Review of Kinetic and Equilibrium Concepts For Biomass Tar Modeling by Using Aspen Plus

Renewable and Sustainable Energy Reviews 52 (2015) 16231644
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
Review of kinetic and equilibrium concepts for biomass tar modeling

by using Aspen Plus
A.M.A Ahmed, A. Salmiaton n, T.S.Y Choong, W.A.K.G. Wan Azlina
Department of Chemical & Environmental Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
art ic l e i nf o
a b s t r a c t
Article history:
Received 26 November 2014
Received in revised form
16 May 2015
Accepted 27 July 2015
Biomass tar has attracted attention in recent years to be modeled or represented by a specic formula or
compound. It is a complex material, and its composition varies according to the process operating
conditions such as gasication or pyrolysis. This paper reviews different tar models in which tar is
represented as different components such as naphthalene, toluene and even as a bulk tar, based on
operating temperatures range and their thermal stability or assumptions that have been made to model
the process. All these models are done by Aspen Plus simulator based on kinetic and thermodynamic
equilibrium, whereby different reactor models are used to represent processes in relevant with tar
production or cracking. Results for the operation of combined heat and power (CHP) biomass bubbling
uidized bed gasication, which integrated with solid fuel cell (SOFC) or coupled with an internal
combustion engine (ICE), show different accuracy in terms of cold gas or electrical efciencies,
depending on how tar is approximated (either as one hydrocarbon compound or mixture of
hydrocarbons). Likewise, for three-stage and one uidized bed unit, the performance is predicted
through estimation of the cold gas efciency and high heating value (HHV) of the produced gas, where
the tar representation has also an impact on the accuracy of the predictions.
& 2015 Elsevier Ltd. All rights reserved.
Keywords:
Biomass tar
Modeling
Aspen Plus
Kinetic
Thermodynamic equilibrium
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1625
Gasication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1625
Principles of chemical equilibrium and kinetic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1626
Biomass tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1628
4.1.
Tar denition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1628
4.2.
Tar composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1629
4.2.1.
Primary tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1629
4.2.2.
Secondary tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1629
4.2.3.
Tertiary tar products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1629
4.3.
Sampling and characterization of tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1630
4.3.1.
Tar sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1630
4.3.2.
Characterization of tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1631
4.4.
Tar reaction mechanism and kinetic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1631
Aspen Plus tar models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1631
5.1.
Combined heat and power (CHP) biomass bubbling uidized bed gasication unit coupled with an internal combustion engine (ICE) 1631
5.2.
Integrated atmospheric pressure solid oxide fuel cell (SOFC) with biomass steam gasication process and combined heat and power (CHP)
system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1633
5.3.
Biomass gasication fuel cell (BGFC) and biomass gasication combined cycle (BGCC) systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1634
5.4.
Biomass integrated gasication combined cycle (BIGCC) technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1635
5.5.
Complete life cycle inventory of a biomass gasication integrated with heat and power (CHP) plant . . . . . . . . . . . . . . . . . . . . . . . . . . 1635
5.6.
Pressurised steam/O2-blown uidized-BEd gasication for biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1638
Corresponding author. Tel.: 60 3 89466297; fax: 60 3 86567120.

E-mail address: mie@eng.upm.edu.my (A. Salmiaton).
http://dx.doi.org/10.1016/j.rser.2015.07.125
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
1624
A.M.A Ahmed et al. / Renewable and Sustainable Energy Reviews 52 (2015) 16231644
Nomenclature
rG
reaction Gibbs energy (kJ/mol)
A, B
reactants in chemical equation
a, b, c, d stoichiometric coefcient of components a, b, c, d
A, k0, k0,app pre-exponential factor (1/s)
C
carbon
C, D
products in chemical equation
C10H8
naphthalene
C12H8
acenaphtylene
C14H10a anthracene
C14H10p phenanthrene
C16H10 pyrene
C2H4
ethylene
C2H4O2 acetic acid
C2H6
ethane
C3H3
2-cyclopropenylium
C3H8
propane
C6H6
benzene
C6H6O phenol
C7H8
toluene
C7H8O benzyl alcohol
C8H8
styrene
C9H8
indene
CH4
methane
Ci
concentration of component i
CmHy
hydrocarbon with smaller carbon number
CnHx
tar
CO
carbon monoxide
CO2
carbon dioxide
E, Ea, Eapp activation energy (kJ/mol)
fact
activity factor
G
Gibbs free energy (kJ/mol)
GS/MS gas chromatographymass spectrometry
H2
hydrogen
H2O
water
H2S
hydrogen sulde
hcg
cold gas efciency
HCl
hydrogen chloride
HCN
hydrogen cyanide
HHV
high heating value
ht
thermal efciency
k
rate constant
LHV
lower heating value
n
stoichiometric coefcient of components CO, CO2, C
n
stoichiometric coefcient of H2O
n, x, r
stoichiometric coefcient of H2
N2O
nitrous oxide
NH3
ammonia
NO
nitrogen oxide
NOx, SOx Gaseous emissions
O2
oxygen
p
stoichiometric coefcient of tar
pi
partial pressure of component i
q
stoichiometric coefcient of light hydrocarbons
R
universal gas constant
ri
rate of reaction of component i
SOx
sulphur oxides
T
temperature
TsK
solid structure temperature (K)
v0
volumetric owrate (m3/h)
W
X
weight (kg)
conversion
Subscripts
app
cg
m
n
t
tar
x
y
apparent
cold gas
number of
number of
thermal
tar
number of
number of
atoms of C in light hydrocarbon

atoms of C
atoms of H2
atoms of H2 in light hydrocarbon
Greek letters
a, b, c, d chemical potential of components a, b, c, d
W/v0
Abbreviations
BFB
bubbling uidized bed
BGCC
biomass gasication combined cycle
BGFC
biomass gasication fuel cell
BIGCC
biomass integrated gasication combined cycle
B-IGFC biomass-integrated gasication fuel cell systems
CHP
combined heat and power
CR
char converter
DDGS
distiller dried grains with solubles
DSS
dried sewage sludge
DWG
distillers wet grains
EFFLUSEP ash separator efuent stream name in Aspen Plus
ER
equivalence ratio
FB
uidized bed
FBD
uidized bed devolatizer
GE
general electric
ICE
internal combustion engine
IEA
International Energy Agency
IGCC
Integrated gasication combined cycle
IPA
iso-propanol solution
LS
seal
NCGR
non-catalytic gas reformer
NREL
National Renewable Energy Laboratory
PAH
polyaromatic hydrocarbons
PTR
pneumatic transported riser
RCSTR
continuous stirred tank reactor model in Aspen Plus
REQUIL equilibrium reactor model in Aspen Plus
RGIBBS Gibbs reactor model in Aspen Plus
RPLUG plug ow reactor in Aspen Plus
RSTOIC stoichiometric reactor model in Aspen Plus
RYIELD yield reactor model in Aspen Plus
SOFC
solid oxide fuel cell
SOR
steam to oxygen ratio
STAGSIFYrecycle stream name in Aspen Plus
STBR
steam to biomass ratio
STR
steam reforming reactions
TARIN
stream name for tar in Aspen Plus
TES
thermal energy storage
TNEE
Tunzini Nessi Entreprises dEquipements process
5.7.
Staged-gasication system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.8.
Different systems and different tar representation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Appendix A.
Supplementary information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1625
1638
1640
1642
1643
1643
1. Introduction
2. Gasication
The continual increase of energy demand and the impact of fossil

fuel on the environment have made heavy stress on the developed
countries to look for another alternative for energy supply. Many
researches have reviewed and discussed alternatives technologies
such as thermal energy storage (TES), which considered as a friendly
energy source, utilizing biomass [15]. The availability of biomass and
its clean relationship with environment, has given it the priority to be
under intensive research. The lignocelluloses polymers such as cellulose, hemicelluloses and lignin represent the major portion of the
enormous amount of biomass annually produced on land [6].
Cellulose is basically consist of -glucosidic units in the polymer
chain. It forms approximately of 50 wt% on a dry basis of biomass
components [7]. The other constituent is hemicelluloses which take
place a lower percent than celluloses [7]. It contains backbones of 1,4 linked major sugar units which make its chemical composition close
to cellulose [6]. The morphology of hemicellulose and cellulose are
strongly associated with each other in the plant cell walls [6]. On other
hand, the last constituent lignin can mainly be found in woody
biomass and cellulosic [7]. Moreover, the lignin is also found in
terrestrial biomass as aromatic polymers that contains phenyl propane
units, and those units contain benzene rings which substituted by
methoxyl and hydroxyl groups [7].
Thermal degradation of biomass under severe temperature conditions leads to produce many different types of condensable hydrocarbons (tar) and depends on that severe temperature. The tar
removal technologies such as reformer or cracking are the main target
by the industrial gasication units since its existence causes severe
problems to the facilities that utilize the produced gases from
gasication or pyrolysis units. Hence, many mathematical models
have been created and developed to estimate or to optimize the
operating conditions which predict the tar condensation temperature,
and to evaluate the performance of gasication unit. Other models are
developed by using simulation programs, and Aspen Plus is one of
them. This simulation software consists of many physical relationships
such as material and energy balance, thermodynamic equilibrium and
rate equations which enable the designer to predict process behavior.
This paper reviews many models of gasication and pyrolysis processes involving tar formation during the process and its removal
using either reforming or cracking. These reviewed models are
designed by Aspen Plus by which the tar is assumed to be one of
the stable constituents, like naphthalene, toluene and benzene in
comparison with the other constituents that forming the tar.
It is a chemical process that occurs in a decient oxygen environment to convert carbonaceous wastes to useful gaseous with a high
heating value or chemical feedstock. In contrast, combustion takes
place in oxidizing environment [8]. Through many years, this process
had been utilized as an energy source for industry and transportation.
In recent years, owing to the global warming issues, the seeking for
independence in energy production and the oscillation in prices of
crude oil motivated some countries to develop integrated gasication
combined cycle (IGCC) plants.
The typical gasication process follows the scheme illustrated in
Fig. 1, and consist of many steps [8]. These steps overlap and there are
no clear boundaries between them, however in modeling purposes
these steps are done in series for simplication, and they are as
follows.

Preheating and drying

Pyrolysis
Char gasication
Combustion
nitially, gasication begins with drying step in order to remove the

moisture from the feedstock and followed by thermal decomposition
or thermal degradation which produces gases, tar and char. These
products react with each other and with gasifying agent such as
oxygen, air and steam to form the nal gasication products. The
chemical reactions of gasication are listed in Table 1 [710].
Many reactors can be used to perform gasication process. The
type of gassolid contacting reactors used shows different gasication
reactions sequence [6]. The main reactors for gasication are as
follows:
Moving-bed reactor: The simple type that explains this kind of

the reactors is the updraft gasier reactor, Fig. 2. In this type,
the fuel is fed from the top and the produced gases leave from
the top also [6]. The gasifying agents (oxygen, air, steam or their
mixtures) are preheated and enter the reactor from the bottom
through a grid. The gases will then rise through the reactor
meeting the descending fuel or ash.
Fig. 3 shows the reaction steps in downdraft gasiers will differ
from those in updraft gasiers [6]. The gasifying agents and
biomass are both fed into the gasier lower part. The pyrolysis
Fig. 1. Potential paths for gasication.
1626
and combustion products ow downward, and the hot gases also

move downward meeting the remaining hot char, where gasication takes place.
Fluidized-bed reactor: In a bubbling uidized bed, the solid fuel
is fed either from the top or the sides, and the gasifying agents
are served from the bottom of the reactor [9], Fig. 4. The direct
contact of the solid fuel and the hot bed material brings the fuel
quickly to the bed temperature which enhances the drying and
pyrolysis steps. The gasication reactions occur as the gas rises.
Entrained-ow reactor: This kind of reactors is commonly
operated at 1400 1C and 20 to 70 bar. The solid fuel is in a
powder condition and can be entrained by gasifying agent. This
type of reactors is preferred to be used with IGCC plants [6].
There are two types of the reactor; in the rst one, side feeding
for both biomass and gasifying agent is used [6], Fig. 5a,
whereas in the second one, the feeding is from the top for
both biomass and gasifying agent [6], Fig. 5b.
Table 1
Gasication Reactions at Standard Temp. (25 1C).
Reaction type
Carbon reactions
R1 (Boudouard)
R2 (watergas or steam)
R3 (hydrogasication)
R4
Oxidation reactions
R5
R6
R7
R8
Shift reaction
R9
Methanation reactions
R10
R11
R14
Steam-reforming reactions
R12
R13
a
Source: [9].
Source: [7].
Source: [9].
d
Source: [10].
b
c
Reaction
C CO222CO 172 kJ/mola

C H2O2COH2 131 kJ/molb
C 2H22CH4 74.8 kJ/molb
C 0.5 O2-CO 111 kJ/mola
b
C O2-CO2 394 kJ/mol

CO0.5O2-CO2 284 kJ/mold
CH4 2O22CO2 2H2O 803 kJ/molc
H2 0.5 O2-H2O 242 kJ/mold
COH2O2CO2 H2 41.2 kJ/mold
2CO2H2-CH4 CO2 247 kJ/mold
CO3H22CH4 H2O 206 kJ/mold
CO2 4H2-CH4 2H2O 165 kJ/molb
CH4 H2O2CO 3H2 206 kJ/molc
CH4 0.5 O2-CO2H2 36 kJ/molc
3. Principles of chemical equilibrium and kinetic

Chemical thermodynamics mainly deals with prediction of a
spontaneity tendency of the reactants mixture change into products,
to predict the reaction mixture composition at equilibrium, and to
predict the mechanism involved during the modication of the
composition by changing the process conditions. Only one thing to
remember, thermodynamic never considers the rate of the reaction.
The spontaneous change in thermodynamic at constant temperature
and pressure is Go0. Up to these conditions, a reaction mixture
proceeds setting its composition to attain minimum Gibbs energy. In
Fig. 6(a), we see very small variation in the Gibbs energy of the mixture
means a very small conversion extent of the reactants before G has
attained its minimum value and the reaction cannot be proceeded. If G
changes as shown in Fig. 6(c), then a high percent of products must
form before G attains its minimum and the reaction proceeds. In some
cases, no signicant amount of reactants or products can be found in
the equilibrium mixture. However, other reactions have a Gibbs energy
varies as shown in Fig. 6(b), and means a considerable amount of both
reactants and products exist at equilibrium [11].
The reaction Gibbs energy (rG) can be interpreted in two way
[11]. First, at specic composition of the reaction mixture, it is the
difference of the chemical potentials of the products and reactants.
Secondly, we can consider of rG is the slope of the graph of G
plotted versus the change in composition of the system since rG
is the change in G divided by the change in composition, Fig. 7.
For the reaction:
aA bB-cC dD
In Gibbs energy of a reaction equation, each reactant multiplied

by their stoichiometric coefcient and subtracted from the products that also multiplied by their stoichiometric coefcients

2
r G cC dD aA bB
The chemical composition of a substance is decided by the mixture
composition that contains this substance, and becomes high when its
concentration or partial pressure is high. So, rG is changed as the
composition changes, Fig. 8. For the chemical reaction in Eq. (1), we
notice rGo0 which means the slope of G is negative when the
mixture is rich in the reactants A and B because A and B are then
high. In contrast, rG40 and the slope of G is positive when the
mixture is rich in the products C and D because C and D are also
high. When rGo0 the mixture composition forms more products;
while rG40, the reverse reaction is promoted to form the reactants
Fig. 2. Gasication reactions illustrated in stages in an updraft gasier.
1627
Fig. 3. Downdraft gasier and gasication reactions.
Fig. 5. Entrained-ow gasier types: (a) side-fed reactor, and (b) top-fed reactor.
Fig. 4. Scheme of a bubbling uidized-bed gasier.
again, means products decomposition occur [11]. At rG0 (the point

at which the slope is zero), the reaction will not take place to form
either products or reactants, Fig. 8. That is, the reaction is at
equilibrium at constant temperature and pressure [11]. RGIBSS and
REQUIL (Aspen Plus reactors models) are based on previously mentioned criteria.
On contrary, chemical kinetic deals with how fast reactants and
products are consumed and formed, the response of reaction rates
to change with the presence of a catalyst, and identify the steps by
which a reaction happens. The reason behind studying the rates of
reactions is the practical importance of being able to estimate how
rapidly the equilibrium of the reaction achieved. The factors that
the rate depends on (under our control) are pressure, temperature,
and presence of a catalyst. Choosing the suitable conditions has a
great role in optimizing the rate of the reaction. One more reason
for studying the reaction rates is to realize the mechanism of the
reaction and the sequence of its elementary steps [11].
A kinetic of any reaction which are represented by the rate
equation should be well understood, by studying and investigating
the details of a rate equation, and those are: the order of the
reaction, rate constant and kinetic parameters such as A (pre
exponential factor) and E (activation energy). The rate equation is
used to describe the rate of a reaction quantitatively, and to
express the functional dependence of the rate on temperature
and on the species concentrations. In symbolic form, the rate
equation can be written as follows [12],
r A r A T; all C i
From Eq. (3) two independent variables are seen; T is the

temperature and the term all Ci is present to remind us that the
reaction rate can be affected by the concentrations of the reactant
(s), the product(s), and any other compounds that are present,
even if they do not participate in the reaction [12]. Another form of
rate equation may include partial pressure of a substance pi,
especially for gases.
The coefcient k, which appears in the reaction rate equation, is
called the rate constant (as in Eq. (4)) [11]. This rate constant depends
on the temperature but it is independent of the concentration of the
species participates in the reaction.
Rate k AB
The measuring units of k are always used as a conversion factor

for the product of concentrations of species, which appear in the
rate equation, to units expressed as a change in concentration
divided by time. For example, if the rate law is the one shown
above, with concentrations expressed in mol/dm3, so the units of k
will be dm3/mol/s as follows:
3
dm = mol= s mol=dm mol=dm mol =dm = s
The three terms of the left hand side of Eq. (5) are k,
concentrations of [A] and [B], respectively, and at the same time
the right hand of the equation denotes the rate. In gas-phase
studies, concentrations are commonly expressed in molecules
cm 3, so the rate constant for the reaction above would be
expressed in cm3/molecules/s. We can use the approach just
developed to determine the units of the rate constant from rate
laws of any form. For example, the rate constant for a reaction with
rate law of the form k [A] is commonly expressed in s 1 [11].
As mentioned above in the symbolic form of rate equation, it is also
can be written as a function of temperature and composition [13], or
r i f 1 temperature U f 2 composition
k U f 2 composition
1628
Fig. 8. Reaction tendency related to rG.
Fig. 6. Variation of Gibbs energy of a reaction mixture during reaction course.
Fig. 7. Variation of Gibbs energy at a specic composition of the system.
Fig. 9. Arrhenius plot.
The temperature-dependent term or the reaction rate constant

is well dened by Arrhenius law:

k k0 U exp E=RT
8
analysis of tar and also gases are the predominant product of

gasication, few previous studies on biomass gasication include the
analysis of tars were done [14].
Most of the data nowadays available on biomass-derived tars was
obtained from pyrolysis studies at low reaction temperatures [14].
Nonetheless, the amount and make-up of tar species evolved in the
pyrolysis of biomass at temperatures below 600 1C may usually have
little correspondence to tars extracted in the gasication of biomass/
oxidant at temperatures above 700 1C. To conclude, one way to solid
engineering information, an ability of operating of gasication systems
and controlling emissions from the process is understanding the
fundamentals of tar formation in biomass gasication [14].
The parameters of Arrhenius law are k0 and E which represent

frequency or pre-exponential factor and activation energy, respectively. These parameters also called the Arrhenius parameters. The
calculations of these parameters are done by plotting lnk (rate
constant) versus 1/T (absolute temperature), from which a straight
line obtained, Fig. 9. Experiments approved that Arrhenius law
shows a good tting over a wide range of temperature [13].
The mathematical expression of this conclusion is that the rate
constant varies with temperature as mentioned below [11].
ln k intercept slope 1=T
This expression is normally written as the Arrhenius equation:

ln k ln A Ea =RT
10
Since the rate shows dependence on the temperature, so we

can estimate the rate of a reaction at different temperature but
with same concentration [7], suggesting E constant, Arrhenius law
expressed by Eq. (11)

r2
k2 E 1
1
ln ln
11

r1
k1 R T 1 T 2
4.1. Tar denition

One of the denitions of the tar regards it to be a complex
mixture of condensable fraction of the organic products which
produced from gasication and predominately aromatic hydrocarbons. Due to variable product gas composition that needed for a
specic end-use application and different procedures for sampling
and analyzing the tar collected, many operational denitions for
tar could be found [15].
biomass O or H2 O -CO; CO2 ; H2 O; H2 ; CH4 other hydrocarbons
-tar char ash
12
4. Biomass tar
-HCN NH3 HCl H2 S other sulfur gas
Biomass gasication mainly produces different products: gases,

condensable tars, and solids (char and ash). Tars are condensable
organic compounds formed in thermochemical processes such as
gasication and pyrolysis. The tar species is a wide range of different
boiling points hydrocarbons that is mainly consist of single-ring to
ve-ring aromatic hydrocarbons. Due to difculty of sampling and
In Eq. (12), many different products from biomass gasication

can be seen and range from light gases such as CO, H2, CO2, CH4,
H2O and N2 to organic (tars). Besides that, inorganic (H2S, HCl,
NH3, alkali metals) impurities and particulates also found in the
products. The organic impurities extend from low molecular
weight hydrocarbons to high molecular weight polynuclear
1629
Fig. 10. Tar compounds transformation scheme proposed by Elliott.
Table 2
Tar compounds for different tar classes.
Tar
Class name
class
Property
Very heavy tars, cannot be detected by GC
2
3
4
5
GC-undetectable
Representative compounds
Determined by subtracting the GC-detectable tar fraction from the

total gravimetric tar
Heterocyclic aromatics Tars containing hetero atoms; highly water soluble compounds
Pyridine, phenol, cresols, quinoline, isoquinoline, dibenzophenol
Light aromatic (1 ring) Usually light hydrocarbons with single ring; do not pose a problem Toluene, ethylbenzene, xylenes, styrene
regarding condensability and solubility
Light PAH compounds 2 and 3 Rings compounds; condense at low temperature even at
Indene, naphthalene, methylnaphthalene, biphenyl,
(23 rings)
very low concentration
acenaphthalene, uorene, phenanthrene, anthracene
Heavy PAH compounds Larger than 3-ring, these components condense at highFluoranthene, pyrene, chrysene, perylene, coronene
(47 rings)
temperatures at low concentrations
composition of biomass pyrolysis products and gasier tar from

various processes also done by Elliott [17].
Table 3
Composition of Tar.
Source: Adopted from Milne et al. [16].
Component
Weight
(%)
Benzene
Toluene
Other 1-ring aromatic
hydrocarbons
Naphthalene
Other 2-ring aromatic
hydrocarbons
3-Ring aromatic hydrocarbons
4-Ring aromatic hydrocarbons
Phenolic compounds
Heterocyclic compounds
Others
37.9
14.3
13.9
9.6
7.8
3.6
0.8
4.6
6.5
1.0
aromatic hydrocarbons. Although the lower molecular weight

hydrocarbons are undesirable products in fuel cell applications
and methanol synthesis, it can be used as fuel in gas turbine or
engine applications. The higher molecular weight hydrocarbons
can be termed as tar. The specications of tar are being
refractory and difcult to remove by neither thermal, catalytic
nor physical processes. Moreover, tar can be condensed or polymerized into more complex structures causing problems (chocking
and attrition) in downstream applications such as heat exchangers, pipes or on particulate lters. Besides that, the total efciency
could be reduced and the cost of the process is raised as a result of
the generation of tar [15].
Formation of tar happens by a series of complex reactions
during gasication process, and is highly dependent on the
reaction conditions. Tar secondary reactions happen in the gas
phase after increasing in temperature of the reaction that convert
oxygenated tar compounds to light hydrocarbons, aromatics,
oxygenates and olens and subsequently form higher hydrocarbons and larger PAH (polyaromatic hydrocarbons) in tertiary
processes [16].
A scheme proposed by Elliott and summarized by Milne [16]
that explains the tar formation is presented in Fig. 10. This scheme
shows the transformation of tar over different temperature starting from mixed oxygenates compounds (primary tar) to larger PAH
[17]. Table 2 shows various types of chemical components corresponding each tar class based on Gas chromatographymass
spectrometry (GC/MS) analysis of tar [15]. A review study for the
4.2. Tar composition

Tar is a complex mixture of various hydrocarbons as shown in
Table 3. It consists of oxygen-containing compounds, derivatives of
phenol, guaiacol, veratrol, syringol, free fatty acids, and esters of
fatty acids [18]. In addition, Table 3 shows that benzene has a
maximum percent among other constituents of a typical tar [8,16].
The reaction temperature, the type of reactor and the feedstock are
the factors that affect the yield and the composition of tar.
There is another classication for tar and this would be:
primary, secondary, alkyl tertiary and condensed tertiary [16].
Short descriptions of these sorts of tar are as follow [8]:
4.2.1. Primary tar
Primary tar is a product of pyrolysis at temperatures 673973 K
[19]. It contains oxygenated, primary organic and condensable
molecules. The main constituents of biomass: cellulose, hemicellulose and lignin are responsible for formation of the primary
products by direct breakdown of the aforementioned constituents
of biomass. Many compounds such as acids, sugars, alcohols,
ketones, aldehydes, phenols, guaiacols, syringols, furans, and
mixed oxygenates in this group are listed by Milne et al. [16].
4.2.2. Secondary tar
Primary tar at temperature above 500 1C starts rearranging,
forming more non-condensable gases and heavier molecules
called secondary tar. Phenols and olens are considered to be
important constituents of this kind of tar [8].
4.2.3. Tertiary tar products
The contents of this kind of tar are: alkyl tertiary product which
mainly contains methyl derivatives of aromatics, such as methyl
acenaphthylene, methylnaphthalene, toluene, and indene [16];
and the other content is condensed tertiary aromatics that make
up a polynuclear aromatic hydrocarbon (PAH) series. This series is
not branched with atoms as a substitute of hydrogen in the main
chain. Benzene, naphthalene, acenaphthylene, anthracene/phenanthrene, and pyrene are the constituent of this series. Both
secondary and tertiary tar are produced from the primary tar.
When tertiary products appear, no primary tar can be found [16].
1630
4.3. Sampling and characterization of tar

Sampling and analysis of tars and particulates (gasication
products) were done by many different techniques. Therefore, a
working group from the Biomass Gasication Task of the IEA
Bioenergy Agreement was delegated to develop a criterion for
measuring produced gas quality [20]. The new procedure Tar
Protocol adopted different air or oxygen-blown gasier types
(updraft, downdraft/xed bed or uidized bed gasier), operating
conditions (0900 1C and 0.660 bar), and concentration ranges
(1300 mg/N m3) [15].
Moreover, a lot of development has been made for on-line
methods, which is concerned in collecting, identifying and quantifying tars in syngas (product gas). Three types for these methods
are available: gas conditioning, sampling and analytical phases. A
scheme proposed for the tar sampling and analysis procedure is
shown in Fig. 11 [20]. Several methods were adopted for sampling
of tars like trapping of compounds onto cold surfaces and lters,
absorption of tars into cold organic solvents or adsorption onto
suitable adsorbents [20]. Gas chromatography (GC) or gravimetrically is used in analytical phase analysis of tar compounds [20].
4.3.1. Tar sampling

European Tar Protocol has presented a sampling unit for
collecting and analyzing tar from the produced gas in gasication
[20]. In this unit, six impinger bottles are ordered in a series way,
the rst ve bottles are lled with iso-propanol (IPA) solution,
while the remaining one is left empty, Fig. 12 [20]. For the bottles
(1, 2 and 4) are heated to 35 1C, while the rest for the other three
bottles (3, 5 and 6) are cooled down to 20 1C. For the sake of
obtaining better gas dispersion, the bottles 2, 3 and 5 are equipped
with glass-sinters. The sixth bottle is needed as a droplet collector,
thats why it is kept empty. A particular lter is prepared to receive
the sample gas and followed by six impinger bottles to collect tar
and moisture into the IPA solution, Fig. 12. The order of the bottles
are 1, 2, 3, 4, 5, and 6 to guarantee heat circulation from hot to hot,
cold, hot, cold and cold [20]. All these bottles are placed in a styrox
box with a thick styro-foam wall between the warm and cold
baths [20]. Flow rate of gases that pass through the bottles is
controlled by a regulator which in turn is connected to a pump.
After the process of tar collection is nished, the contents of
bottles are collected then tubing and glass parts washed with IPA
solution and the collected solution is made to volume [20].
Fig. 11. Tar sampling and analysis procedure.
Fig. 12. Tar sampling unit.
Fig. 13. Characterisation and analysis of tars.
4.3.2. Characterization of tar

Two kinds of tar are detected from biomass gasication: heavy
tar which condenses and trapped onto cold surface and lters
(isopropanol is used to collect it), and light tar which gathered
from impinger bottles, Fig. 13 [20].
The collected light tar is analyzed by using two methods, of
which the gravimetric analysis is the simplest [20]. The procedure
of this analysis implies recording the weight of the tar left in a
ceramic dish after a 50 ml of isopropanol tar mixture initially
evaporated in a fume hood for a whole night and then heating up
the mixture in a chamber at 105 1C for 60 min [20]. Later, the tar
concentration in the produced gas is calculated from the total gas
ow rate [20]. The second method shows a different technique,
where the 50 ml of isopropanol tar mixture is separated in a
distillation process that consist of a water bath of 75 1C for 30 min
[20]. The products of this process are two fractions of hydrocarbons: the fraction dissolved in the isopropanol which is called
light hydrocarbons and a distillation residue [20]. Moreover, a
third fraction of hydrocarbons is available in the decanted water
which called water soluble hydrocarbons [20]. For tar analysis
purposes, gas chromatography with mass detection (GCMS) is the
major analysis technique [20]. Standard gas chromatography
parameters are: column temperature program: 50 1C for 5 min to
325 1C at 8 1C/min, stop for 5 min; injector:split, 1:75; injector
temperature: 275 1C; detector temperature: 300 1C; injection
volume: 12 l; carrier gas: hydrogen or helium, column pressure
adjusted so that the linear velocity of hydrogen is 3055 cm/s and
helium 2040 cm/s [20].
4.4. Tar reaction mechanism and kinetic

Cracking, steam and dry reforming are reactions that responsible for tar decomposition, as shown below [21].
Cracking : pCn Hx -qCm Hy rH2
13

Steamreforming : Cn Hx nH2 O - n x=2 H2 nCO
14

Dryreforming : Cn Hx nCO2 - x=2 H2 2nCO
15
Carbonformation : Cn Hx -nC x=2H2
16
where Cn Hx and Cm Hy stand for tar and hydrocarbon with smaller

carbon number than Cn Hx , respectively.
At typical gasication temperatures, the tar composition is
mainly consist of polycyclic aromatic hydrocarbons (PAHsbenzene, naphthalene, phenanthrene, anthracene, etc.) and some
methylated aromatics [2225]. Tar with such composition means
potential problems will appear, and that for two reasons: (1) they
are very stable, refractory, and difcult to crack further and (2) they
cause catalyst deactivation by formation of coke on catalyst surface
[26]. For these reasons, many authors choose these compounds to
represent tar in tar modeling in order to calculate the kinetic
parameters of tar as done by Devi et al. [21] and Jess [27] who
choose naphthalene as tar component model, while Simell and
Hirvensalo [28] used benzene as a component model of tar. In
other research, 1-methylnaphthalene was used by Dou et al. [29]
for modeling. The common reaction kinetic equations used in tar
kinetic models are shown in the following [15]:
r tar kapp C tar ; kapp
ln1 X

Eapp
W
; kapp k0;app U exp
RT
v0
17
1631
5. Aspen Plus tar models

Aspen Plus broadly can be dened as a process simulation
program which provides an estimation for parameters of a process
(pressure, temperature, composition and sizing) under specic
conditions by using mass and energy balances relations and phase
equilibrium database. It consists of many built-in unit operations
such as reactors, separators, heat exchangers, distillation and
physical properties of the materials. In addition, this simulation
can handle unconventional materials such as solids which are
considered the main constituent in many processes such as
gasication. Adopting suitable thermodynamic data, realistic operating conditions and precise equipment models, real process
behavior approached. Process simulation program is a useful tool
in planning new process and developing existing one.
Additional characteristics of Aspen Plus are following:

Rigorous Electrolyte Simulation.

Petroleum Handling.
Data Regression.
Data Fit.
Optimization.
User Routines (This property can be done by writing external
subroutines using Fortran Programming Language).
Aspen Plus has been used in different aspects of modeling such

as steam power plant [30], predicting emissions of NO and N2O
from coal combustion [31], catalytic coal gasication in xed beds
[32], biomass gasication in uidized bed reactor [33], and in
combined heat and power (CHP) biomass bubbling uidized bed
gasication unit coupled with an internal combustion engine (ICE)
[34].
In spite of the biomass tar is a complex mixture, many authors
represented it in Aspen Plus in many ways.
5.1. Combined heat and power (CHP) biomass bubbling uidized bed
gasication unit coupled with an internal combustion engine (ICE)
Damartzis et al. [34] assessed a combined heat and power
(CHP) biomass bubbling uidized bed gasication unit coupled
with an internal combustion engine (ICE), as represented in Fig. 14.
A comprehensive mathematical model based on the Aspen Plus
process simulator was adopted by the author. This model was
based on the kinetic and equilibrium criteria along with energy
and mass balances. For the kinetic principles, a RCSTR (Aspen Plus
reactor model) was used to represent the behavior of a uidized
bed since the characteristics of the bed is similar to the features of
the RCSTR reactor by assuming a perfect gas mixture. Whereas
RGIBBS (Aspen Plus reactor model) reactor block was used to
simulate the volatiles release during biomass decomposition
which was already occurred in RYIELD (Aspen Plus reactor model)
block, and this RGIBBS follows the chemical equilibrium. The tar
produced from pyrolysis was modeled as a mixture of three
components: benzene, toluene and naphthalene. The quantitative
measurement of this tar mixture was assumed to be a 20% w/w
conversion of the original biomass to tar and a composition of 60%,
20% and 20% for benzene, toluene and naphthalene, respectively
[35]. The kinetic data for the formation of the 3 tars compounds
and their decomposition to CO2, H2 and CO was taken from the
literatures, and the tar reactions considered in this model are
listed in Table 4 [3638].
A sensitivity analysis was accomplished for two main parameters in the gasication process: equivalence ratio (ER) and
temperature. Syngas (H2 CO) yield was assessed according to
various values of ER (0.2, 0.3 and 0.4), and three temperatures
1632
Fig. 14. Process ow diagram.
Table 4
Kinetic parameters considered in the model for the tar oxidation reactions.
Reactions
k0 (s 1)
E (kJ/mol)
Ref.
Tar oxidation reactions

C6H6 7.5 O2-6CO2 3H2O
C6H6 4.5 O2-6CO 3H2O
C7H8 3.5 O2-7CO 4H2
C10H8 5 O2-10CO4H2
9.55 108
1.35 109
2.08 109
2.07 104
1.25 102
1.25 102
1.65 102
80.2
[36]
[36]
[37]
[38]
Fig. 16. Syngas yield variations with temperature.
Fig. 15. Syngas yield variations with air equivalence ratio.
values 750, 800 and 850 1C, see Fig. 15. The yield showed high
signicant at peak at low temperature (750 1C) and ER (between
0.2 and 0.3). This is because of low oxygen rate supplied to the
unit. In another word, the complete combustion reaction is not
favored at these conditions. Moreover, at low temperatures, the
produced gas residence time is low, which means high conversion
of H2 and CO. However, the yield at (850 1C) had higher end value
(59.6%) than (800 1C) (58.6%), due to rate of endothermic reactions
increase at high temperatures.
Fig. 17. Gas composition as a function of operating temperature: validation of

experimental results and simulation predictions. Symbols: experiment (: CO, :
H2, : CO2, : CH4), simulation: lines.
Otherwise, the impact of the temperature on the yield of the

gas was examined for three equivalence ratios (0.2, 0.3 and 0.4), as
shown in Fig. 16. In case of high temperatures and ER equals to
0.3 and 0.4, the yield was decreased because of high oxygen
content, where the complete oxidation of char is favored to
Fig. 18. Gas composition as a function of ER: validation of experimental results and
simulation predictions. Symbols: experiment (: CO, : H2, : CO2, : CH4),
simulation: lines.
1633
produce CO2 than CO. Conversely, at equivalence ratio (0.2), more

syngas is predicted, where pyrolysis is the major controlling step.
Furthermore, endothermic Boudouard reaction is favored at low
oxygen rate, and more CO produced from CO2.
The experimental data at the Aristotle University pilot reactor
for olive kernel gasication was used to validate the model. Fig. 17
shows the gas composition for different temperatures and specic
air ratio (ER 0.2), whereas Fig. 18 depicts the dependence of gas
composition on different air ratios but one temperature
(T 750 1C) is xed. It can be observed that the model well tted
the experimental data, which had the same trends under various
operating conditions. The deviations (between 2.1% and 8%) was
explained by using a bed of olivine in the experimental work,
which act as a catalyst.
In addition, energetic assessment of the integrated system was
estimated through two indices: the cold gas (hcg) and thermal
efciency (ht), see Fig. 19. The two indices justied both experimental results and model predictions in Figs. 15 and 16. In Fig. 19,
the behavior of the system was explained by dening two vertical
axes, left axis denotes to the cold gas efciency and represented by
a straight line, while right axis denotes to the thermal efciency
and represented by a dashed line. Due to high temperatures and
high values of ER, both efciencies decreased in the same way as
the syngas yield showed previously in Figs. 15 and 16. This
decrease has a direct impact on gas low heating value (LHV) since
this parameter is proportional to the mole fractions of the syngas.
Nevertheless, the total output power that estimated by the model
was inaccurate. It may be attributed to the approximation of the
tar yield and composition by considering it as a mixture of
3 components.
5.2. Integrated atmospheric pressure solid oxide fuel cell (SOFC) with
biomass steam gasication process and combined heat and power
(CHP) system
Fig. 19. Cold gas and thermal efciencies.
Panopoulos et al. [39] investigated the integration of a near

atmospheric pressure solid oxide fuel cell (SOFC) with a novel
allothermal biomass steam gasication process together with a
combined heat and power (CHP) system of nominal output range
less than MWe by using Aspen Plus, Fig. 20. The developed steady
state model used thermodynamic equilibrium criteria for representing the process, where it was divided into four subsections:
gasication, heat pipes, gas cleaning and SOFC. The subsections
related to SOFC and heat pipe models were incorporated with
FORTRAN calculator block. This block was used for calculating the
electrical output power from SOFC, and to estimate: total thermal
Fig. 20. Aspen Plus biomass gasication modeling ow sheet.
1634
Fig. 21. Prediction of HCl concentration for different STBR.
better to run with STBR0.6 to get high production of gases and

excess of heat demand is not required.
Tar problems start when it condenses, hence the gas cleaning
stage was examined to ensure no lose in product gas sensible heat
and water vapor condensation, and no tar condensation in downstream equipment. Therefore, the dew point of tar was adopted to
be 523 K instead of 473 K (dew point temperature of presently
identied tar species), to guarantee that the process will be on the
safe side and to account the heavier tar species. Another reactor
model (REQUIL) was used to estimate the temperature at which
the impurities (HCl and H2S) reach their lower levels without
condensation of tar. This temperature was calculated according to
the equilibrium principles. This model also discussed the relation
between tar formation issues and the gas cleaning subsection. This
subsection favored lower water vapor (i.e. lower STBR, steam to
biomass ratio) and temperature to reach 1 ppm of HCl concentration, which can be done at 773 K even for high water vapor and
that means no tar condensation will occur, as represented in
Fig. 21. While for H2S removal, to reach less than 0.1 ppm requires
a temperature about 573 K for low STBR0.6, Fig. 22. As a result,
tar condensation can be avoided. For STBR 2 the cleaning process
have to be done at less than 523 K, which means some heavier tar
condensation might be predicted. Eventually, the model of gas
cleaning subsection failed to reach the required H2S without
concentration of tar condensation at low temperatures.
5.3. Biomass gasication fuel cell (BGFC) and biomass gasication
combined cycle (BGCC) systems
Fig. 22. Prediction of H2S concentration for different STBR.
resistance, temperature drop and heat transfer rate for heat pipes.
This facility of calculations in Aspen Plus is used whenever there is
need to calculate parameters that could not be possible to
calculate them by equations built in the simulator. However, the
most important subsection that should be reviewed is that related
to gasication since gasication is the process which concerned in
production of tar and syngases. In real gasication process,
thermodynamically unstable products such as tar might be
formed. The equilibrium models are not able to predict tar
formation. So, the model of gasication subsection used corrections apart from thermodynamic principles. This was done by
using a split stream that contains some of carbon, which is
considered one of the constituents of biomass, see Fig. 20. Moreover, tar amount was set in order to allow 15 g/m3n in dry basis
produced gas, where RSTOIC (Aspen Plus reactor model) was used
to represent tar formation. The tar value that selected previously
was according to the literatures of steam gasication experiments
with catalytic in situ FB (uidized bed) tar reduction [40]. The next
reactor model RYIELD, was used to convert the non-conventional
biomass to its elemental composition. The simulation started by
choosing the property estimation model in ASPEN PLUS, which
was the RedlichKwongSoave cubic equation of state method.
Later, tar was modeled as naphthalene because it is the most
stable compound in the biomass tar. The elemental composition
rather than tar and methane (CH4) was fed to RGIBSS reactor
model, where equilibrium calculations are done. In this subsection,
the parameter steam to biomass ratio (STBR) was studied. The
minimum STBR was thermodynamically estimated to be 0.4 and
this value was to guarantee the complete conversion of the carbon
into the gaseous products. It was suggested that the model was
In this study, two systems were under comprehensive investigation and comparison by Jhuma et al.: biomass gasication fuel
cell (BGFC) and biomass gasication combined cycle (BGCC)
systems [41]. This model compared the energetic and emissions
performance of the two systems. A detailed process simulation
was done by Aspen Plus in order to develop systematic site-wide
process integration strategies. For BGFC, Fig. 23, the tar in this
study (TARIN, as represented in Aspen ow sheet) was modeled as
phenol (the major constituent of tar) as revealed in numerous
studies [42,43], and it was fed into RGIBBS (the reactor model for
the uidized bed reactors). In another word, equilibrium model
was adopted instead of kinetic model. The stream of the tar which
enters the RGIBBS was taken from primary pyrolysis of a biomass
feedstock, as provided in Table 5a [44] and b [43]. The separation
of tar from syngas was done by ash separator (EFFLUSEP), where
the cooling was below its dew point, but nothing mentioned
which temperature was specied as a dew point temperature.
While for BGCC system, the simulation showed that upstream
processes (gasication, gas cooling and cleaning processes) were
identical to the BGFC system which means that tar representation
should also be the same, see Fig. 24. Unlike BGCC system, the BGFC
system implied a recycle stream (STGASIFY) which compensated
the reforming reactions of tar by the heat required for steam
gasication, while unreacted hydrogen and carbon monoxide in
this stream can guarantee the balance between endothermic
steam gasication and exothermic char combustion. This means
a neutral gasication process can occur.
Eventually, no specic formula of tar was adopted, but tar was
represented as a lump component. It was reported that the net
power generation of 601.89 kW and 295.60 kW for BGFC and BGCC
systems, respectively, indicates the powerful mechanism used in
BGFC system that implicitly included the effects of tar conversion
to syngas (reforming reactions) rather than BGCC system. While
for emission performance of a BGFC process in comparison with
BGCC process, the simulation of BGFC showed a result of less than
0.1 ppm by volume emissions such as H2S, COS, HCN, NH3, nickel
and iron carbonyls, mercaptans, naphthalene and organic
1635
Fig. 23. Simulation sheet in Aspen of material and heat integrated BGFC system.
Table 5
(a) Straw ultimate analysis in wt%; (b) composition of (gas, tar and char) after
primary pyrolysis or devolatilization.
wt%
(a)
C
H
N
O
S
Ash
Moisture
LHV (MJ/kg)
Component
(b)
Total devolatilization
Total gas
H2
CH4
C2
CO
CO2
H2O
Tar
Char
Straw
36.57
4.91
0.57
40.70
0.14
8.61
8.50
14.60
kg/kg biomass
0.9600
0.4760
0.0016
0.0241
0.1227
0.2164
0.0308
0.0804
Total devolatilizationtotal gas
1-Total devolatilization
sulphides, as for BGCC, the results was less than 1 ppm by volume
of emissions.
5.4. Biomass integrated gasication combined cycle (BIGCC)
technology
Another Biomass Integrated Gasication Combined Cycle
(BIGCC) technology is discussed, but this time by De Kam et al.
[45] who explained how to use this process in generation of process
heat and considerable amounts of electricity from dry-grind ethanol
facilities. The aim of this study was to estimate the renewable
energy ratio of ethanol production according to the new conguration of the system. The ethanol process co-products and other
biomass sources are utilized by this technology. An example of

these co-products is Distillers Dried Grains with Solubles (DDGS).
The DDGS is produced from mixing of two process streams:
Distillers Wet Grains (DWG) and concentrated distillers solubles
(also known as syrup), while the biomass sources is corn cobs.
The property analysis of this fuel is taken from Morey [46] and
derived from data of ve dry-grind ethanol plants. Table 6 shows
property data of the biomass used in this model [4648]. The
SilvaGas process was adopted for use in an ethanol plant which
consist of one gasier and one combustor. The representation of this
process in the Aspen Plus simulation was accomplished by using
equilibrium criteria instead of kinetic, as shown in Fig. 25. The
kinetic parameters of gasication reactions are still under investigation because of their detailed reaction mechanisms is complex [45].
Therefore, the two main equipment (gasier and combustor) were
modeled according to the Gibbs free energy minimization principles
and represented as the RGIBBS reactor model of the Aspen Plus
simulator. Tar was modeled as phenol and nothing mentioned
about the reactions that tar can undergo. Moreover, nothing
mentioned about the effects of representing the tar as phenol on
the process and on the nal products distribution. All the attention
was about how much heat and electricity were needed for such
process. Finally, it was suggested that this conguration showed a
high value (5.1) of the renewable energy ratio of ethanol production
rather than a value of (1.7).
5.5. Complete life cycle inventory of a biomass gasication integrated
with heat and power (CHP) plant
The rst detailed process simulation of wood gasication by
Francois et al. revealed a complete life cycle inventory of a
biomass gasication integrated with heat and power (CHP) plant
[49]. The model was able to predict:
Emissions (NOx, SOx, and aromatics).

Gasication products (water, permanent gases, inorganics,
particles and tars).
1636
Fig. 24. Simulation sheet in Aspen of material and heat integrated BGCC system.
Table 6
Property data of biomassa.
Moisture (wt%, wet)

HHV (dry, MJ/kg)
Ultimate (wt%, dry)
Carbon
Hydrogen
Nitrogen
Oxygen
Sulfur
Chlorine
Ash
DDGS
Syrup
Corn stover
Corn cobsb
10.1
21.75
66.8c
19.73
13.0d
17.93
13.0d
18.30e
50.15
6.87
4.78
33.36
0.77
0.18
3.89
42.97
7.04
2.62
39.07
0.96
0.35
6.99
45.44
5.52
0.69
41.49
0.04
0.1
6.72
46.58
5.87
0.47
45.46
0.01
0.21
1.4
Data adapted from Morey [46] unless otherwise noted.

Corn Cob data from Brown [47] unless otherwise noted.
Calculated from ARS Aspen Plus ethanol plant model.
d
Estimated moisture content necessary for storage.
e
Butuk and Morey [48].
b
c
Thermal and electrical efciencies.

Aspen Plus modules in combination with FORTRAN sub-models
and FORTRAN calculators were used to model this process. Kinetic
principles were adopted for char oxidation and pyrolysis secondary reactions of tar by using external FORTRAN subroutines, which
supply kinetic laws for these reactions. The composition of the
syngas was validated with experimental results of Tunzini Nesssi
Entreprises dEquipements (TNEE) process.
The property methods in this simulation were set as RK-Aspen
equation-of-state property model, which able to predict the
thermo-physical properties of hydrocarbon mixtures and light
gases (tar mixture properties can be estimated by this method)
[50]. The gasier in this simulation was modeled as three reaction
zones based on TNEE technology, as represented in Fig. 26 [51].
The three zones are wood gasication, wood pyrolysis and char
combustion.
The rst stage in the gasication is pyrolysis, as shown in
Fig. 27. The pyrolysis was represented as RYIELD block coupled
with FORTRAN sub-routine. This sub-routine includes empirical
correlations used in the pyrolysis module to estimate the gas
composition for a biomass which assumed to contain only C, H and
O [52]. At the outlet of the pyrolyzer, tar would be one of the
gaseous mixture components, which consist of benzene (C6H6),
phenol (C6H6O), toluene (C7H8) and naphthalene (C10H8). In
addition, non-condensable gases and light hydrocarbons could
be found at the outlet of the pyrolyzer. The modeling of tar as a

variety of hydrocarbons should improve the prediction of the dew
point temperature of heavy tars. Gas phase reactions of tar into
lighter hydrocarbons and catalytic cracking of tar (chars was
considered as a catalyst) occurred in the Freeboard section of the
gasier, which was modeled as RPLUG reactor model, Fig. 27.
Kinetic details of these reactions were included in this model [52].
Due to lack of information of exact tar composition after gasier,
especially class 4 and 5, and accurate measurement of tar composition for TNEE pilot plant is not available, pushed the author to
adjust the gasier outlet according to the tar composition of the
Gssing gasier, which composed of C6H6, C7H8 and C10H8 [53].
User blockFortran sub-routine was used after Freeboard block to
supply split fractions of C6H6, C7H8 and C10H8, where naphthalene
(C10H8) mass ow split in styrene (C8H8)class 3; in indene (C9H8),
acenaphtylene (C12H8), phenanthrene (C14H10p) and anthracene
(C14H10a)class 4; and in pyrene (C16H10)class 5, Fig. 27. The split
fractions are given in Appendix A (Fig. S1, Supplementary
materials). Table 7 shows wood and char characteristics and
correlations [52,54].
Tar sludge, which produced from water treatment unit, was
forwarded to the combustor, where its combustion in RSTOIC
block occurred, Fig. 27. The outlet gaseous from the combustor
were containing PAH, which is considered one of the tar constituent, and that consist of naphthalene, acephthylene, anthracene,
phenanthrene and pyrene. An assumption was set which implies
that 2% of PAH in the fuel are not burned.
The catalytic tar reformer was utilizing olivine as a catalyst and
represented as REQUIL reactor model, as shown in Fig. 28. The
steam reforming reactions of all hydrocarbons, water gas shift
reactions and ammonia decomposition were included in the
REQUIL. The model of the reformer was adopted from NREL
(National Renewable Energy Laboratory) model [55]. The purpose
of use of FORTRAN calculator was to control different component
conversion efciencies which are based on Devi empirical results
and tar conversion is one of them, see Table 8 [21,56,57]. Moreover, tar species absorption efciencies by water scrubber were
based on Rabou experimental results, as represented in Table 8
[55,5860]. The Aspen Plus module for the scrubber was modeled
as Flash2 block.
It was suggested that representing tar as a mixture of many
compounds, which belong to many different classes, enabled the
author to predict the total amount of tar produced from gasication (50 g/m3 on dry basis and normal condition), as shown in
Fig. 29. The tar prediction from the model revealed the consistency
1637
Fig. 25. Twin uidized bed steam gasication model in Aspen Plus.
Fig. 26. Scheme of the TNEE dual uidized bed gasier.
of the model results with TNEE plant (56 g/m3, including benzene). However, the assessment of the conventional gas cleaning
conguration (cyclone, bag lter, olivine catalytic tar reformer and
a water scrubber) showed a failure to reach appropriate dew point
of the tar to less than 35 1C instead of 70 1C. The 35 1C tar dew
point is one of the requirements of clean syngas to be used in IC
engine, according to the GEs Jenbacher recommendations [61].
The sensitivity analysis was not accomplished to see the response

of the model, especially the catalytic reactions of tar since these
reactions are sensitive of temperature, which was held constant
(900 1C) in the model of catalytic reformer. Moreover, gaseous
residence time (1.4) and temperature of the free board (960 1C) of
the gasier also xed, which they are considered the most
important parameters that could affect the kinetic of the tar.
1638
Fig. 27. Scheme of the gasication unit model.

Table 7
Properties of wood feedstock and char.
Moisture % on wet basis
Ash (%)
C (%)
H (%)
O (%)
N (%)
S (%)
Cl (%)
LHVanhy.
basis
(MJ/kg)
Wood
40
0.9
48.6
6.0
44.3
0.14
0.02
0.005
18.1
Char
5.3
88.7
1.0
4.7
0.26
0.05
0.008
31.3
Correlations for calculating the , , composition of char in Pyrolyzer [52], with T in K
C/100 2.4977.10 7 T2 0.000660002 T
H/100 1.6601.10 7 T2-4.0765.10 4 T 0.260630036
O/100 1 (C/100 H/100)
High heating value (HHV) and low heating value (LHV) of wood and char [54], with HHV and LHV in MJ/kg and Ash, C, H, O, N, S, mass fraction in %
HHV 0.3491 C 1.1783 H 0.1005 S-0.1034 O 0.0151 N 0.0211 Ash
LHV HHV 2.442 8.936 H/100
5.6. Pressurised steam/O2-blown uidized-BEd gasication for

biomass
Hannula and Kurkela developed a model of pressurised steam/
O2-blown uidized-bed gasication for wood as a biomass [62].
The modeling of catalytic reforming of hydrocarbons and tar formation
was done by Aspen Plus simulation software, where the main gases
composition predicted. Moreover, a parametric study submitted in
order to study the main parameters affecting the gasication.
The two main blocks of this model (block 5 and 9) are mainly
based on equilibrium criteria (RGIBBS represents these blocks), as
shown in Fig. 30. In another words, they are based on the
minimization of Gibbs-free energy. Other blocks were simulated
far from equilibrium, but not kinetic, using conversion correlations
as in Table 9.
The model calculated tar conversion, which was modeled as
naphthalene (C10H8), and other hydrocarbons conversions (CH4,
C2H2, C2H4, C2H6, C3H8, and C6H6) in block 4 (RSTOIC) from the
experimental data. Table 9 shows the conversion equations for the
hydrocarbons as a function of temperature of the freeboard. This
temperature has a strong relation with the total tar concentration.

Moreover, these equations were included in FORTRAN subroutine for
calculations purposes. The tar and the hydrocarbons were considered
inert compounds in block 5 (equilibrium block) in order to prevent
their decomposition.
The model validated with experimental data and showed a
reasonably agreement for the main gases composition H2, CO, CO2
and H2O with average error about 12%. Later, in parametric
analysis, it was suggested that the syngas efciency increases
from 70 to 78% due to high conversion in the reformer and
ltration temperature. In addition, the temperature impact of the
reformer on the conversion at 950 1C instead of 850 1C causes the
decrease of syngas efciency by 2%. Another important parameter
is the moisture content of the fuel, 9% increase in the efciency
when drying occurred from 50% to 10 wt%.
5.7. Staged-gasication system
A new system of staged-gasication based on a uidized-bed
design presented by Nilsson et al. [63]. This system consists of
1639
Fig. 28. Scheme of the syngas cleaning unit model.

Table 8
Cleaning equipment modules and their operating conditions, efciencies and correlations.
Temperature (1C)
Pressure drop (kPa)
Efciencies (% on weight basis)
Particles
d o 5 mm
5 od o 20 mm
d 420 mm
Light hydrocarbons
CH4
C2H4
C2H6
Tars
Unclass C6H6
Class 2 C6H6O
Class 3 C7H8, C8H8
Class 4 C9H8,C10H8,C12H8,C14H10
Class 5 C16H10
Impurities
NH3
H2S
H2S
Cyclone
Catalytic tar reformer
Bag lter
Wet scrubber
960
0.5 [59]
960840
0.2 [55]
120
1.5 [59]
12030
0.6 [59]
5080 [59]
8095 [59]
9599 [59]
80 [60]
80 [60]
80 [60]
100
100
100
20 [55]
50 [55]
90 [55]
89.4 [56,57]
100 [56,57]
93.6 [56,57]
85.1 [56,57]
99.9 [56,57]
25 [60]
25 [60]
35
72
28
69
50
70 [55]
99a
1.7a
100a
[58]
[58]
[58]
[58]
[58]
Efciencies are dened as follow, where m_ C H is the mass ow stream in kg/s of the CxHy component
X %
Cx Hy Cx Hy
100
Cx Hy
Reforming reactions implemented in the catalytic tar reformer [55]

Steam reforming: Cx Hy xH2 O-xCO x y=2 H2
NH3 -1=2N2 3=2H2
Water gas shift: CO H2 O-CO2 H 2
Water scrubber efciencies for NH3, HCl and H2S are calculated from ELECNRTL property model in Aspen.
three stages: devolatilization of the fuel, homogeneous gas

reforming/oxidation of volatiles and heterogeneous reforming
reactions of gas over in situ generated char. Kinetic approach
was used to model each stage. The data required for the kinetic
model was obtained either from experiments by using laboratoryscale uidized bed reactor or taken from literatures. The model
predicted the performance of the new system for gasication of

Dried Sewage Sludge (DSS). The main parameters that studied in
this model: The equivalence ratio (ER), steam to oxygen ratio
(SOR) and reactor temperature.
The model was divided into four sub-models: uidized bed
devolatilizer (FBD), seal (LS), non-catalytic gas reformer (NCGR)
1640
Table 9
Conversion equations used to model the non-equilibrium criteria.
Conversions related to gasication
Carbon
CH4
C2H2
C2H4
C2H6
C3H8
C6H6
C10H8
NH3
Conversions related to reforming
CH4
C2H2
C2H4
C2H6
C3H3
C6H6
C10H3
NH3
0:0155 nG 86:068 %
0:003 nG 7:074 mol=kg
0:00004 nG 0:06454 mol=kg
0:002 nG 2:987 mol=kg
0:001 nG 1:196 mol=kg
0:000155 nG 0:150921 mol=kg
0:27 mol=kg
0:3 mol=kg
0:04154 mol=kg
0:2247nR 127:36 %
0:8439nR 634:66 %
0:3818nR 237:31 %
0:2753nR 143:5 %
100 %
0:1875nR 76:532 %
94.6 %
1:0679nR 899:25 %
G Gasier freeboard temperature [1C]

R Reformer outlet temperature [1C]
Fig. 29. Composition of raw syngas according to (a) permanent gases on wet basis,
and (b) contaminants.
same paper. The yield distribution for this process consist of tar,
which was represented as toluene (C7H8), and called a light tar in
order to distinguish it from the heavy tar which is a product of
secondary tar reactions. Tar yield was calculated in order to fulll
the carbon and hydrogen balances. The oxidation of tar (toluene,
R8-Table 10) was among many oxidation reactions which was
modeled as a RPLUG (Aspen Plus reactor model) in the sub model
(NCGR) [64]. Its conversion reactions were considered a homogenous by using high temperature and heterogeneous by using
char as a catalyst. For the homogenous reactions, two sequential
reactions were adopted for the tar reactions:
Cracking of light tar into heavy tar and light gas (R10-Table 10)
[27].
Reforming of heavy tar into light gas and coke (R11-Table 10)
[27].
Fig. 30. Scheme of the model.
Both reactions were represented as RPLUG, and for the reforming reactions were being found in both sub-models (FBD and
NCGR). The other tar conversion reaction was also modeled as
RPLUG reactor model, where reforming reaction may occur over a
bed of char (R12Table 10) [65], and this reaction was a part of CR
sub-model.
According to the tar content in the produced gas, the model
revealed a good estimation of both light and heavy tar, as
represented in Fig. 32. Their reduction or conversion was correlated with temperature and catalyst existing in each part of the
above mentioned sub-models. In addition, the results showed that
the impact of the temperature of less than 900 1C would not affect
the reforming of tar inside the gasier. This is due to the
temperature decreased during the increasing of the steam to
oxygen ratio, so reforming of tar was reduced, which elevated
the concentration of tar in the produced gas. In conclusion, more
steam added to the gasication is not favored because of the tar
reforming reaction is not enhanced.
5.8. Different systems and different tar representation
and char converter (CR), Fig. 31. In the rst sub-model (FBD), as
shown in Fig. 31, the RYIELD Aspen Plus block reactor model in this
paper modeled the devolatilization process by using a calculator
block. This calculator was considered to be the way to estimate the
yield of the devolatilization as a function of the FBD temperature
by using experimental correlations, which were mentioned in the
Other papers are found in the literatures but they do not

mention which reactor block model was used by Aspen Plus to
simulate the biomass tar reactions or what compound was chosen
to represent the tar. These papers were prepared by Nagel [66],
Heijden [67] and Murakami [68].
1641
Fig. 31. Scheme of the three-stage gasication model.
Table 10
Different tar reforming reactions considered in the model and related stoichiometry and kinetic expressions.
Reaction
Stoichiometry
Kinetic expression
Reference
R8
C7 H8 5:5 O2 - 4H2 O 7 CO
r R8 kR8 C 0:5
C 7 H 8 C O2
[64]
R10
3C7 H8 H2 -C10 H8 3CH4 C 2 H6 6C
r R10 kR10 C C7 H8 C 0:5

H2
[27]
R11
C10 H8 2H2 O - 3CH4 2 CO 5C
0:5
r R11 kR11 C 1:6
C10 H8 C H2
[27]
R12
C10 H8 10H2 O - 10CO 14H2
r R12 kR12 C C10 H8
[65]
Fig. 33. Gasication plant in Aspen Plus.

Fig. 32. Gas content of light and heavy tar: at the exit of the devolatilizer (FBD), gas
reformer (NCGR) and char converter (CR).
Anisole denotes tar originating from the thermal decomposiIn a paper that done by Nagel et al., the gas processing of the
Biomass-Integrated gasication fuel cell systems (B-IGFC) was modeled
by using Aspen Plus and tar was represented as a variety of different
components. These components were reduced to three species:
Acetic acid is the tar originating from thermal decomposition of

cellulose and hemicellulose.
tion of lignin such as m-cresol and syringol [69].
Toluene refers to tar formed in the secondary tar reactions such

as xylene and naphthalene. The steam reforming reactions
(STR) for these compounds are as follows:
C2 H4 2H2 O-2CO 4H2
18
C7 H8 7H2 O-7CO 11H2
19
1642
Table 11
Pyrolysis of fuel at 1073 K in a steam-blown uidized bed and expected C and H conversions, product distribution and composition at the end
of the process.
Conversion to gas (%)
C: 63.0, H: 88.7
Product distribution (wt%)a

Molar composition (vol%) (free of tracer gas)
Char composition (wt%)b
Tar composition (wt%)c
Gas: 75, Char: 22.1, Tars: 2.9

19:3H2 38:2CO 9:5CO2 17:5CH4 9:9C2 H4 5:2C2 H6 0:4C3 H6
63:82C 0:0H 11:57N 14:33O 0:003S 0:36Cl 9:90ash
64:40C 6:23H 11:10N 15:10O 3:01S 0:11Cl 9:90ash
a
b
c
The fraction of tars was from pilot gasication test.

Derived from element mass balance.
From measuring the tar sample taken in pilot gasication test.
Fig. 34. Reactions considered in the model.
C2 H4 O2 -2CO 2H2
20
C7 H8 6H2 O-7CO 10H2
21
No specic kinetic models were found for the STR of these

compounds, instead the power law type kinetic model of Achenbach was assumed [70], and represented by the following equation:

82; 000 J=mol
r Cx HY STR f act U 4274:0 mol=m2 =s=bar U pCx HY U exp
R U TsK
22
with CxHy C2H4, C7H8, C7H8O and C2H4O2 and f act 2.5, 1.5, 1.75
and 2.0.
In addition, no Aspen Plus reactor model was specied for the
reforming reaction of the tar. The air to fuel ratio was a studied as a
parameter, by which keeping the temperature of the cell at its
value when reforming reactions potential decreased. It was concluded that cell design can t with variable temperature, gas
composition.
Murakami et al. revealed in his paper substantial engineering
fundamentals relative to chemical reactions and heat/mass balances
for the development of a bubbling uidized bed (BFB) biomass gasier
coupled to a pneumatic transported riser (PTR) char combustor. First, a
batch uidized bed experiment was conducted to estimate C and H
conversion, products characteristic and gas composition. These data
were the input of the simulation that done by ASPEN PLUS. In this
simulation also no specic ASPEN PLUSs reactor block models were
mentioned such as the type of the reactors (RYIELD, RGIBBS or others),
but just a sketch demonstrated the simulated process, Fig. 33. In
addition, tar was not represented by any previous models mentioned
above. The tar composition was based on elemental analysis of the
product tar from a pilot plant, Table 11.
Tar reforming reaction was also considered, as shown in Fig. 34,
and the necessary tar formation enthalpy was roughly calculated
according to the tar elemental analysis. The model predicted that
all tar generated in fuel pyrolysis was transformed via reforming

reaction, and this was one of the reasons that kept the dual
uidized bed working with cold gas efciency higher than 75% and
temperature of 1073 K.
Heijden and Ptasinski presented an exergy analysis for thermochemical ethanol production from biomass. The exergy analysis
was tested against different types of ethanol catalysts such as Rhbased and MoS2-based (target) and different gasication temperatures. This process was modeled according to thermodynamic
principles. In his paper, tar reforming process was also included
but without specifying any formula for the tar and nothing
mentioned about its reactions as was done in other papers. The
tar was modeled based on assumed conversion. Moreover, no clear
representation for the tar reforming process in Aspen Plus has
been found. In another word, the ASPEN PLUSs reactor models
(RYIELD, RGIBBS, RPLUG and others) are not exactly explained and
how they represent the reforming process. Related to the reforming reactions, it was predicted that low mass owrate of steam was
needed with MoS2-based catalyst (target) rather than Rh-based,
because the former needs a ratio of H2/CO (1.2) while the latter
needs (2.0). The performance of the reformer was related to the
gasication temperature, when an increase in the temperature
corresponds to high steam is required. Thus MoS2-based catalyst
showed high exergetic efciency (44.4%) than Rh-based catalyst
with value of (43.5%).
6. Conclusions
1- Most of papers that reviewed modeled gasier by using
(RGIBBS reactor model), where calculations are done according
to the minimization of Gibbs free energy, assuming complete
conversion of char, and hydrocarbons formation such as tar
cannot predicted by equilibrium models. Representing pyrolysis or gasication reactions according to thermodynamic equilibrium need to be reviewed again since this principle does not
contribute in reactor design. However, some correlations used
together with equilibrium models to predict char and tar
formation, but still valid to specic conditions under which
the correlation was established. So, it is suggested to use kinetic
for both char reactivity and reforming or oxidations reactions of
tar, where more syngas produced especially for tar reactions
and eventually the efciency of the desired process shall give
accurate results. In addition, kinetic reactor models is advised
to be used such as (RPLUG and RCSTR) in order to improve the
predictions.
2- The strength of this software in modeling of gasication and
pyrolysis is lied in existing of FORTRAN calculator block and
FORTRAN subroutine, where complex kinetic issues and design
specication can be programmed and compiled using FORTRAN
programming language. However, there are some weakness in
using this software especially hydrodynamic problems that
cannot be modeled, and kinetic related reactor blocks (RPLUG

and RCSTR) are based on ideal mixing behavior.
3- Tar is a complex mixture of many components and its removal
is one of the most important factors that employed in assessing
of gasication process besides reforming processes and pyrolysis. The approximation of tar as a narrow range of components leads to inaccurate results since tar represents a wide
range of hydrocarbons. The use of wide variety of tar components in any model would accurately estimate the efciency of
that process and the possibility to predict the tar dew point
temperature. This temperature is considered to be another
important factor that leads to estimate the condensation of
tar and eventually to avoid formation of tar in downstream
facilities
Appendix A. Supplementary information

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.rser.2015.07.125.
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Review of Kinetic and Equilibrium Concepts For Biomass Tar Modeling by Using Aspen Plus

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Renewable and Sustainable Energy Reviews 52 (2015) 16231644

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Review of kinetic and equilibrium concepts for biomass tar modeling

Corresponding author. Tel.: 60 3 89466297; fax: 60 3 86567120.

atoms of C in light hydrocarbon

a, b, c, d chemical potential of components a, b, c, d

The continual increase of energy demand and the impact of fossil

Preheating and drying

nitially, gasication begins with drying step in order to remove the

Moving-bed reactor: The simple type that explains this kind of

Fig. 1. Potential paths for gasication.

and combustion products ow downward, and the hot gases also

Fluidized-bed reactor: In a bubbling uidized bed, the solid fuel

C CO222CO 172 kJ/mola

C O2-CO2 394 kJ/mol

3. Principles of chemical equilibrium and kinetic

In Gibbs energy of a reaction equation, each reactant multiplied

Fig. 2. Gasication reactions illustrated in stages in an updraft gasier.

Fig. 3. Downdraft gasier and gasication reactions.

again, means products decomposition occur [11]. At rG0 (the point

From Eq. (3) two independent variables are seen; T is the

The measuring units of k are always used as a conversion factor

dm = mol= s  mol=dm  mol=dm mol =dm = s

Fig. 8. Reaction tendency related to rG.

Fig. 6. Variation of Gibbs energy of a reaction mixture during reaction course.

Fig. 7. Variation of Gibbs energy at a specic composition of the system.

Fig. 9. Arrhenius plot.

The temperature-dependent term or the reaction rate constant

analysis of tar and also gases are the predominant product of

The parameters of Arrhenius law are k0 and E which represent

This expression is normally written as the Arrhenius equation:

Since the rate shows dependence on the temperature, so we

4.1. Tar denition

-HCN NH3 HCl H2 S other sulfur gas

Biomass gasication mainly produces different products: gases,

In Eq. (12), many different products from biomass gasication

Fig. 10. Tar compounds transformation scheme proposed by Elliott.

Very heavy tars, cannot be detected by GC

Determined by subtracting the GC-detectable tar fraction from the

composition of biomass pyrolysis products and gasier tar from

aromatic hydrocarbons. Although the lower molecular weight

4.2. Tar composition

4.3. Sampling and characterization of tar

4.3.1. Tar sampling

Fig. 11. Tar sampling and analysis procedure.

Fig. 12. Tar sampling unit.

Fig. 13. Characterisation and analysis of tars.

4.3.2. Characterization of tar

4.4. Tar reaction mechanism and kinetic

Carbonformation : Cn Hx -nC x=2H2

where Cn Hx and Cm Hy stand for tar and hydrocarbon with smaller

5. Aspen Plus tar models

Rigorous Electrolyte Simulation.

Aspen Plus has been used in different aspects of modeling such

Fig. 14. Process ow diagram.

Tar oxidation reactions

Fig. 16. Syngas yield variations with temperature.

Fig. 15. Syngas yield variations with air equivalence ratio.

Fig. 17. Gas composition as a function of operating temperature: validation of

Otherwise, the impact of the temperature on the yield of the

produce CO2 than CO. Conversely, at equivalence ratio (0.2), more

Fig. 19. Cold gas and thermal efciencies.

dm = mol= s mol=dm mol=dm mol =dm = s