STHLBERG, P.
Research Engineer
Technology
Biologinkuja 35
SF 02150 ESP00
STASSEN, H.E.M.
Director
BTG (BIOMASS TECHNOLOGY GROUP B.V.)
P.O. Box 217
NL 7500 AE ENSCHEDE
STEFFENSEN, U.
UNIVERSITT HA MBURG
Bundesstrae 45
D 2000 HAMBURG 13
STENHOLM, M.
DKTEKNIK
Gladsaxe Mllevej 15
DK 2860 SBORG
STEPPAT, H.
Dipl.Ing.
Kufsteinerstrae 18
D 8205 KIEFERSFELDEN
674
STILES, H.N.
Consulting Engineer
BTG BIOMASS TECHNOLOGY GROUP B.V.
P.O. Box 217
NL 7500 AE ENSCHEDE
VAN DER WEIDE, J.

Research Manager
TNO DELFT
PO Box 237
NL 2600 AE DELFT
STOIKOS, T.
Researcher
CHEMICAL PROCESS ENGINEERING
RESEARCH INSTITUTE
PO Box 19517
GR 54006 UNIVERSITY CITY
THESSALONIKI
VAN HEEK, K.H.

Professor
BERGBAUFORSCHUNG GmbH
FranzFischerWeg 61
D 4300 ESSEN 13
STREHLER, .
Professeur
TECHN. UNIVERSITY MUNICH
Weihenscephan Bayer
Landesanstalt flir Landtechnik
Am Staudengarten 3
D 805 FREISING
STRIPP, O.F.
HERBOLDENGINEERING GmbH
Sdetenstrae 2
D 6920 SINSHEIM
VELCICH, G.
Development Engineer
DANEC0 DANIELI ECOLOGIA S.p.A
Via Linussio
Z.I.U.
I 33100 UDINE
WANDRASZ, J.
Professor
POLITECHNIKA SLA SKA
Wyckiat Mechaniczny
111 Konarskiego 18
POLEN 44100 GLIWICE
SWISTER, M.
Etudiant
LABORATOIRE DE CHIMIE ORGANIQUE
Facult des Sciences
Ile du Sauley
F 57 045 METZ
WANZL, W.
Dr.rer.nat
BERGBAUFORSCHUNG GmbH
FranzFischerWeg 61
D 4300 ESSEN 13
SWITTEN, S.
Secrtaire A dministration
MINISTRE DE LA RGION WALLONNE
(IGE)
Avenue Prince de Liege, 7
5100 NAMUR
WICHERT, J.
Dipl. OK
FLEUS
UNIVERSITT BREMEN
Kufsteinerstrae NWI
D 2800 BREMEN 33
TARALAS, G.
Msc.
Department of Chemical Technology
S 10044 STOCKHOLM
WILLIAMS, P.
Lecturer
Department of Fuel and Energy
UNIVERSITY OF LEEDS
UK LEEDS LS2 9JT
THESSN, G.
MSc (ME)
FLKT AB
Box 81001
S 10481 STOCKHOLM
WINTHER, E.B.
B.Sc..E.
ELKRAFT POWER COMPANY Ltd.
5, Lautruphfit
DK 2750 BALLERUP
675
WOLF, .
Rechtsanwalt
PKA
Robert Bosch Strae 82
D 7080 AALEN
WOLPERT, V.M.
WOLPERT & JONES (Studies) Ltd.
Hunters, Holly Hill
Colemans Hatch
UK EAST SUSSEX TN7 4EP
YING, Y.
UNIVERSITT HAMBURG
Institut fUr Technische und
Bundesstrae 45
D 2000 HAMBURG 13
ZANZI, R.
MSc.
THE ROYAL INSTITUTE 0F TECHNOLOGY
Department of Chemical Technology
S 10044 STOCKHOLM
ZEPPI, C.
Research Engineer
ENEL / CRTH
120, Via A. Pisano
I 56100 PISA
677
INDEX OF AUTHORS
ABATZOGLOU, N.S., 420
AMMAR, S., 158
ANTONELLI, L. , 85
ANTONINI, G., 425
ARAUZO, J., 613
AZNAR, M.P., 624, 629
BARTON, J.R., 57, 391
BASSELIER, J.J., 568
BATALLER, ., 435
BECKER, J.J., 635
BEENACKERS, A.A.CM., 129, 312, 396
BELLMANN, U., 190
BENNINI, S., 640
BETTENS, B., 209
BILBAO, R., 613
BILITEWSKI, ., 98
BLASIAK, W., 468
BONFITTO, E., 586
BONINO, G., 527
BRANDANI, V., 430
BRIDGE, S.A., 541
BRIDGWATER, A.V., 43, 129, 195, 274,
347, 394, 411, 541, 598, 651
BRUNETTI, ., 586
BUEKENS, ., 274, 492, 574, 580
CAPART, R., 158, 530, 593
CARRE, J., 93
CASTILLO, S., 640
CEBRIAN, ., 624
CHURIN, E., 326, 399
COLLIN, R., 468
CONTI, L., 246
CORDERO, ., 435
CORELLA, J., 618, 624, 629
CYPRES, R., 209
CZERNIK, S., 201
DELGADO, J., 629
DELMON, B., 326
DEL RE, G., 430, 586
DESBENE, P.L., 568
DESMAZIERES, ., 568
DEVESA, J., 230
DE WOLF, F., 580
DIEBOLD, J., 14, 342
DI GIACOMO, G., 430, 586
DISS, J.M., 417
DOUBLE, J.M., 651
EARP, D.M., 238
ELAMIN, ., 158
ENGELBRECHT, A.D., 296
ESNOUF, C , 106, 425, 554
ESSAYEGH, M., 568
FABRY, R., 387, 405

FERRER, G.L., 3, 405
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Thermochemical processing of renewable resources and

solid fuels has become a strong contender partially to
replace the energy dependence of the European Community on imported hydrocarbon fuels; the Commission
is supporting R&D as well as demonstration projects in
this field. Similarly in the USA, Canada and the developing countries numerous projects have been carried out on
fundamental, as well as industrial scale, projects on
pyrolysis and gasification. Such technologies are therefore of increasing importance worldwide, not only because they can be utilized to dispose of various industrial
wastes ri an environmentally acceptable way.
Though interesting results and experiences have certainly been achieved, several problems still remain and
their solution will strongly influence the commercialisation of pyrolysis and gasification all over the world.
It was the need to evaluate critically the progress
achieved in this field and to draw up recommendations
for future work which prompted the Directorate-General
for Energy of the Commission of the European Communities to organise this international conference with
the assistance of the Directorate-General for Telecommunications Information Industries and Innovation.
While invited speakers from the Commission, EC
countries, the USA, Canada and the World Bank presented
overviews on all aspects of pyrolysis and gasification
processes such as feedstock, pretreatment and characterisation, gasification and pyrolysis technologies, products upgrading and utilization as well as environmental
and economic aspects, researchers and industrialists from
20 countries presented their results and views in oral as
well as poster presentations. The workshops and panel
discussions gave the opportunity to all participants to
express their opinion so that realistic recommendations
for future R&D and demonstration activities could be
drawn up.
About 200 participants representing administration,
governmental institutions, universities and industry
attended the conference. This is fresh proof of the
significance in recent years of pyrolysis and gasification
technologies.
ISBN 185166 4491

Pyrolisis and Gasification

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Commission of the European Communities

PYROLYSIS AND GASIFICATION

Proceedings of an international conference held in Luxembourg, 23-25 May

ELSEVIER APPLIED SCIENCE

ELSEVIER SCIENCE PUBLISHERS LTD

Library of Congress CIP data applied for

Publication arrangements by Commission of the European Communities, Directorate-General

Thermochemical processing of renewable resources and solid fuels has become a

ACTIVITIES AND RESULTS OF THE COMMISSION DEMONSTRATION

COMMUNITY R&D STRATEGY IN THE FIELD OF BIOMASS PYROLYSIS

PROGRESS IN PYROLYSIS AND GASIFICATION OF BIOMASS:

OVERVIEW OF THERMOCHEMICAL CONVERSION OF BIOMASS IN CANADA

RAPPORTEUR'S REPORT ON SESSION I

PRETREATMENT AND CHARACTERIZATION OF FEEDSTOCKS

PROCESSING OF URBAN WASTE TO PROVIDE FEEDSTOCK FOR

CHARACTERIZATION OF CARBON CONTAINING MATERIALS WITH RESPECT

BIOMASS FUELS AND GASIFICATION

USAGE OF CARBON BLACK AND ACTIVATED CARBON IN RELATION TO INPUT

RAPPORTEUR'S REPORT ON SESSION II

GASIFICATION AND PYROLYSIS OF BIOMASS IN EUROPE

THE GEORGIA TECH ENTRAINED FLOW PYROLYSIS PROCESS

PILOT PLANT DEMONSTRATION OF USED TIRES VACUUM PYROLYSIS

FLUIDIZED BED PYROLYSIS OF SEWAGE SLUDGE

CHEMICALS FROM ALMOND SHELLS BY PYROLYSIS IN FLUIDIZED BED

BIOMASS PYROLYSIS IN MOLTEN SALTS FOR FUEL PRODUCTION

FLASH PYROLYSIS OF SULCIS COAL

RAPPORTEUR'S REPORT ON SESSION IV

ELECTRICAL ENERGY FROM BIOMASS'

FLUIDIZED BED GASIFICATION OF WOOD: PERFORMANCE OF A

A NATIONAL PROGRAM ON IMPLEMENTATION OF BIOMASS GASIFICATION

GASIFICATION AND PYROLYSIS OF STRAW - RESEARCH IN DENMARK

AN INVESTIGATION INTO THE GASIFICATION OF LOW QUALITY

PRESSURIZED FLUIDIZED BED GASIFICATION OF PEAT

RAPPORTEUR'S REPORT ON SESSION V

WHAT CAN WE DO WITH PYROLYSIS OILS?

COMPOSITION, PURIFICATION AND USE OF PRODUCER GAS

RAPPORTEUR'S REPORT ON SESSION VI

WASTE MANAGEMENT AND PYROLYSIS:

RAPPORTEUR'S REPORT ON SESSION VII

WORKSHOP 3 - GASIFICATION TECHNOLOGY AND ECONOMICS

WORKSHOP 4 - PYROLYSIS AND UTILIZATION

THE USE OF WOOD AS FUEL IN MALAYSIA

THERMOCHEMICAL DENSIFICATION OF BIOMASS

PREPARATION AND USE OF CHARCOAL : WATER SLURRIES

TREATMENT OF PYROLYSIS OIL WITH COMPRESSED CARBON DIOXIDE

ACTIVATED CARBON FROM EUCALYPTUS KRAFT LIGNIN

ACTIVATED CARBONS FROM CHROMIUM-TANNED LEATHER WASTE

MOTOR FUELS FROM PYROLYTIC LIGNINS

ROLE OF CHROMIUM OXIDE IN THE TEXTURE OF CARBONS FROM LEATHER

INFLUENCE OF THE POROSITY OF CARBON IN Fe/Carbon CATALYSTS

DEVELOPMENT AND CONSTRUCTION OF A SAMPLING LINE FOR WOOD

FURNACE FOR BIOFUELS THERMAL UTILIZATION

INVESTIGATION OF TOXIC COMPONENTS IN PRODUCTS FROM MUNICIPAL

RESEARCH ON TAR CRACKING AND APPLICATION OF TAR

THE FUEL PROPERTIES OF HYDROCARBON LIQUIDS DERIVED FROM

ENVIRONMENTAL AND PUBLIC HEALTH ASPECTS OF GASIFIER SYSTEMS

CHARACTERIZATION OF WOOD CONSTITUENTS BY PYROLYSIS

CHARACTERIZATION OF WOOD BY PYROLYSIS

ENERGAS SEWAGE SLUDGE PYROLYSIS

CARBONISATION OF LARGE WOOD PIECES IN A LABORATORY RETORT:

MILD PYROLYSIS PROCESS IMPROVES STEAM CYCLE EFFICIENCY

FLASH PYROLYSIS OF BIOMASS FOR LIQUID FUELS

GASIFICATION OF REFUSE, A PROCESS OF SFW

A CATALYTIC GASIFICATION PROCESS OF BIOMASS