Product characterization of fast

pyrolysis of dry distillers grains with

solubles and palm kernel cake using a
heated grid reactor
Nitrogen chemistry and reactor modeling
MSc Thesis
Report number 2404
Delft University of Technology
Faculty of Mechanical, Maritime and Materials Engineering (3mE)
Energy Technology
J. Gout
May 17, 2010
Professor Prof. dr. ir. A.H.M. Verkooijen
Supervisor Dr.ir. W. de Jong
Daily supervisor J. Giuntoli, MSc
Summary
Due to climate change, dependence on fossil fuels, growing imports and rising
energy costs, the importance of renewable energy sources in Europe is contin-
uously growing. The use of biomass is one of the ways to increase the share
of renewable sources, since biomass can be used for heat and power production
and the production of transport fuels. Biomass can be converted directly into
power and heat by thermal conversion, or indirectly by converting it to gaseous
or liquid fuel. In all of these processes, pyrolysis plays an important role. Py-
rolysis or devolatilization is the process in which organic materials are heated
in an inert atmosphere to produce organic condensable vapors, gases and char-
coal. The organic vapors can be condensed to produce pyrolysis oil that can
be further upgraded to transportation fuels. Also in the combustion process,
pyrolysis is the rst step in the release of volatiles. This step accounts for up to
95% of the weight loss during combustion of biomass[1].
The purpose of this study is to gain more insight into the pyrolysis behavior
of DDGS and PKC under fast heating rate conditions relevant to industrial
applications like gasication. The aspects that are investigated are the volatile
yields and composition, mainly focusing on NO
x
precursors like NH
3
and HCN.
For this purpose, the measurements were carried out on an experimental setup
previously described and used by Di Nola [1] and Tamboer[2]. The parameters
that were varied are temperature, heating rate and holding time. Also, the eect
of leaching in water on the pyrolysis behavior of biomass is addressed. Because
the possibilities for monitoring the reactor temperatures are limited, a CFD
model was made. This model can provide a better insight in the phenomena
concerning heat transfer and uid ow within the reactor.
The parameters that were varied during the experiments are peak temper-
ature, heating rate and holding time. The temperatures were varied between
500 and 1300

C, for the heating rate, 600 and 1000K/s were chosen. Finally,
the holding time was varied from 5 to 15 seconds.
Non-contact measurements using a pyrometer showed that the actual grid
temperature is signicantly higher than indicated by the thermocouple. A rela-
tion between these temperatures was presented.
From the modeling it was concluded that there are not hot spots in the
reactor other than surrounding the grid. Also, the gradient of the temperature is
limited in the center of the grid, but substantial towards the electrodes. Finally,
in a rst approximation of the thermal history of the sample appeared to dier
signicantly from that of the grid.
In the experimental section the issue of temperature dierence between the
grid and thermocouple was taken into account. The results show that the be-
havior of both potential fuels have a similar behavior in terms of weight loss
1
and volatile product composition as a function of temperature. The leaching
in water does not signicantly inuence the weight loss and volatile product
composition as a function of temperature. When comparing with low heating
rate experiments performed by Giuntoli et al.[3], the yields dier signicantly
for the species CO
2
, H
2
O, NH
3
and HCN.
The main NO
x
precursor found in this study was HCN, while no HNCO was
found. In PKC, NH
3
was found in quantities that were too small to quantify.
The yields of both NH
3
and HCN were found to increase with temperature.
The lower yields in NO
x
precursors compared to low heating rate pyrolysis is
suggested to be caused by the reduced hydrogenation of char-N.
For future work on the presented CFD model, it is recommended to improve
the model by including relations for the thermal behavior of the pyrolysis sam-
ple. Also, the release of volatile species could be incorporated in the model to
provide a better insight in the mixing behavior and possible secondary reactions.
On the experimental part, it is recommended to quantify the amount of
adsorbed NH
3
and investigate whether other components such as H
2
O and HCN
might also adsorb. On the temperature, it is recommended to use the following
relation to predict the actual grid temperature: T
Grid
1.15 T
Thermocouple
Finally, to reduce the dierence in temperature between the sample and the
grid, thinner samples should be used.
2
Acknowledgements
Hereby I want to thank the people that supported me during this nal project.
First of all Jacopo, my daily supervisor. From the start on the experiments to
the writing of my report, you have been very helpful in guiding me and giving
me useful feedback. Duco Bosma I want to thank for helping me to get familiar
with the heated grid setup. I also would like to thank my supervisor Wiebren for
the useful feedback during our progress meetings and o course Prof. Verkooijen
for giving useful comments on my work.
O course I also want to thank my colleague students in the department
that were working on their (nal) project during my nal project. I had a good
time enjoying your company during lunch and coee breaks.
Jeroen Gout
3
Nomenclature
Symbols
a Speed of sound [m/s]
A
n
Frequency factor for species n [s
1
]
C Concentration [ppm] or [kg m
3
]
C
p
Heat capacity [kJ kg
1
K
1
]
d Sample diameter [mm]
D
AB
Binary diusion coecient [m
2
s
1
]
D
e
Eective diusivity [m
2
s
1
]
H Heat of reaction [J kg
1
]
E
n
Activation energy for species n [J mol
1
]
F Body force vector [N m
3
]
I Identity matrix [-]
J External current density [A m
2
]
k Thermal conductivity [W m
1
K
1
]
k
n
Reaction constant for species n [s
1
]
m Weight [mg]
Ma Mach number [-]
n Normal vector [-]
p pressure [Pa]
Q Heat production W m
3
Q
j
Current source [A m
3
q
s
Production/absorption coecient [W m
3
s
1
]
r Particle radius [m]
t Time [s]
T Temperature [K] or [

C]
t
s
Sample thickness [mm]
u Velocity vector [m s
1
]
u Velocity in x-direction [m s
1
]
v Velocity in y-direction [m s
1
]
V Electric potential [V]
w Velocity in z-direction [m s
1
]
4
Greek symbols
Thermal expansion coecient [T
1
]
Ratio of specic heats [-]
Emissivity [-]
Dynamic viscosity [Pa s]
Dilatational viscosity [Pa s]
Density [kg m
3
]

c
Restriction factor [-]

e
Electric conductivity [S m
1
]
Tortuosity [-]

p
Pellet porosity [-]
Subscript
amb ambient
a.r. As received basis
d.b. Dry basis
d.a.f. Dry and ash free basis
d Down
u Up
Constants
g Gravitational acceleration 9.81 [m s
1
]
R Universal gas constant 8.314 [J K
1
mol
1
]
Stefan-Boltzmann constant 5.6704 [W m
2
K
4
]
5
Abbreviations
CFD Computational uid dynamics
DDGS Dry distillers grains with solubles
DKP Diketopiperazine
FTIR Fourier transform infrared spectrometer
HHV Higher heating value
HR Heating rate
HT Holding time
PKC Palm kernel cake
PKE Palm kernel expeller
6
Contents
1 Introduction 11
1.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.2 Biomass residues . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.1 DDGS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.2 PKC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3 NO
x
emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.4 Literature on nitrogen in biomass . . . . . . . . . . . . . . . . . . 16
1.5 Leaching in water . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.6 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.7 Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2 Experimental setup 22
2.1 Literature review on fast pyrolysis equipment . . . . . . . . . . . 22
2.2 Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.1 Pyrometer . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3 Experimental procedure . . . . . . . . . . . . . . . . . . . . . . . 26
2.3.1 Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3.2 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3.3 Running the experiments . . . . . . . . . . . . . . . . . . 27
2.3.4 FTIR sampling . . . . . . . . . . . . . . . . . . . . . . . . 27
2.4 Experimental considerations . . . . . . . . . . . . . . . . . . . . . 28
2.5 Setup improvements . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.6 Discussion and conclusions . . . . . . . . . . . . . . . . . . . . . . 34
2.6.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3 Modeling 35
3.1 Model dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2 Heat transfer modeling . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2.1 Subdomain equations . . . . . . . . . . . . . . . . . . . . 38
3.2.2 Boundary equations . . . . . . . . . . . . . . . . . . . . . 39
3.3 Conductive media modeling . . . . . . . . . . . . . . . . . . . . . 39
3.3.1 Subdomain equations . . . . . . . . . . . . . . . . . . . . 39
3.3.2 Boundary equations . . . . . . . . . . . . . . . . . . . . . 40
3.4 Weakly compressible Navier Stokes modeling . . . . . . . . . . . 40
3.4.1 Subdomain equations . . . . . . . . . . . . . . . . . . . . 40
3.4.2 Boundary equations . . . . . . . . . . . . . . . . . . . . . 41
3.5 Mesh properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.6 Results & validation . . . . . . . . . . . . . . . . . . . . . . . . . 43
7
3.6.1 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.6.2 Validation . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.7 Biomass temperature modeling . . . . . . . . . . . . . . . . . . . 53
3.8 Release of volatiles . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.9 Discussion and conclusions . . . . . . . . . . . . . . . . . . . . . . 57
3.9.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4 Experimental results 59
4.1 Analyzing the results . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.2 The inuence of the nal temperature . . . . . . . . . . . . . . . 59
4.2.1 Weight loss . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.2.2 Slow vs. fast pyrolysis . . . . . . . . . . . . . . . . . . . . 61
4.2.3 Nitrogen species . . . . . . . . . . . . . . . . . . . . . . . 62
4.2.4 H
2
O, CO, CO2 and CH4 . . . . . . . . . . . . . . . . . . 65
4.2.5 Partitioning . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3 The inuence of the holding time and heating rate . . . . . . . . 69
4.4 Discussion & conclusions . . . . . . . . . . . . . . . . . . . . . . . 72
4.4.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5 Conclusions and recommendations 74
5.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
5.2 Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Appendices 82
A Biomass properties 83
B Quantication method 86
C Reactor dimensions 98
D Model settings 102
D.1 Mesh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
D.2 Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
D.3 Scalar expressions . . . . . . . . . . . . . . . . . . . . . . . . . . 104
D.4 General heat transfer . . . . . . . . . . . . . . . . . . . . . . . . . 104
D.4.1 Subdomain . . . . . . . . . . . . . . . . . . . . . . . . . . 104
D.4.2 Boundary settings . . . . . . . . . . . . . . . . . . . . . . 104
D.5 Conductive media . . . . . . . . . . . . . . . . . . . . . . . . . . 105
D.5.1 Subdomain settings . . . . . . . . . . . . . . . . . . . . . 105
D.5.2 Boundary settings . . . . . . . . . . . . . . . . . . . . . . 105
D.6 Weakly compressible Navier Stokes . . . . . . . . . . . . . . . . . 105
D.6.1 Subdomain settings . . . . . . . . . . . . . . . . . . . . . 105
D.6.2 Boundary settings . . . . . . . . . . . . . . . . . . . . . . 105
D.7 Solver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
D.7.1 Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . 105
D.7.2 Manager . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
8
E Devolatilization results 109
E.1 Inuence of the nal temperature . . . . . . . . . . . . . . . . . . 109
E.2 Inuence of the holding time . . . . . . . . . . . . . . . . . . . . 111
E.3 Inuence of the heating rate . . . . . . . . . . . . . . . . . . . . . 115
9
Chapter 1
Introduction
1.1 Background
Due to climate change, dependence on fossil fuels, growing imports and rising
energy costs, the importance of renewable energy sources in Europe is contin-
uously growing. Already in 1997 the European Union set a target for 12%
renewable energy in gross inland consumption to be achieved 2010[4], however,
this target was unfortunately not met. The current suggested target is set
to 20% renewable energy by 2020. This target is also adopted by the Dutch
government[5].
The use of biomass is one of the ways to increase the share of renewable
sources, since biomass can be used for heat and power production and the pro-
duction of transport fuels. According to the Platform Biobased Raw Materials,
30% of fossil raw materials in the Netherlands could be replaced by biobased
materials in 2030[6]. This will require a replacement of 60% of transportation
fuels, 20% of production of chemicals materials, 17% of heat production and
25% of electricity production.
Biomass can be converted directly into power and heat by thermal conver-
sion, or indirectly by converting it to gaseous or liquid fuel. In all of these
processes, pyrolysis plays an important role. Pyrolysis or devolatilization is the
process in which organic materials are heated in an inert atmosphere to produce
organic condensable vapors, gases and charcoal. The organic vapors can be con-
densed to produce pyrolysis oil that can be further upgraded to transportation
fuels. Also in the combustion process, pyrolysis is the rst step in the release of
volatiles. This step accounts for up to 95% of the weight loss during combustion
of biomass[1].
There are, however, some drawbacks for biomass. Unlike coal, which has
been studied extensively for already quite some time[7], the thermal behavior
of biomass has only been under investigation for a comparatively short time.
Also, because of the diversity of available biomass, the dierence in composition
between the dierent types of biomass is very large. One of the compounds
that can vary in amount between dierent types of biomass, is nitrogen. This
compound can be found in amounts of less than 1% up to about 10 wt% on dry
and ash free basis[1]. The problem of this fuel bound nitrogen is that it causes
the formation of the harmful NO
x
emissions. Since the amount and origin of
11
nitrogen in biomass diers signicantly, it is dicult to predict the amount of
NO
x
and N
2
O emissions in combustion processes. Besides the nitrogen, biomass
also contains signicant amounts of alkalis like potassium, sodium, chloride and
sulfur, which can cause fouling and slagging as well as corrosion of thermal
conversion equipment[8].
To overcome the issues raised in the previous paragraph, research on the the
pyrolysis of biofuels is necessary since this is the rst step in the combustion
process. In this work, the product yields and composition of volatiles released
during pyrolysis for two types of biomass were investigated as a function of
temperature, heating rate and holding time. The obtained results can provide
a better understanding of the thermo-chemical conversion, which can be used
to design processes involving pyrolysis, gasication or combustion.
1.2 Biomass residues
Biomass can generally be divided into four dierent classes[1]:
Wood and woody materials
Herbaceous and other annual growth crops (e.g. straw, grasses)
Agricultural by-products and residues (e.g. shells, hulls, pits and animal
wastes)
Refuse-derived fuels (RDF) and non-recyclable papers, often mixed with
plastics
In this study the focus is on agricultural by-products, namely dry distillers
grains and solubles (DDGS) and palm kernel cake (PKC). They are by-products
from bio-ethanol production from corn and the production of palm oil, respec-
tively. Bio-ethanol is a rst generation biofuel, since it competes with food
production. By using DDGS as a fuel, the eciency of energy conversion from
corn can be improved. Palm oil can be either used in food or a basis for biodiesel.
Both types of biomass residues have become widely available, since they are be-
ing produced on a large scale with production still increasing (see gure 1.1).
They are currently used as animal feed because of their nutritional value and
considerable protein content. Only recently, these types of biomass are being
considered as potential fuels[9, 3, 10], so the knowledge on pyrolysis behavior is
limited.
1.2.1 DDGS
DDGS are a byproduct of dry grindethanol production from corn. This process
accounts for 67% of the production of ethanol from corn. In this process, clean
corn is mixed with water to form a mash. The mash is cooked and enzymes
are added to convert starch into sugar. The next step is the addition of yeast
to ferment the sugars, producing a mixture containing ethanol and solids. This
mixture is distilled and dehydrated to produce fuel-grade ethanol. The solids
remaining after distillation are dried to produce DDGS [13].
One of the possible uses of DDGS is to use it as a biofuel in ethanol plants,
serving as an alternative for natural gas or coal. Tiany et al.[9] made an
12
(a) Palm oil production[11] (b) Ethanol co-product production[12]
Figure 1.1: Historic production data on palm oil and ethanol residues
economic model for the use of DDGS in 50 and 100 million gallons/year ethanol
production plants. From this modeling, it appears that the energy content of
DDGS is such that it can supply both the process heat and electricity needed for
ethanol production, while an energy surplus is available for power generation
for sale to the grid. When gasifying DDGS, the renewable energy ratio of
ethanol production in these plants can be increased from 1.5 to 3.8 (dened
as (Energy in ethanol + co-product energy + electricity to grid energy)/ fossil
energy input)[14]. Also, the well-to-wheel greenhouse gas emissions for ethanol
compared to gasoline can be reduced by 39% (from 100,000 to 60,000 CO
2
-
equivalent grams per million Btu of fuel produced and used)[15] while using
DDGS for powering the ethanol production.
It is expected that with the increasing ethanol production, the amount of
DDGS produced will exceed the demand from the market. This is partly caused
by the fact that the amount of DDGS that can be fed to some types of cattle
is limited. This is caused by a form of fat present in DDGS, of which certain
types of livestock (dairy cows, swine and poultry) can only receive a limited
daily intake[9]. The saturation of the DDGS market for cattle feed will lower
the DDGS prices, favoring the use of DDGS as a fuel. For the base case in the
work of Tiany et al., already the rate of return for a biomass powered ethanol
production plant is higher than for a conventional one.
13
1.2.2 PKC
Palm kernel cake (PKC), also called palm kernel expeller (PKE), is a by-product
from mechanical palm oil production. This process consists of six unit pro-
cesses:(1) fruit bunch sterilization,(2) bunch threshing,(3) fruit digestion,(4)
pressing,(5) clarication and centrifugation and (6) nut drying, cracking, and
kernel recovery[16]. Most of the worlds palm oil is produced in Malaysia and
Indonesia. In 2006 their combined production amounted to 31.8 million tons
of palm oil, 87% of the world production[11]. For every ton of oil palm fruit
bunch that is put into the oil rening process, 0.012 tons of kernel are produced
as solid waste[10]. Just like DDGS, PKC is mainly used as a feed for livestock
because of its considerable protein content[17].
1.3 NO
x
emissions
The nitrogen contained in biomass causes the formation of nitrogen oxides dur-
ing combustion. NO
x
include various compounds like NO and NO
2
. These
compounds play an important role in atmospheric reactions that create harm-
ful particulate matter, smog and acid rain. These eects cost society billions
of dollars each year from illnesses and deaths[18]. NO
x
contributes to the for-
mation of ne particles that can cause respiratory diseases. It can also cause
eutrophication of water, which causes oxygen depletion and the degradation of
water quality and aquatic ora and fauna. Furthermore, NO
x
can react with
organic chemical species to form toxic products[1].
14
1.4 Literature on nitrogen in biomass
In the last years, several studies on nitrogen chemistry related to biomass and
the formation of NO
x
precursors have been carried out. An extensive literature
study on the N-chemistry related to biomass was presented by Becidan[19].
Becidan stated that nitrogen in biomass is not only originating from proteins,
as suggested in some studies. The protein in biomass can account for 30 up to
90% of the nitrogen. However, other sources of nitrogen can be found in the
form of non-proteins. These non-protein-N can be found in the form of:
Free amino acids and polypeptides
Non-protein amino acids
Nucleic acids and mononucleotides
Alkaloids
Inorganic-N
Chlorophyll
Quaternary-N
Other minor N-compounds
Studies on NH
3
and HCN release have been performed in two ways: studies
on biomass and studies on model compounds. Model compounds are chemical
compounds that depict a single chemical functionality of N. The main classes of
studied model compounds are amino acids/proteins and N-heterocycles as they
are two representative biomass N-functionalities.
Studies on the pathways of decomposition have shown that most of NH
3
and HCN are not primary products of model compounds decomposition but
rather products of secondary decomposition[20, 21, 22, 23]. Furthermore, the
pyrolysis of proteins gives a variety of fragments, depending on the protein[20].
This means that a multitude of reactions is involved.
For the two main groups of model compounds, the decomposition mech-
anisms were studied by Becidan[19]. These groups are protein/amino acid-
s/oligomers/polypeptides and N-heterocycles, as mentioned before. For the
rst group, ve pathways are presented as shown in gure 1.2. The two main
primary pathways are:
Dehydration through formation of cyclic amides
Decarboxylation with consequent amine formation
Three other, less important pathways are:
Intermediary formation of -lactam
Amide intermediaries formation
Cross-linking of proteins side groups to produce char-N and NH
3
15
Figure 1.2: Primary decomposition paths for amino acids[19].
The most important secondary reactions that follow on the primary path-
ways are the following:
Cleavages of DKP
Reactions of primarily formed amines
Reactions of primarily and secondary formed -lactam
Reaction of primary nitriles from primary amines
Reactions of N-containing char compounds
The mechanisms suggested for the N-heterocycles pyridine and pyrrole, two
important N-heterocycles, involve breaking of bonds in the ring and/or rupture
of the C-N bond followed by random cleavage/recombination of the resulting
diradical[24]. The suggested mechanisms usually consist of numerous steps (75
for pyrrole mentioned in [25]) where HCN is formed through a sequence of
reactions and not during the initial steps[26]. A study on pyridinic- and pyrrole-
type compounds [27] shows signicant amounts of NH
3
. The presence of -OH
groups would increase the amount of NH
3
at the expense of HCN[28]. The
involved mechanism is however unclear.
Model compounds can help in explaining the decomposition of biomass, how-
ever only to a limited extend. Because of the interactions between N-compounds
and non N-compounds, the yields of biomass decomposition can not be ex-
plained by only looking at the model compounds. From the work of Becidan
and other literature on N-chemistry related to biomass, the following two tables
were made, stating the main NO
x
precursors found at low and high heating
rates:
16
Table 1.1: Main NO
x
precursors for biomass in literature for isothermal/ slow
pyrolysis
Biomass Main precursor Reference
Bagasse HCN [29]
Cane trash HCN [30]
Whey protein HCN [31]
Soy beans NH
3

Yellow peas NH
3

Bark pieces T dependent
Miscanthus T dependent [32]
Wood pellets HCN
Bagasse HCN [33]
S peat NH
3
[34]
C peat NH
3

Pine bark NH
3

LS peat NH
3

CB peat NH
3
[28]
C peat NH
3

Birch bark NH
3

Fir bark NH
3

Pine bark NH
3

Miscanthus NH
3
[35]
Brewer spent grain NH
3
[36]
Fiberboard NH
3

Coee waste NH
3

Chicken litter Similar [1]
Meat and bone meal NH
3

Table 1.2: Main NO
x
precursors for biomass in literature for fast pyrolysis
Biomass Main precursor Reference
S peat NH
3
[34]
C peat NH
3

Sewage sludge NH
3
[36]
Brewer spent grain NH
3

Fiberboard NH
3

Coee waste NH
3

Chicken litter HCN [1]
Meat and bone meal T dependent
17
Table 1.3: Proximate and elemental analysis of evaluated biomass residues
(% dry basis) DDGS DDGS leached PKC PKC leached
Proximate analysis
1
Moisture
2
8.9 8.5 7 9.2
Volatiles 78.2 76.2 75.5 75.1
Fixed carbon 14.7 17 18.4 19.5
Ash 7.1 6.8 6.1 5.4
Elemental analysis
1
C 49.00 48.80 49.99 47.76
H 6.34 6.32 6.01 6.05
N 4.47 4.50 2.35 2.71
S 0.43 0.44 0.53 0.38
O 32.65 33.2 36.0 37.7
HHV [MJ/kg] 19.81 20.50 17.81 18.85
1.5 Leaching in water
Abother diculty associated with the use of biomass is the problems associated
with the ashes that are formed. The ashes can cause problems like deposition,
slagging, fouling, sintering and agglomeration. The ashes consist of inorganic
compounds, for biomass mainly alkali metals like potassium in the form of
inorganic salts. These salts can be dissolved in the moisture or connected to
carboxylic or other functional groups. Biomass is also rich in elements like
chlorine and sulfur, compared to wood fuels. One of the troublesome reactions
that is associated with the ashes, is the formation of alkali silicates which have
very low melting points which can cause depositing on reactor walls[8].
The ash thermal behavior can be improved by using leaching in water as
a pretreatment. This procedure was presented by Arvelakis et al.[8] and is
used to reduce ash content of the biomass and lower the amount of the so-
called troublesome elements like potassium, sodium chlorine and sulfur. To
see whether this treatment inuences the volatile product yield or composition,
both untreated and leached samples were investigated in this study.
The DDGS and PKC used in this study were soaked into water for 24 hours
with a water/mass ratio of 44.4g/L and 88.8 g/L, respectively. After the water
treatment the biomass was dried. The eect of leaching in water on the biomass
is limited, ss can can be seen in table 1.3. The leaching slightly increased
the heating value of both fuels, this can be attributed to the reduction in ash
content. Also, the amounts of Na, Cl and S are reduced in both fuels (table
1.4). The potassium content is slightly reduced in PKC, in DDGS the decrease
is negligible. Since the ash content and amount of potassium remain virtually
unchanged after leaching, the eect of this treatment is limited and this will
probably also show in the pyrolysis results.
1
Performed with automatic procedure on a Carlo Erba EA 9010 manufactured by Fisons.
2
On as received basis
18
Table 1.4: Elemental ash analysis of evaluated biomass residues
(% dry basis) DDGS DDGS leached PKC PKC leached
Al
2
O
3
0.2 0.4 4.8 5.3
SiO
2
22.4 28.8 16.2 23.3
CaO 3.2 2.4 10.2 7.1
MgO 12.7 6.2 11.4 6.5
Fe
2
O
3
0.4 0.5 11.5 14.3
K
2
O 22.7 22.4 15.1 12.3
Na
2
O 2.8 1.8 0.4 0.1
TiO
2
0.01 0.01 0.2 0.2
SO
3
2
11.5 2.0 9.2 2.4
Cl

2.9 0.9 3.3 0

P
2
O
5
31.7 18.8 25.9 28.9
1.6 Objectives
The purpose of this study is to gain more insight into the pyrolysis behavior
of DDGS and PKC under fast heating rate conditions relevant to industrial
applications like gasication. The aspects that are investigated are the volatile
yields and composition, mainly focusing on NO
x
precursors like NH
3
and HCN.
For this purpose, the measurements were carried out on an experimental setup
previously described and used by Di Nola [1] and Tamboer[2]. The parameters
that were varied are temperature, heating rate and holding time. Also, the
eect of leaching in water on the pyrolysis behavior of biomass is addressed.
Because the possibilities for monitoring the reactor temperatures are lim-
ited, a CFD model was made. This model can provide a better insight in the
phenomena concerning heat transfer and uid ow within the reactor. The main
research question that is posed in this study is the following:
How do the parameters of temperature, heating rate and holding time inuence
the yields and composition of volatiles released and the partitioning of nitrogen
during fast pyrolysis of DDGS and PKC?
Besides the main research question, a number of subquestions are posed:
What is the actual temperature of the heated grid in the experiments?
What does the temperature distribution within the reactor look like?
What does the velocity prole of the reactor look like?
Can yields of volatiles from low heating rate experiments be used to predict
the yields at high heating rates?
Which reaction mechanisms are likely to be relevant in the partitioning of
nitrogen?
How does the pretreatment of water leaching inuence the yields and
composition of volatiles released and the partitioning of nitrogen during
pyrolysis of DDGS and PKC?
19
1.7 Outline
In chapter 2 is introduced with a short literature review on fast pyrolysis equip-
ment is presented, followed by a description of the used experimental setup
and its components. Following, the experimental procedure is discussed and
some improvements are presented, both on quantication of the results as the
temperature measurement.
After the experimental setup is presented, a CFD model of the reactor is in-
troduced in chapter 3. First the dimensions of the model are presented, followed
by the incorporated phenomena. For each phenomenon, the used equations are
discussed. Finally, the results and validation with experimental data are pre-
sented. After validation, the temperature and decomposition of the biomass are
evaluated in some more detail.
In the following chapter, chapter 4, the results of the experiments are pre-
sented and analyzed. For the dierent parameters of temperature, heating rate
and holding time the volatile yields and compositions are evaluated. Special
attention is paid to the yield of the NO
x
precursors NH
3
and HCN.
Finally, the conclusions and recommendations are drawn.
20
Chapter 2
Experimental setup
In this chapter, the experimental setup is discussed. After a short introduction of
fast pyrolysis apparatuses, the experimental setup and procedure are presented.
Also, some considerations and improvements on both the setup and procedure
are discussed. Finally, a short discussion and conclusions on the chapter are
presented.
2.1 Literature review on fast pyrolysis equip-
ment
Fast pyrolysis experiments using a heated grid (also called a wire mesh or screen
heater) reactor have been used before in dierent studies[37, 38, 39, 7, 40, 41,
42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 1, 58]. The advantage
of this apparatus is that the time of pyrolysis can be precisely controlled and a
good mass balance can be obtained. Both can be controlled within a few percent.
Also, secondary reactions are minimized because the volatiles are released in a
relative cold environment[7]. One of the drawbacks of the system is the fact that
the temperature of the sample is not well-known and can not be easily measured.
Also, the temperature and temperature distribution of the grid are not very well
known[59]. The temperature of the grid can dier from the temperature of the
thermocouple because of poor heat transfer or heat loss to the thermocouple.
Because of the low heat capacity of the grid, also the temperature prole of the
grid or wire mesh can be non-homogeneous. Additionally, possible hot spots in
the reactor could cause secondary reactions.
For fast pyrolysis, also other equipment is available. The Curie-Point re-
actor and entrained ow reactor are capable of heating rates of 500-10
4
K/s
and 5x10
4
K/s, respectively[2]. In the Curie-Point reactor, the sample holder
is heated by electro magnetic induction. Curie-Point heaters generally have
the same questions with respect to the ability of the ferromagnetic material to
transfer heat to the sample[7] as for the heated grid.
In a drop tube furnace, the most widely used version of the entrained ow
reactor, particles entrained in a carrier gas are injected along the axis of a hot
furnace tube into a owing preheated gas stream[7]. There are a number of
advantages of this technique. The reactor can provide high heating rates and
high temperatures. Also, residence times are reasonably well controlled and
21
known. A disadvantage of the technique is the fact that the released volatiles
remain hot so secondary reactions will take place. Also, the temperature history
of the particles is not very well known.
Figure 2.1: Schematic top view of the heated grid reactor[60]
2.2 Experimental setup
The experimental setup used in this study, has been designed and used before by
Di Nola[1] and Tamboer[2]. It consists of a heated grid reactor that is connected
to a Fourier transform infra red (FTIR) spectrometer. In gure 2.1 a schematic
of the reactor is presented. In the reactor, a foil or wire mesh is supported by
two electrodes. The grid is heated using resistive heating achieved by applying
an electric current. The current is controlled by a computer, which makes it
possible to control temperature and heating rate of the grid. The gases in the
reactor are circulated by a pump through heated circulation lines. Both the
reactor and the circulation lines are heated to avoid condensation of pyrolysis
products and to limit the adsorption. The circulation lines connect the reactor
to the gas cell, which is a cylindrical chamber with ZnSe windows on both sides.
Through the gas cell, the volatile products are analyzed by the FTIR.
The FTIR in the setup is a Thermo-Nicolet NEXUS FT-IR, as shown in
gure 2.2. For details on this apparatus, please see the work of Di Nola[1]. The
sample compartment is replaced with the heated grid reactor, while the gas cell
is lined up with the detector mirror. The FTIR is continuously purged with
nitrogen to maintain an inert atmosphere. To cool the detector compartment,
liquid nitrogen is used. The software used with the FTIR is the Thermo Nicolet
OMNIC software package version 6.1. This package provides software for control
of the FTIR and analyzing the obtained data. More details on the quantication
using FTIR data can be found in appendix B.
The complete setup schematically looks like the representation in gure 2.3.
22
Figure 2.2: Thermo-Nicolet NEXUS FTIR[60]
Figure 2.3: Heated grid setup overview[1]
23
2.2.1 Pyrometer
The pyrometer used in the experiments for investigating the grid temperature
is an Impac IGA5 MB20 pyrometer. The pyrometer is mounted to the table
on which the FTIR with heated grid setup was standing. The pyrometer can
be precisely positioned in x and y direction since it is mounted on two 25mm
travel motion control translation stages, see gure 2.4. The pyrometer measures
the temperature in a spot of 1.1mm diameter at a distance of 90mm. The
measurement was done through the window of the reactor lid. This does not
inuence the measurement since this is 3mm thick BK7 glass, which is for 99.9%
transparant for the used wavelength[61].
Figure 2.4: Pyrometer setup schematic
24
2.3 Experimental procedure
Since the setup has been designed and used Di Nola[1] and Tamboer[2], an
experimental procedure has already been specied. However to ensure repro-
ducibility of the experiments, the experimental procedure followed in this study
will be shortly discussed. Also, some optimizations were made during this study.
2.3.1 Parameters
The parameters that were varied during the experiments are peak temperature,
heating rate and holding time. Table 2.1 shows the parameters that were used
in this study. The temperatures were varied between 500 and 1300

C just
like in the work of Di Nola[1]. These temperatures cover the range at which
industrial processes involving pyrolysis are operated. For the heating rate, 600
and 1000K/s were chosen to compare with the work of Di Nola. Finally, the
holding time was varied from 5 to 15 seconds. The holding time of 15 seconds
was chosen because the used sample weight in this study was 5-7 mg instead of
3-5 mg, so there might be a bigger inuence of heat transfer limitations. Since
this appeared to be the case only at 500

C, at higher temperatures a holding

time of 10 seconds is used.
Heating rate [K/s]
Temperature [

C] 600 1000
500 5-10-15 10
600 10 -
700 10 -
800 10 -
900 10 -
1000 10 -
1100 10 -
1200 10 -
1300 5-10-15 10
Holding time [s]
Table 2.1: Experimental parameters
2.3.2 Procedure
The rst step in preparing for the experiments was preparing the samples. The
biomass was pressed into slab type pills of 3 mm in diameter. The use of pills
instead of powder was chosen to ensure a similar behavior in terms of heat
transfer in every experiment. Also, for modeling of the pyrolysis and recovery
of the char a disc shape is more convenient. The untreated DDGS was delivered
in pellets, so these had to be ground into powder before being pressed into pills.
This was done by hand with a pestle and mortar. The palm kernel cake (PKC)
was delivered in powder form so no grinding was needed. The biomass was
pressed into discs of 5-7 mg, which resulted in pills of about 0.7 mm thickness.
This amount was chosen since it allowed for reasonably thin pills, while providing
25
a sucient amount of biomass necessary for the detection of minor species like
NH
3
and HCN.
The second step was preparing the setup itself. The FTIR had to be lled
with liquid nitrogen to cool the detector. This was done at least 30 minutes
before the experiments, to give the detector time to cool down. Also, the re-
actor and the circulation lines had to be heated up. Thirty minutes before the
measurements, the heaters were set to 130

C.
2.3.3 Running the experiments
The experimental procedure that was used is the following:
Weigh the sample.
Place the sample on the grid.
Flush the reactor with helium for 2 minutes at 300ml/min.
Close the in- and outlet.
Collect a background measurement.
Start the 3 minute sample series collection.
Ten seconds after the series collection started, start heating of the sample.
When the series collection is complete, open the in- and outlet and retrieve
the sample.
Weight the sample.
The samples were weighted on a scale with sensitivity of 0.01 mg, however
the sample weight was determined with an accuracy of 0.1 mg because of small
uctuations.
2.3.4 FTIR sampling
For the FTIR sampling, the same settings were used as suggested by Tamboer[2].
This means the mirror velocity was set to 1.8988 [m/s] at a resolution of 0.25
cm
1
and the number of scans per sample was set to three. This means every
measurement takes 9 seconds, so every series consists of 21 samples.
26
2.4 Experimental considerations
In the work of Di Nola[1], the volatile composition was determined immediately
after devolatilization. This was done to prevent secondary reactions. This
approach is questionable, since this probably does not allow for the volatiles to
fully mix and reach a homogeneous gas composition. To see at which time the
volatile composition can be considered homogeneous, experiments were done
with decomposing CaCO
3
. During the decomposition of CaCO
3
, CaO and CO
2
are formed. Since this experiment was done in a helium atmosphere, secondary
reactions involving CO
2
are not likely to occur. It appeared that the amount
of detected CO
2
remains quite constant after approximately two minutes, see
gure 2.5. Therefore it was decided to use the spectrum two minutes after the
peak in the CO
2
concentration for the nal quantication.
0 0.5 1 1.5 2 2.5 3 3.5
3500
3550
3600
3650
3700
3750
3800
3850
3900
3950
t[min]
C
o
n
c
e
n
t
r
a
t
i
o
n

[
p
p
m
]
Figure 2.5: CO
2
concentration over time after CaCO
3
decomposition at 1200

C,
heating started at t=0s.
For the detection of NH
3
there is not only the issue of mixing but also ad-
sorption on the reactor walls. Since the reactor is made of steel, it is very likely
that the reactor surfaces adsorb NH
3
to some extent. From FTIR measure-
ments on chicken litter, an ongoing decrease in time suggest that there is indeed
adsorption (gure 2.4). To see to what extent adsorption is likely to occur,
the setup was ushed with 1%vol NH
3
in helium. After the ushing, another
measurement on chicken litter was done. While measuring over time, after the
rst decrease in concentration another increase in concentration of NH
3
was
observed (gure 2.7). This suggests that there is indeed desorption of the NH
3
that was adsorped during the ushing.
To correctly quantify the amount of NH
3
that was released during the ex-
periments, the adsorption has to be taken into account. To do so, the release of
HCN was considered. Since both HCN and NH
3
probably originate from similar
compounds, so the timescale for their release was considered to be similar. This
assumption is supported by the fact that both NH
3
and HCN show a similar
27
0 0.5 1 1.5 2 2.5 3 3.5
50
0
50
100
150
200
250
t[min]
C
o
n
c
e
n
t
r
a
t
i
o
n

[
p
p
m
]
Figure 2.6: NH
3
concentration over time, released from chicken litter at T =
800

C
HR=600K/s and HT=15s, heating started at t=10s.
0 0.5 1 1.5 2 2.5 3 3.5
0
50
100
150
200
250
300
350
t[min]
C
o
n
c
e
n
t
r
a
t
i
o
n

[
p
p
m
]
Figure 2.7: NH
3
concentration over time after ushing with NH
3
, released from
chicken litter at T=800

C HR=600K/s and HT=15s, heating started at t=10s.

28
steep peak in the concentration(gure 2.8), unlike species like CO
2
which are
released much slower and show a much broader peak. So the trend from HCN
can be used to predict the trend without absorption of NH
3
. After two min-
utes, the HCN concentration is approximately 70% of the peak value. The NH
3
concentration was thus calculated as 70% of the peak value.
0 0.5 1 1.5 2 2.5 3 3.5
0
0.2
0.4
0.6
0.8
1
1.2
t[min]
F
r
a
c
t
i
o
n

o
f

m
a
x
i
m
u
m

d
e
t
e
c
t
e
d

c
o
n
c
e
n
t
r
a
t
i
o
n


HCN
NH3
Figure 2.8: NH
3
and HCN concentration over time, released after heating at
T=1300

C, HR=600 K/s and HT=10s, heating started at t=10s.

29
2.5 Setup improvements
In the setup the temperature is measured by a thermocouple. The temperature
of the thermocouple can be lower than the grid temperature because of heat loss
through the thermocouple surface or bad contact between the thermocouple
and the grid[59]. Besides these errors, the wiring of the thermocouple could
also introduce an error. A thermocouple consists of a junction of two dissimilar
metals, which generates a voltage if the junction is heated. This phenomenon is
called the Seebeck eect and occurs for all dissimilar metals[62]. In the heated
grid setup an S-type thermocouple is connected to stainless steel connectors,
which are in turn connected to thermocouple extension wire. This means that
the circuit of the thermocouple consists of several dissimilar metal junctions.
Since the reactor was kept at a temperature of 130

C during the experiments,

the connections between the thermocouple and the connectors to the extension
wire will probably show a signicant Seebeck eect. This error was discovered
in the starting value of previous measurements, see gure 2.10.
Figure 2.9: Schematic of improved wiring.
To reduce the error introduced by the thermocouple wiring, the heated part
of the thermocouple extension wires replaced by a piece of stainless steel welding
wire (gure 2.9). In this way, the connection between the extension wire and the
stainless steel is at ambient temperature instead of the reactor temperature. As
a result, the initial temperature error was signicantly lower. When the reactor
temperature was set to 130

C, the thermocouple gave an initial temperature of

about 100

C. A similar temperature was measured in the reactor with a K-type

thermocouple. Before, the thermocouple gave an initial temperature of about
300

C when the reactor was set to 110

C, see gure 2.10.

It has been suggested that measuring the temperature with a thermocouple
might introduce a signicant error[59]. To obtain a more accurate value for the
actual temperature on the grid surface, an infrared pyrometer (IMPAC IGA 5
MB20, a=90mm) was used. When the emissivity of the surface to be measured
is accurately known, this device can give an accurate temperature measurement
without inuencing the thermal behavior of the surface. Since the surface emis-
sivity increases with increasing temperature because of physical changes in the
foil, the foil has been heated for 1 minute at a set point temperature of 1100

C
in a Helium atmosphere. After this treatment, the surface has a light gray, dull
appearance. The emissivity of this surface has been determined by heating the
30
0 2 4 6 8 10 12 14
0
100
200
300
400
500
600
700
800
900
t [s]
T

[

C
]


T
set
T
TC
(a) This study (b) Previous work
Figure 2.10: A temperature curve from this study (left) and a previous study
on the same setup[63] (right)
foil with a ceramic heater to approximately 300

C. At this temperature, the

temperature was determined with a 0.1 mm K-type thermocouple. The pyrom-
eter has been pointed to this same spot and the emissivity has been adjusted
to measure the same temperature. The surface appears to have an emissivity of
0.75. It was assumed that the emissivity does not change signicantly over the
temperature range used in the experiments, since no additional visual changes
occur after heating.
400 500 600 700 800 900 1000 1100 1200
500
600
700
800
900
1000
1100
1200
1300
1400
T set [C]
T

[

C
]


Measured @ =0.75
Measured @ =1
Measured @ =0.5
Set point
Figure 2.11: Measured temperature at dierent emissivities.
To approximate the real temperature during the experiments, the emissivity
setting of the pyrometer was set to 0.75 and the temperature was measured for
set points ranging from 500 to 1100

C. The result can be found in gure 2.11.

To see the inuence of an error in emissivity, the range of temperatures has
was measured with emissivity settings 0.5 and 1. It can be seen that even at
31
emissivity of 1 (which will give the lowest possible temperature), the measured
temperature was still 70-120

C higher than that of the thermocouple. This

indicates that the thermocouple temperature is very likely to be too low. If the
emissivity at higher temperatures is going towards 0.5, the temperature might
be signicantly higher than what was measured at emissivity of 0.75. This is
however very unlikely since emissivity tends to increase with temperature.
The trend of temperature deviation between the thermocouple and the py-
rometer appeared to be quite linear. To determine the relation between the two
temperatures, a linear function was tted to the average measured temperature,
see gure 2.12. This function was used to determine the set point for the setup
during the experiments. The set points were set in increments of 5

C, see table
2.2.
500 600 700 800 900 1000 1100
500
600
700
800
900
1000
1100
1200
1300
T
set
[C]
T

[

C
]


T
predicted
=1.15*T
set
Measured
Figure 2.12: Relation between actual temperature and setpoint
Experiment temperature Set temperature
500 435
600 525
700 610
800 700
900 785
1000 870
1100 960
1200 1045
1300 1135
Table 2.2: Temperature set points for experiments [

C]
32
2.6 Discussion and conclusions
In the description of the experimental setup, some improvements were suggested.
One of the suggestions was to quantify the volatile yields after allowing the
volatile products to fully mix. The drawback of this approach is that secondary
reactions might occur and some species might be adsorbed in the system. For
NH
3
it was considered very likely that adsorption takes place. The species HCN
and H
2
O, however, show also a greater decrease over time than CO, CO
2
and
CH
4
(approximately 30% and 10%, respectively). This can be caused by a faster
release mechanism, but could also be caused by adsorbtion.
2.6.1 Conclusions
From the evaluation of the experimental setup, the following conclusions can be
drawn:
When quantifying the volatile species in the heated grid setup, mixing of
the volatiles has to be taken into account.
NH
3
is likely to adsorb in the setup, this has to be considered in the
quantication.
Changing the hot parts of the thermocouple connection wire from the
reactor to the computer signicantly reduces the measuring error.
The temperature of the grid is signicantly higher than indicated by the
thermocouple.
The actual grid temperature can be predicted using the relation:
T
Grid
1.15 T
Thermocouple
.
33
Chapter 3
Modeling
In this chapter, a CFD model will be discussed that was made during this study.
First, the purpose of the model is presented, followed by the model geometry.
Next, the equations used are discussed, and nally the validation with experi-
mental data. After validation of the model, the temperature of the biomass is
investigated using the model. This is followed by a suggestion for expanding
the model with the release of volatiles. Finally, the results of the modeling are
discussed.
The heated grid or heated wire mesh setup has been used before in numer-
ous fast pyrolysis studies[1, 54, 58] (see chapter 2 for more references). It has
been recognized however, that there is a level of uncertainty in the temperatures
present in both the grid and biomass sample[59, 7]. Because of the fast heat-
ing rates and small dimensions, it is dicult to measure temperatures without
inuencing the system. To provide a better understanding of the temperatures
that are present in the system, a CFD model was made.
The temperature of the heated grid is controlled using a ne wire thermo-
couple. The temperature of this thermocouple can be lower than that of the
grid due to poor contact. Also, due to heat loss through the thermocouple, the
actual grid temperature can be lower at the spot where the thermocouple is in
contact with the grid. One of the purposes of the model is to gain a better
insight in the actual temperature of the grid. Furthermore, this model can help
to detect possible hot spots in the reactor volume. The model can later on be
used as a basis for modeling the release of volatiles in the experiments. The
model was made using the COMSOL Multiphysics 3.5a software[64].
3.1 Model dimensions
In the model presented here, only the reactor itself was modeled. The system
boundary is shown in gure 3.1. The boundary was chosen because the condi-
tions here are well known (wall temperature, inlet velocity and temperature).
The model looks as in gure 3.2. The exact dimensions of the model can be
found in Appendix C.
34
Figure 3.1: System border for the physical model.
Figure 3.2: Overview of the reactor model.
35
3.2 Heat transfer modeling
The model was built using three dierent modules to take into account the
dierent relevant phenomena. The following COMSOL modules were used:
General heat transfer
Conductive media
Weakly compressible Navier Stokes
The rst module, general heat transfer, takes into account the three funda-
mental heat transfer mechanisms: convection, conduction and radiation. The
following assumptions were made for this module:
The reactor inlet temperature is constant over time.
The reactor wall temperature is uniform and constant over time.
The reactor lid temperature is uniform and constant over time.
Heat transfer through radiation is only signicant for the grid.
The basis for these assumptions is discussed in the section that presents the
boundary equations.
3.2.1 Subdomain equations
In the model, each volume is dened as a subdomain with its own equations.
The heat transfer subdomain equation that is solved, is the following:
C
p
T
t
+ (kT) = Q + q
s
T C
p
u T (3.1)
Density [kg/m
3
]
Where is the density [kg/m
3
], C
p
is the specic heat capacity [kJ/kg*K],
T is the temperature [K], k is the thermal conductivity [W/m*K], Q is the heat
source [W/m
3
], q
s
is the production/absorption coecient and u is the velocity
vector [m/s]. The rst left hand term takes into account the thermal storage in
the volume, the second term takes into account the conduction. On the right
hand side, the rst two terms account for heat production, the third one accounts
for convection. This equation is solved for each subdomain, the convection term
is only used for the uid subdomain and not for the solid subdomains.
Table 3.1: Boundary settings heat transfer
Boundary Equation
Inlet T = T
0
Outlet - n (kT) = 0
External boundaries T = T
0
Internal boundaries - n
u
(k
u
T
u
) n
d
(k
d
T
d
) = 0
Grid boundaries - n
u
(k
u
T
u
) n
d
(k
d
T
d
) =
_
T
4
amb
T
4
_
36
Table 3.2: Boundary temperatures.
Boundary Temperature [

C]
Reactor wall 110
Reactor lid 95
Inlet 110
3.2.2 Boundary equations
The heat transfer boundary equations can be found in table 3.1. For the inlet,
a temperature was set. The temperature at this boundary was assumed to be
equal to that of the circulation line walls and was assumed not to change sig-
nicantly during the experiments. The outlet boundary was set to convective
ux, which means only convective heat transfer is possible at this boundary.
The external boundaries were also set to a constant temperature, because the
reactor was kept at a constant temperature by heating elements and has a high
thermal mass so the temperature will not change signicantly during the experi-
ments. The internal boundaries were set to continuity, except for the boundaries
between the grid and the uid. The grid temperature during the experiments
ranges from 500 to 1300

C, so heat transfer by radiation was considered be

signicant. The heat source/sinkboundary setting allows for the incorporation
of radiation. The radiation from the grid was set to surface-to-ambient, which
implies that there is no interaction with other surfaces in terms of radiation.
This was done because the other surfaces were at relative low temperatures and
the surface area of the grid is small compared to the surrounding surfaces so
the eect of reection was expected to be minimal. The equation used for the
grid boundaries looks as follows:
n
u
(k
u
T
u
) n
d
(k
d
T
d
) =
_
T
4
amb
T
4
_
(3.2)
Where n is the vector normal to the surface, is the surface emissivity and
is the Stefan Boltzmann constant [5.6707e-8 W m
2
K
4
].
The temperatures for the boundary settings were determined using a 0.1mm
sheathed K-type thermocouple. The obtained temperatures are shown in table
3.2.
3.3 Conductive media modeling
Since the grid is heated using resistive heating, the electric eects have to be
taken into account. This module is only used for the grid and the connected
electrodes, where it calculates the heating as a function of the current. The
current as a function of time in the model is the same as the input to the real
setup.
3.3.1 Subdomain equations
The used subdomain equation is the following:
(
e
V J
e
) = Q
j
(3.3)
37
Where
e
is the electric conductivity [S m
1
], V is the electric potential, J
is the external current density vector [A m
2
] and Q
j
is the current source [A
m
3
]. From the current density, the heat production is calculated in the heat
transfer module.
3.3.2 Boundary equations
The boundary equations for the conductive media are very straightforward, since
there is one inward current ow and one ground while the other boundaries are
electric insulation, see table 3.3.
Table 3.3: Boundary settings conductive media
Boundary Equation
Electrode 1 bottom J
n
= I(t)
Electrode 2 bottom V = 0
Other boundaries n J = 0
3.4 Weakly compressible Navier Stokes model-
ing
The weakly compressible Navier Stokes module was used to calculate the uid
ow. This model is based on the incompressible Navier Stokes equation, but
takes into account the eect of the temperature on the density. The following
assumptions were made:
The ow is incompressible.
The ow is laminar.
Buoyancy eects can be accounted for by the simplied Boussinesq ap-
proximation.
Since the equation is based on the incompressible Navier Stokes equation,
it can only be used for low Mach numbers. Usually, Ma=0.3 is taken as a
limit for incompressible ow[65]. At the outlet, the velocity is the highest and
thus the Mach number will be at its maximum. The outlet velocity can be
calculated from the volume ow which is known to be 2.6 l/min from the pump
specications and the cross sectional area which is 4.97e-5 m
2
. Assuming the
outlet to be at the reactor temperature, 110

C, the speed of sound in helium

is a = (RT)
1/2
= (1.66 2077 383.15)
1/2
= 1149, the Mach number at the
outlet of the model is[65]:
Ma =
|u|
a
=
0.87
1149
= 7.6e 4 0.3 (3.4)
So the assumption of an incompressible uid is valid.
38
3.4.1 Subdomain equations
The weakly compressible Navier Stokes equation looks as follows:

u
t
+u u =
_
pI +
_
u + (u)
T
_
(2/3 ) ( u) I
_
+F (3.5)

t
+ (u) = 0 (3.6)
Where u is the velocity [m s
1
], p is the pressure [Pa], the dilational vis-
cosity [Pa*s], I the identity matrix and F the internal force [N m
3
]. For the
Buoyancy eect, the Boussinesq approximation can be used. This approxima-
tion replaces the continuity equation by the incompressible form[65]:
u = 0(3.7)
This approximation is valid when the ow can be regarded incompressible.
However, also the temperature variations must be limited. The approximation
can be used when the following condition holds:

= T 1 (3.8)
Because of the high grid temperatures, this condition will not hold for the
ow close to the grid. It was however not possible to use the compressible
continuity equation with the standard COMSOL equations. If necessary, this
equation could be implemented in the model later on. For now the Boussinesq
approximation was implemented as follows:
F = (
0
) g (3.9)
3.4.2 Boundary equations
The boundary conditions for the weakly compressible Navier Stokes equations
are very straightforward. At the inlet, a uniform velocity was assumed. This
does not represent the actual ow pattern, but this simplication will not sig-
nicantly inuence the overall solution . The velocity was calculated from the
volumetric ow rate of the pump which is assumed to be according to its spec-
ications. At the outlet, the pressure was specied. At other boundaries, no
slip was assumed. The boundary settings are shown in table 3.4.
Table 3.4: Boundary settings weakly compressible Navier Stokes
Boundary Equation
Inlet u = - U
0
n
Outlet p = p
0
Other boundaries u = 0
39
3.5 Mesh properties
For the meshing of the model, the meshing was done one sub domain at a time.
Since the grid is a plate, the number of elements is by default very large. To re-
duce computational time, the meshing for the grid was set to extremely coarse.
Other subdomains were meshed with normal element size. To see whether the
coarse meshing of the grid can be justied, the model was solved in transient
mode for both the coarse mesh and a rened mesh at a thermocouple tempera-
ture of 500

C. The number of elements in the grid and uid, the most important
sub domains, are presented in table 3.5.
Table 3.5: Number of elements in the grid and uid sub domain
Sub domain Elements in coarse mesh Elements in rened mesh
Fluid 48081 78569
Grid 2620 10066
To judge whether the number of meshed elements is sucient, a plot of both
the grid temperature and peak temperature over time were made, see gures
3.3 and 3.4. The ner mesh shows a smoother temperature distribution, but
the coarse mesh appears to mesh with sucient detail. Also, in the trend of the
peak temperature no signicant dierence can be identied. It was therefore
decided to use the coarse mesh.
(a) Coarse mesh (b) Finer mesh
Figure 3.3: Grid temperature distribution for coarse and ner mesh at
T
thermocouple
=500

C and t=10s.
40
(a) Coarse mesh (b) Finer mesh
Figure 3.4: Peak temperature over time for coarse and ner mesh at
T
thermocouple
=500

C.
3.6 Results & validation
3.6.1 Results
One of the most interesting results is the temperature distribution within the
foil. In the work of Prins et al.[59] the temperature distribution of a foil was
determined using a camera for recording visible emission. The result is shown in
gure 3.5. Please note that temperatures below 600

C have no physical meaning

in this gure since this was outside the calibration range of the camera. The
picture shows the temperature distribution of a 0.1 mm nickel/chromium foil
of 10x16 mm while the temperature indicated by the thermocouple was 725

C.
While the foil used in the model in this study has dierent properties (0.05 mm
18/8 steel 8x14 mm), the model was solved using a similar temperature to make
a rough comparison. For this purpose the model was solved in steady state for
a thermocouple temperature of 700

C and a reactor temperature of 25

C (since
the reactor of Prins et al. was not at elevated temperature). The result is shown
in gure 3.6.
If the distribution of the temperature within the two gures is compared,
both show that the temperature at the center of the foil is reasonably uniform.
The gradient towards the side in x-direction of the model appears to be larger,
which makes sense since the foil is thinner and thus has a lower heat capacity.
Also the temperature of the electrodes in the setup of Prins et al. is unknown,
which can inuence the gradient. Another dierence is the fact that the peak
temperature of the model is slightly below the thermocouple temperature, while
Prins et al. found a slightly higher temperature.
If we look at the temperature distribution in the y-z and x-z plane of the
reactor (gures 3.7 and 3.8), the distribution of the temperature shows virtually
no Buoyancy eects. Because of the low velocities, conduction is the governing
phenomena close to the grid. There are however some Buoyancy eects visible,
if we look at the arrow plot and velocities in the y-z plane, see gures 3.9 and
41
Figure 3.5: Temperature distribution of the grid found by Prins et al. for
T
thermocouple
=725

C .
Figure 3.6: Temperature distribution of the grid in the model for
T
thermocouple
=700

C in steady state, T
reactor
=25

C.
42
Figure 3.7: Temperature distribution in the y-z plane of the reactor for
T
thermocouple
=1000

C, HR=400K/s and HT=10s at t=10s.

3.10. Probably the Buoyancy forces actually are stronger than predicted by the
model, because the Boussinesq approximation is not valid close to the grid. The
compressible Navier Stokes equation that should be used here is not available
within the COMSOL package.
43
Figure 3.8: Temperature distribution in the x-z plane of the reactor for
T
thermocouple
=1000

C, HR=400K/s and HT=10s at t=10s.

Figure 3.9: [v,w] velocity eld arrows in the y-z plane for T
thermocouple
=1000

C,
HR=400K/s and HT=10s at t=10s.
44
Figure 3.10: Distribution of the velocity in z direction for the same conditions
of the previous plots.
3.6.2 Validation
To validate the results from the physical model in a quantitative way, the results
from modeling were compared to what was measured by both a thermocouple
and a pyrometer. The pyrometer was positioned in such a way that it measured
the spot temperature of the grid where the thermocouple is in contact with
the grid from below. This is at the center of the grid, where temperature was
considered to be the highest.
In gure 3.11 the temperatures measured by both the thermocouple and
pyrometer are presented, as well as the current and prediction of the model. One
of the rst things that draws the attention is the peak in the model prediction.
This is probably caused by the solver settings, since the predicted temperature
at higher temperatures also tends to be a bit instable (gure 3.12). Overall it
appears that the model works quite well in terms of dynamic response, since
the heating rate was predicted adequately. Please note that the line of the
pyrometer only starts at 250

C, since this is the lower limit of the operational

range.
A plot of the temperatures measured by the pyrometer and thermocouple
over a range of temperatures is presented in gure 3.13, together with the model
predictions. The temperature that was estimated at low temperature settings
is similar to what was measured by the thermocouple (see gure 3.11). At
higher temperatures, the temperature tends towards the trend measured by
the pyrometer. However, it is unlikely that the temperature indicated by the
thermocouple is correct, since even if the grid were to have an emissivity of 100%,
the temperature would still be signicantly higher according to the pyrometer as
was shown in the previous chapter. Since the appearance of surface of the grid
changed after heating, it could be the case that also the temperature dependance
of the electric and thermal properties have changed.
45
0 2 4 6 8 10
0
100
200
300
400
500
600
700
800
t [s]
T

[

C
]
0 2 4 6 8 10
0
3
6
9
12
15
18
21
24
I

[
A
]
(a) Temperature and current as a function of time.
0 2 4 6 8 10
0
100
200
300
400
500
600
700
t [s]
T

[

C
]


T
thermocouple
T
pyrometer
T
model
(b) Measured and predicted temperature.
Figure 3.11: Temperature and current for the reactor with parameters
T=500

C, HR=600 K/s and HT=10s

0 2 4 6 8 10
100
200
300
400
500
600
700
800
900
1000
t [s]
T

[

C
]


T
thermocouple
T
pyrometer
T
model
(a) T=800

C.
0 2 4 6 8 10
0
200
400
600
800
1000
1200
1400
t [s]
T

[

C
]


T
thermocouple
T
pyrometer
T
model
(b) T=1100

C.
Figure 3.12: Measured and predicted temperatures for the reactor with param-
eters T=800

C (left) and T=1100

C (right), HR=600 K/s and HT=10s

46
At higher temperatures (>800

C) the predictions of the model are quite

close to the ndings from the pyrometer. Only at the set point of 1100

C, the
model is starting to overestimate. This is probably caused by the fact that most
temperature dependent properties were only dened up to 1200-1400K and lin-
ear extrapolation is used here. Since the predictions at higher temperatures are
reasonably accurate, probably the Boussinesq approximation does not introduce
a signicant error in this range.
400 500 600 700 800 900 1000 1100 1200
400
500
600
700
800
900
1000
1100
1200
1300
1400
T
set
[C]
T

[

C
]


T
set
T
pyrometer
T
model
Figure 3.13: Trend for the measured temperatures and model predictions
Figure 3.14: Lines where the temperature is determined
Besides the peak temperature, also the distribution of the temperature over
the surface was investigated. Since the pyrometer gives a spot measurement
of the temperature, the distribution had to be determined using an array of
measurements. The temperatures over the x and y centerlines of the grid were
determined as shown in gure 3.14. This was done after the grid had been at
the set temperature for a few minutes to ensure that the grid and its electrodes
were not signicantly changing over time. The results are given in gures 3.15
and 3.16.
47
Apart from the temperature dierence, the temperature prole at 500

C cor-
responds quite well with the experimental values. Only close to the electrodes,
the gradient in the model is higher. This is however not very important, since
only the center of the grid is used for pyrolysis experiments. If we look at the
temperature distribution at 800

C, the distribution in x direction corresponds

quite well but in y direction the experimental results show an eccentric trend,
this was also visually observed in some experiments. This is probably caused by
bad contact at the electrodes as was also suggested by[59]. This phenomenon
occurred in some of the experiments and proved dicult to avoid. However since
the gradient in y direction is limited, the inuence on the pyrolysis temperature
is small.
8 6 4 2 0 2 4 6 8
x 10
3
200
250
300
350
400
450
500
550
600
x[m]
T
[

C
]


Model
Measured
(a) T-x distribution.
4 3 2 1 0 1 2 3 4
x 10
3
200
250
300
350
400
450
500
550
600
y[m]
T
[

C
]


Model
Measured
(b) T-y distribution.
Figure 3.15: Grid temperature distribution over x and y for set point T=500

C
8 6 4 2 0 2 4 6 8
x 10
3
300
400
500
600
700
800
900
1000
x[m]
T
[

C
]


Model
Measured
(a) x
4 3 2 1 0 1 2 3 4
x 10
3
300
400
500
600
700
800
900
1000
y[m]
T
[

C
]


Model
Measured
(b) y
Figure 3.16: Grid temperature distribution over x and y for set point T=800

C
48
Table 3.6: Biomass sample properties
variable value unit
d 3 mm
t
s
0.7 mm
1200 kg m
3
k 0.07 W m
1
C
p
1200 J kg
1
K
1
0.75 -
3.7 Biomass temperature modeling
In the heated grid setup used in this study, the temperature of pyrolysis was mea-
sured on the grid. This temperature will dier from the average biomass tem-
perature to some extent. However, measuring the temperature of the biomass
with a thermocouple will inuence the temperature of the biomass, since the
sample and thus its heat capacity is very small. Measuring the temperature in
a non-contact measurement with a pyrometer is also dicult, due to the fact
that the emissivity changes during pyrolysis and infrared absorbing gases are
emitted that would inuence the measurement. By making a CFD model of
the biomass, more information about the biomass temperature can be gained
without the previous mentioned problems.
Modeling the biomass can be done in the CFD model of the reactor that was
made. One of the diculties when modeling the thermal behavior of biomass is
the fact that the thermal properties are not well known and that they are a func-
tion of temperature and conversion rate. To make a rst approximation of the
temperature in the DDGS during pyrolysis, some assumptions on the thermal
properties were made. The thermal conductivity k for DDGS was obtained from
the work of Rosentrater[66]. The density was calculated by using the mass and
volume of the samples from the experiments in this study. The heat capacity
is unknown, so this has to be estimated. Since DDGS does not dier too much
from wood in terms of density and elemental composition, the heat capacity
of DDGS is assumed to be similar to wood. For wood, the heat capacity can
range from approximately 1.2 to 2.3 kJ/kg*K, depending on moisture content
and temperature[67]. To get a rst impression of the temperature distribution
during pyrolysis, a biomass sample with a heat capacity of 1.2 kJ/kg*K and
one with a heat capacity of 2.3 kJ/kg*K were modeled. For the emissivity of
the sample, = 0.75 was assumed. This value was also used by Ragland et al.
calculations on the combustion of wood[68]. The emissivity was specied at the
contact surface with the uid and is specied as radiation to ambient, just as
was done for the grid. The contact between the sample and grid was assumed to
be ideal, so the boundary condition was specied using the continuity equation.
The properties of the sample are presented in table 3.6.
As can be found in gure 3.17, the temperature dierence between the
biomass average and grid peak is signicant. Also the holding time is sig-
nicantly shorter for the modeling with the higher heat capacity. This indicates
that the thermal history of the sample can not be taken to be the same as that
of the grid. However to determine the thermal history of the sample with more
accuracy, improvement on the modeling is necessary.
49
0 2 4 6 8 10 12 14
0
200
400
600
800
1000
1200
t [s]
T

[

C
]


Biomass volumetric average
Grid peak
(a) Cp=1.2kJ/kg*K
0 2 4 6 8 10 12 14
200
400
600
800
1000
t [s]
T

[

C
]


Biomass volumetric average
Grid peak
(b) Cp=2.3kJ/kg*K
Figure 3.17: Peak and (volumetric) average biomass temperature over time for
T
thermocouple
=1000

C, HR=600K/s and HT=10s.

The model for biomass temperature prediction can be improved using a
method similar to the one in the work of Damartzis et al.[58]. In the work of
Damartzis, the pyrolysis of biomass was modeled using the particle approach.
This method takes into account both heat transfer and reaction kinetics, making
the thermal properties dependent on the degree of biomass conversion. The used
equation in this study looks as follows:
(C
B
c
PB
+ C
C
c
PC
)
T
t
=
1
r
2

r
kr
2
T
r
+ (H)
dC
B
dt
(3.10)
Where C is the concentration [kg m
3
], c
p
is the heat capacity, T is the
temperature [K], r is the particle radius [m] and H is the heat of reaction [J
kg
1
]. The subscripts C and B refer to the char and biomass, respectively. This
equation is a spherical form of the energy equation that is also solved in the
physical model that was made in this study. The term for biomass conversion
is dened as:
dC
B
dt
= k
1
C
B
k
2
C
B
(3.11)
Where k
1
and k
2
are the kinetic rate constants for the rate of formation of
gaseous compounds (volatiles and tar) and char, respectively. The kinetic rate
constants are dened using the Arrhenius equation:
k
1
= A
1
e
E1/RT
quation
Where A is the frequency factor [s
1
], E is the activation energy [J mol
1
], R
is the gas constant [J mol
1
K
1
and T is the temperature [K]. The parameters
for this equation, the frequency factor A and activation energy E, can be ob-
tained from tting the relation of char formation as a function of temperature.
The relations for the thermal properties are obtained from literature.
50
3.8 Release of volatiles
The release of volatiles from a biomass sample could be a useful extension to
the model that was made during this study. Assuming that the sample temper-
ature can be accurately predicted using the modeling approach as described in
the previous section, the release of volatile species can be described as a function
of temperature within the sample. The kinetics for the species can be obtained
from low heating rate experiments as presented by Guintoli et al.[3]. While the
formation of volatile species can be described by the Arrhenius equation, the
distribution of these species in the solid and gas can be modeled using the Con-
vection and diusion module is COMSOL. The binary diusion coecients for
most species can be determined as a function of temperature using Appendix D
in the book of Turns[69]. The eective diusivity in the solid can be determined
using the relation as presented by Fogler:
D
e
=
D
AB

c

(3.13)
Where D
e
is the eective diusivity, D
AB
is the binary diusion coecient,

p
is the pellet porosity,
c
is the restriction factor and is the tortuosity[70].
The pellet porosity can be calculated using the relation given in the work of
Damartzis et al.[58], the restriction factor and tortuosity can be taken as the
common values suggested by Fogler.
51
3.9 Discussion and conclusions
From the quantitative validation (gures 3.12 and 3.13), it appears that the
model is able to predict the peak temperatures and heating rate quite well for
temperatures between 900 and 1200

C. Also, the temperature distribution is

well approximated for both low(500

C) and higher(800

C) temperatures (gures
3.15 and 3.16). Assuming that the thermocouple was placed correctly in the
middle of the grid, there was no signicant inuence of heat loss through the
thermocouple according to the pyrometer measurements. This hints towards
the conclusion that the thermocouple gives a lower temperature because of bad
contact between the thermocouple and the grid. This is in agreement with the
suggestion of Prins et al.[59] that a foil will be less inuenced in terms of heat
loss through the thermocouple.
From the grid (gure 3.6) and reactor temperature distribution (gure 3.7),
it appears that the physical model behaves quite well. Also, there are no hot
spots visible other than near the grid that would cause secondary reactions to
take place. It could however be that secondary reactions take place in this zone
immediately after release or when circulating the volatiles. The latter is however
not very likely to have a big inuence since the total reactor volume is circulated
about two times within the holding time. The fraction of the gas that will go
through the hot zone in this time will be limited.
The Buoyancy eect in the model is calculated using the Boussinesq approx-
imation. Since this approximation is only valid for incompressible ows with
a limited gradient in temperature, the use of this approximation is not com-
pletely valid. Since the temperature deviation at higher temperatures is lower,
it appears that the approximation can be used.
For improving on the modeling of the biomass temperature, the modeling
approach of Damartzis et al.[58] can be used. This approach was presented to
model fast pyrolysis of a particle, but because of the small sample size it probably
can be applied for modeling the sample in this study without introducing a large
error. The approach of Damartzis et al. allows for the thermal properties of
biomass to be calculated as a function of temperature and conversion. The
conversion can be calculated as presented in the section on devolatilization in
this study. The modeling approach of Damartzis et al. can be used to obtain
the kinetics for weight loss as well.
In the work of Damartzis et al., the model for fast pyrolysis of a particle
appears to correspond to experimental data quite well. The approach was, how-
ever, signicantly dierent from what is presented in this work, since Damartzis
takes the biomass temperature as a starting point. The basis of this study was
to question the temperature of the biomass in the rst place. In the work of
Damartzis, the biomass consists of a 200 mg layer in a folded wire mesh where
the thermocouple measures the bulk temperature. It can be questioned whether
this is a valid starting point because it is known that the grid itself already has
a temperature gradient.
52
3.9.1 Conclusions
Evaluating the results of the modeling, a number of important conclusions can
be drawn:
There are no hot spots in the reactor other than around the grid.
Only in the center of the grid the gradient in temperature is low, so correct
placement of the sample is important.
According to a rst approximation, the temperature and heating rate of
the sample dier signicantly from the grid.
53
Chapter 4
Experimental results
In this chapter, the results of the fast pyrolysis experiments will be discussed.
First, the quantication method is discussed briey. Then, the inuence of
the temperature on the volatile composition and yields is discussed. This also
involves the comparison between slow and fast pyrolysis. Following, the inuence
of holding time and heating rate is investigated.
4.1 Analyzing the results
The volatile yields of the experiments are quantied using Quant Pad soft-
ware, part of the OMNIC 6.1 software package. For the quantication, a cal-
ibration method has been dened to determine the quantities for each species
from the infrared absorption lines obtained with the FTIR. The description of
this method can be found in appendix B. This quantication method gives the
volatile amounts in ppm. To relate the volatile yields to the sample weight, it
has to be converted to mg. This can be done using the densities and reactor
volume. The densities are calculated using the ideal gas law. The equation for
the conversion to mg looks as follows:
m[kg] = C [ppm] V
_
m
3

[kg/m]
The reactor volume V is 200ml, the density is calculated at the initial reactor
conditions which are a pressure p 1.013 bar and the temperature T=110

C.
The weight loss and species yields are presented of dry and ash free basis
(d.a.f.) except for H
2
O, which is presented on as received basis. The d.a.f.
weight can be calculated as follows:
m
d.a.f.
[mg] = m
a.r.
_
100 moisture [wt
a.r.
%]
100
__
100 ash[wt
d.b.
%]
100
_
(4.1)
Now the d.a.f. yield for species i is calculated using:
Y ield
i,wt%,d.a.f.
=
m
i
m
sample,d.a.f.
54
4.2 The inuence of the nal temperature
In this section the inuence of the nal temperature on the volatile yields and
composition is evaluated. Please note that the temperatures are those after
correction using the tted relation presented in chapter 2.
4.2.1 Weight loss
400 600 800 1000 1200 1400
80
85
90
95
100
105
W
e
i
g
h
t

l
o
s
s

[
w
t
%

d
.
a
.
f
.
]
400 600 800 1000 1200 1400
80
85
90
95
100
105
400 600 800 1000 1200 1400
80
85
90
95
100
Temperature [C]
W
e
i
g
h
t

l
o
s
s

[
w
t
%

d
.
a
.
f
.
]
400 600 800 1000 1200 1400
80
85
90
95
100
105
Temperature [C]
Figure 4.1: Weight loss as a function of the nal temperature. Clockwise,
starting from top left: DDGS, leached DDGS, leached PKC and PKC.
The inuence of the nal temperature on the weight loss is quite similar
for each type of biomass, as can be seen from gure 4.1. Both the dierence
between the two types of biomass and their leached and untreated state does not
seem to signicantly inuence the weight loss. This is to be expected since their
elemental composition is quite similar. Giuntoli et al.[3] also found no eect
of the leaching on the weight loss characteristics. At 1300

C, for the DDGS it

appears that the weight loss is still increasing while for PKC it appears the nal
yield has been reached at about 86-87%. The shape of the weight loss curves is
similar as found by Damartzis et al.[58] for olive residues, although the yields
and temperatures dier.
The weight loss found for DDGS is higher than what was found by Giuntoli
et al., who found a weight loss of 78-79% for untreated and leached DDGS at
900

C. The weight loss found in this study is about 83% at 900

C, increasing
up to about 87% at 1300

C. According to the weight loss curve of slow pyrolysis

of DDGS, the primary devolatilization of DDGS should be complete at about
600

C[3]. It is possible that during the slow pyrolysis, some volatile compounds
have condensed in the char at lower temperatures and that they start decom-
posing at higher temperatures. For fast heating rates these compounds will be
released at once, giving a higher weight loss.
55
The spread in the measurements is probably caused by uncertainty in the
weight determination and diculties with char recovery. The error that is in-
troduced by weighing is about 0.8% (on an initial weight of 6 mg), since the
scale weighs the weight in 0.01 mg but it was read to 0.1 mg. The error in the
char recovery is dicult to quantify, but the recovery will tend to be slightly
too low because of residues left on the grid. The recovery appears however to
be reasonably well since overall virtually no residue was left on the grid.
4.2.2 Slow vs. fast pyrolysis
In table 4.1 the yield of DDGS in slow pyrolysis, from the work of Giuntoli
et al.[3], and fast pyrolysis are compared. Please note that the yields for CO,
CO
2
, NH
3
and HCN are given before isothermal heating. In the slow heating
rate experiments, the setup is kept at 900

C for 60 minutes after the initial

heating. The mentioned species show an additional release when kept at 900

C
for a long time. This can be attributed to a secondary devolatilization step,
associated with decomposition of the rearranged structure of the solid[71]. Since
this process is limited by mass transfer, this step will not take place during fast
pyrolysis. It is thus more accurate to compare the yields before isothermal
heating.
Table 4.1: Volatile yields for slow and fast pyrolysis at 900

C
Gas compound Slow pyrolysis Fast pyrolysis
DDGS DDGS leached DDGS DDGS leached
CO
2
[wt% d.b.] 8.2
1
9.5
1
12.3 13.2
CO [wt% d.b.] 6.3
1
7.3
1
7.6 7.7
CH
4
[wt% d.b.] 1.5 1.6 1.1 1.2
H
2
O [wt% a.r.] 5.4 2.5 9.8 10.8
NH
3
[wt% d.b.] 1.4
1
1.8
1
0.1 0.2
HCN [wt% d.b.] 1.2
1
1.8
1
0.6 0.7
HNCO [wt% d.b.] 0.5 0.5 0 0
It appears that the fast pyrolysis yields for CO and CH
4
are similar to the
yields at low heating rate. The CO
2
yields however show an increase of about
50%. In the work of De Jong[57] on miscanthus the yields of CO are also similar
for both low and high heating rate, while the yields for CO
2
are much (16 times)
lower for high heating rate. De Jong suggested CO
2
could be formed from the
decomposition of carboxylic acids which would be favored in slow pyrolysis.
The lower yields at high heating rates in de work of De Jong could be explained
by the relative cold environment in which no CO
2
can be released from the
carboxylic acids. The increase in CO
2
yields in fast pyrolysis found in this
study, is however dicult to explain. It could be that a major part of the
release of CO
2
from carboxylic acids takes place in the gas phase. Since the
heated grid is surrounded by a hot zone, it could be that more CO
2
is released
here compared to slow pyrolysis. In the work of Becidan et al.[72] the yields
for CO
2
from biomass are similar at both slow and fast heating rate. In both
experiments the same setup is used with the same thermal history for the gas
1
Non-isothermal yield
56
phase. The reactor used in these experiments allows for substantial secondary
gas phase reactions since the gases are heated. This would hint towards the
release of CO
2
in the gas phase. To gain a better insight on the release of
CO
2
, future research could focus on the yields of carboxylic acids as was also
suggested by De Jong.
Also the H
2
O yields show an increase of almost 100% and over 400% for
DDGS and leached DDGS, respectively. A possible explanation could be that
the H
2
O is consumed in a reaction mechanism in the solid at low heating rate
which does not occur at high heating rates. The production of H-radicals to
hydrogenate char-N and form NH
3
could be such a reaction[30].
For NH
3
the yield at high heating rate is only about 10% of the one at slow
pyrolysis, while the HCN yield is about 50%. These large dierences were also
observed in the work of Di Nola for NH
3
and HCN. For chicken litter, Di Nola
saw a decrease at high heating rate of about 95% for NH
3
and 90% for HCN.
For meat and bone meal, the NH
3
reduced with about 85% and HCN decreased
50%.
The lower yield in NH
3
suggests that hydrogenation of char-N is not a main
source of NH
3
, since this mechanism would be favored by high heating rates[29].
However since the amount of H
2
O at high heating rates in this study is increased
while the NO
x
precursors decrease, this might suggest that NH
3
is formed from
hydrogenation with H radical from H
2
O at low heating rates. At high heating
rates the H
2
O might be released before releasing H-radicals. Why the yields for
the NO
x
precursors decrease with increasing heating rate, can not be explained
by the mechanisms suggested by Becidan[19].
4.2.3 Nitrogen species
The experimental setup was calibrated for the nitrogen species NH
3
, HCN,
HNCO, NO and NO
2
. Only the rst two were found in signicant amounts. This
makes sense since these are the most important precursors for NO
x
, while HNCO
is a minor species and NO and NO
2
are mostly formed during combustion. NH
3
was only detected in signicant amounts in the volatile products of DDGS, not
of PKC. Some NH
3
was found for PKC, however the quantities were too small
to be quantied. This is probably caused by the lower amount of nitrogen in
the PKC. The leaching slightly increases both the yield of NH
3
and HCN. This
is similar to what has been found by Giuntoli et al.[3] (see table 4.1).
The amounts of HCN and NH
3
in the fast pyrolysis experiments are signi-
cantly lower than what was found for low heating rates. A similar observation
can be found in the work of Di Nola[1] as was mentioned before. Also at lower
heating rates, Di Nola also found a decrease in NH
3
and HCN yields with heat-
ing rates increasing from 10 to 100 K/min. This trend was also found by De
Jong[57] on the pyrolysis of miscanthus. This is contradictory to what has been
found by Becidan[72], who found an increase in nitrogen yields with increasing
heating rates from 8.3 to 115 K/min. The main dierence between the studies
is that Di Nola and De Jong used a TG-FTIR setup, while Becidan used a steel
tube reactor coupled to an FTIR. The sample size of 75g in the experiments
done by Becidan is signicantly larger than the sample size in the TG-FTIR[36].
The larger sample size allows for more gas-solid interactions in the sample. Also
the gas was heated in the reactor in the experiments of Becidan, so this should
be considered when comparing to this study. The trend found by Becidan is
57
however also found in other studies[30, 73]. Di Nola suggested that the decreas-
ing nitrogen volatile yields with increasing heating rates are a result of heat
and mass transfer limitations. This explanation is at least questionable, since
these eects would be even larger in the experiments of Becidan. It suggests
however that the volatile yields are at least to some extend inuenced by the
used equipment.
400 600 800 1000 1200 1400
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
Temperature [C]
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]


DDGS
DDGS leached
(a) NH3 yield over initial weight
400 600 800 1000 1200 1400
0
1
2
3
4
5
6
7
Temperature [C]
N
H
3

N

y
i
e
l
d

[
w
t
%

o
f

i
n
i
t
i
a
l

N
]


DDGS
DDGS leached
(b) NH3 yield over initial N
Figure 4.2: HCN yield as a function of temperature
The amount of NH
3
released from DDGS appears to be a linear function,
while the leached DDGS is linear with a maximum at 1200

C (gure 4.2). Since

decarboxylation, one of the two main suggested nitrogen pathways[19], is a
strong function of temperature unlike hydrogenation[74], it is likely that this
is an important phenomenon in these experiments. As previously mentioned,
hydrogenation is considered to be important at low heating rates. This would
help to explain the dierence in H
2
O and NH
3
yields.
The trend for HCN is quite linear from temperatures of 800

C and up (gure
4.3). This is similar to what was found by Di Nola[1] and is a trend that is often
reported in literature[19]. The bend in the trend of HCN release from leached
DDGS is probably caused by the fact that at this point most of the nitrogen is
released. This was not observed for the other biomass. Also for HCN a large
part was released below 500

C in slow pyrolysis, while the yield in fast pyrolysis

are signicantly increasing for higher temperatures in fast pyrolysis. This also
suggests dierent reaction mechanisms at high heating rates.
If we look at the HCN release over initial N, it appears that the conversion
for both DDGS and PKC is almost equal. For the NH
3
yield in untreated and
leached DDGS this is not the case, since the N content hardly changes after
leaching.
The ratio of HCN over NH
3
is increasing with temperature, this was also
found by Di Nola and Hansson[31] (gure 4.4). The gure also shows that leach-
ing favors the release of NH
3
. It could be that leaching changed the structure
of the biomass in such a way that NH
3
is released easier. It could however
also be that dierence in grinding introduced a dierence in structure, since the
58
400 600 800 1000 1200 1400
0
0.5
1
1.5
2
2.5
Temperature [C]
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]


DDGS
DDGS leached
PKC
PKC leached
(a) HCN yield over initial weight
400 600 800 1000 1200 1400
0
5
10
15
20
25
30
Temperature [C]
H
C
N

N

y
i
e
l
d

[
w
t
%

o
f

i
n
i
t
i
a
l

N
]


DDGS
DDGS leached
PKC
PKC leached
(b) HCN yield over initial N
Figure 4.3: HCN yield as a function of temperature
untreated DDGS was ground by hand while the leached DDGS was received in
powder form.
500 600 700 800 900 1000 1100 1200 1300
1
2
3
4
5
6
7
8
9
10
11
T [C]
H
C
N
/
N
H
3

[
m
g
/
m
g
]


DDGS
leached DDGS
Figure 4.4: Ratio of HCN over NH
3
59
4.2.4 H
2
O, CO, CO2 and CH4
Besides the NO
x
precursors, the yields for H
2
O, CO, CO2 and CH4 are deter-
mined. The amount and trend of H
2
O release is similar for both fuels. Since
the water release is almost constant over the temperature range (gure 4.5),
this will probably originate from the moisture content for the largest part. This
assumption is supported by the fact that the moisture content for all fuels is
approximately 9%. Overall the behavior of the H
2
O yield is similar to what has
been found by Di Nola[1] for chicken litter and meat and bone meal.
400 600 800 1000 1200 1400
0
2
4
6
8
10
12
14
16
18
20
Temperature [C]
Y
i
e
l
d

[
w
t
%

a
.
r
.
]


DDGS
DDGS leached
(a) DDGS
400 600 800 1000 1200 1400
0
2
4
6
8
10
12
14
16
18
20
Temperature [C]
Y
i
e
l
d

[
w
t
%

a
.
r
.
]


PKC
PKC leached
(b) PKC
Figure 4.5: H
2
O yield as a function of temperature
Just like the behavior of the H
2
O yield, the behavior of the CO (gure 4.6)
and CO
2
(gure 4.7) yield are quite similar for DDGS and PKC. For DDGS the
yield of CO
2
is a little higher, while for PKC the CO yield is a little higher. The
behavior of the CO yield is quite linear from 700-800 till 1300

C. The yields
start at about 5% at 800

C and reach up to about 19% to 23% for leached

DDGS and the other fuels, respectively. This trend corresponds to what has
been found by De Jong[57] and Di Nola et al.[60], who studied coal and dierent
types of biomass in a heated wire mesh setup. The research of De Jong was
done on miscanthus, which gave quite similar yields in terms of CO (7.2%daf
CO). Leaching seems to delay the CO yield to some extend for the DDGS.
One of the sources of CO is cellulose, since this compound releases mainly
CO[75]. Since the yields for CO are still increasing at 1300

C, this compound
probably also originates from restructuring within the biomass since this process
is limited by mass transfer as discussed before. It is also possible that some CO
is formed due to tar cracking, which seems to take place according to the carbon
partitioning (gure 4.11). Di Nola found similar behavior for chicken litter in
terms of CO release.
The CO
2
release is linear with temperature up to 1200

C, going from about

10 to 15 wt%. In the work of Di Nola et al. the trend for CO
2
appears also
to be quite linear, although the amounts are quite dierent between dierent
materials. The yield of CO
2
in the work De Jong was found to be independent
of temperature and signicantly lower. CO
2
shows behavior that is signicantly
60
dierent from the behavior of CO and CH
4
and will probably originate from
other reaction mechanisms. In the slow pyrolysis experiments, most of the CO
2
from DDGS was released at temperatures below 500

C. This explains that in

these results already at 500

C a signicant amount of CO
2
is released.
400 600 800 1000 1200 1400
0
5
10
15
20
25
Temperature [C]
Y
i
e
l
d

[
w
t
%

d
.
b
.
]


DDGS
DDGS leached
PKC
PKC leached
Figure 4.6: CO yield as a function of temperature
400 600 800 1000 1200 1400
0
2
4
6
8
10
12
14
16
18
20
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Temperature [C]


DDGS
DDGS leached
PKC
PKC leached
Figure 4.7: CO
2
yield as a function of temperature
The CH
4
yields are again very similar for all biomass in this study. Also
this compound probably originates partly from cellulose, as this is the main
cellulosic compound for DDGS[76]. Just as for the CO yield, the CH
4
yield
is still increasing at 1300

C. This could be explained by the cracking of tar

compounds like toluene and cresol, which contain a methyl group.
61
400 600 800 1000 1200 1400
0
0.5
1
1.5
2
2.5
3
3.5
4
Y
i
e
l
d

[
w
t
%

d
.
b
.
]
Temperature [C]


DDGS
DDGS leached
PKC
PKC leached
Figure 4.8: CH4 yield as a function of temperature
4.2.5 Partitioning
The partitioning of the volatiles of the dierent fuels look very similar. In gures
4.9 and 4.10, the volatile composition as a function of temperature is presented.
Please note that H
2
O was left out, since presenting this species on d.a.f. free
basis would not be appropriate for this species.
400 600 800 1000 1200 1400
0
5
10
15
20
25
30
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Temperature [C]


CO
CO2
CH4
(a) Main volatile species
400 600 800 1000 1200 1400
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Temperature [C]


NH3
HCN
(b) Nitrogen volatile species
Figure 4.9: Volatile composition for DDGS
62
400 600 800 1000 1200 1400
0
5
10
15
20
25
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Temperature [C]


CO
CO2
CH4
(a) Main volatile species
400 600 800 1000 1200 1400
0
0.2
0.4
0.6
0.8
1
1.2
1.4
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Temperature [C]


HCN
(b) Nitrogen volatile species
Figure 4.10: Volatile composition for PKC
The partitioning of carbon, hydrogen and nitrogen between volatiles, char
and tar has been determined for DDGS at 900 and 1200

C. The char C,H,N

content was determined according to ASTM 3178 by BELAB AB, Sweden. The
mass balance can not be closed since the amounts of tar, H
2
and N
2
are unknown.
In gure 4.11 these compounds are presented as tar.
1 2 3 4
0
10
20
30
40
50
60
70
80
90
100
sample
%


Volatiles
Char
Tar
1 2 3 4
0
10
20
30
40
50
60
70
80
90
100
sample
%


Volatiles
Char
Tar
1 2 3 4
0
10
20
30
40
50
60
70
80
90
100
sample
%


Volatiles
Char
Tar
Figure 4.11: The partioning of carbon (left), hydrogen (middle) and nitrogen
(right). The samples are DDGS at 900

C (1) and 1200

C (2) and leached DDGS

at 900

C (3) and 1200

C (4).
It appears that at 1200

C, still a considerable amount (about 15%) of carbon

is left in the char. This is to be expected since the biomass has a considerable
amount of xed carbon. Also, at higher temperatures volatiles are not only
increasing at the expenses of the char content, but also the tar content. This is
probably caused by thermal cracking of the tars, mainly forming CO.
63
Most of the hydrogen is released already at 900

C. Also here, tar cracking

appears to take place since the amount of volatiles is increasing at the expenses
of tar hydrogen. This will mainly be in the form of CH
4
which can be formed
from methyl groups, as discussed before.
Also for nitrogen still a considerable amount is left in the char at 1200

C.
This makes sense since less nitrogen species were found, compared to low heating
rate experiments. At higher temperatures also nitrogen appears to be formed
from tars.
4.3 The inuence of the holding time and heat-
ing rate
The parameters of holding time and heating rate are also evaluated in this study.
The holding time is the time that the biomass is kept at peak temperature.
The holding time was not found to be of inuence for holding times between
2 and 10 seconds in the study of Di Nola[1]. This measurement was however
done at 1200

C. In this study the holding time was studied, both at 500 and
1300

C. It was found that at 500

C the holding time does inuence the volatile

yields with an increase of about 15% between 5 and 10 seconds, see gure
4.12. The volatile yield does not signicantly change between 10 and 15 seconds
holding time, but for a holding time below 10 seconds there clearly are heat
transfer limitations. Since after 10 seconds the weight loss appears to be still
not complete, the holding time for DDGS at 500

C is set to 15 seconds instead

of 10. The volatile composition shows the same behavior as the weight loss, see
appendix C.
4 6 8 10 12 14 16
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
(a) T=500

C
4 6 8 10 12 14 16
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
(b) T=1300

C
Figure 4.12: Weight loss as a function of the holding time.
64
Heating rates of 600 and 1000

C/s were evaluated. Also the inuence of

the heating rate was evaluated at 500 and 1300

C. At both temperatures, no
signicant inuence of the heating rate was found. This corresponds to what is
found by Di Nola[1].
550 600 650 700 750 800 850 900 950 1000 1050
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
Heating rate [C/s]
(a) T=500

C
550 600 650 700 750 800 850 900 950 1000 1050
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
Heating rate [C/s]
(b) T=1300

C
Figure 4.13: Weight loss as a function of the heating rate.
65
4.4 Discussion & conclusions
The results obtained from the experiments show clear trends on the inuence
of temperature during fast pyrolysis. However as discussed in chapter 3, the
temperatures should be treated with caution because of the dierence between
the grid and sample. When looking at the volatile yields of slow and fast pyrol-
ysis, more research is needed to give a solid explanation for the dierences. An
important part of the uncertainty is caused by discrepancies between literature
on nitrogen chemistry associated with biomass.
4.4.1 Conclusions
From the ndings in this chapter on experimental results, a number of important
conclusions can be drawn. The following conclusions are important to mention:
The studied potential fuels show very similar behavior in terms of weight
loss and volatile release as a function of temperature.
Leaching in water does not signicantly inuence the weight loss and
volatile product composition as a function of temperature.
Yields of CO
2
are higher at high than at low heating rate, probably due
to release from carboxylic acids in the hot gas.
Yields of H
2
O are higher at high than at low heating rate, probably be-
cause this compound is consumed in reactions like generation of H-radicals
at low heating rate.
Yields of NH
3
and HCN are lower at high heating rate, probably due to
less hydrogenation with H-radicals from H
2
O.
HCN is the main NO
x
precursor found in both fuels, while NH
3
levels of
PKC were too low to quantify.
Leaching in water increases the yield of NH
3
, while HCN remains virtually
the same.
The ratio of HCN/NH
3
release increases with temperature.
Tar cracking appears to take place, according to the partitioning of C,H
and N containing species between volatiles, tar and char.
Holding time inuences the yields at 500

C between 5 and 10 seconds, but

not at 1300

C.
The dierence between heating rates of 600 and 1000K/s does not cause
not cause signicant changes in volatile yields.
66
Chapter 5
Conclusions and
recommendations
5.1 Conclusions
The main research question posed during this study was:
How do the parameters of temperature, heating rate and holding time inuence
the yields and composition of volatiles released and the partitioning of nitrogen
during fast pyrolysis of DDGS and PKC?
Answering this question, the following conclusions can be drawn:
Overall, increasing the pyrolysis temperature increases the yields of all the
volatile species.
The dierence in heating rate does not inuence the pyrolysis product
composition for values of 600 and 1000 K/s.
The holding time at peak temperature is signicantly inuencing the
volatile yield for times shorter than 10 seconds at 500

C. At 1300

C
no inuence of holding times longer than 5 seconds was found.
In the experimental results it appears that the behavior of DDGS and PKC
is quite similar in terms of weight loss and volatile composition as a function
of temperature. Also the eect of leaching was found to be neglegible. When
comparing with low heating rate experiments performed by Giuntoli et al.[3],
the yields dier signicantly for the species CO
2
, H
2
O, NH
3
and HCN.
The main NO
x
precursor found in this study was HCN, while no HNCO
was found. In NH
3
was only found in signicant quantities in DDGS, while the
amounts in PKC were too small to quantify. The yields of both NH
3
and HCN
were found to increase with temperature. The lower yields in NO
x
precursors
compared to low heating rate pyrolysis is suggested to be caused by the reduced
hydrogenation of char-N.
From the modeling of the reactor, no hot spotswere found in the uid except
for the area around the grid. Also, the gradient in grid temperature appears
67
to be limited in the center, while sharply increasing towards the electrodes.
This means that the surface temperature of the sample can be considered quite
homogeneous when placed in the center of the grid. From a rst approximation
in the modeling, the temperature and heating rate of the biomass sample diers
signicantly.
During the evaluation of the experimental setup, it was discovered that the
volatiles need some time to reach a homogeneous distribution along the reactor
volume. This has to be taken into account when quantifying the volatile prod-
ucts. Also, NH
3
appears to be adsorbed to some extent during the experiments.
Last but not least, the temperature of the grid is signicantly higher than in-
dicated by the thermocouple, this has to be taken into account when reporting
results of this setup.
5.2 Recommendations
During this study, a model of the experimental setup was made. The temper-
ature prediction for the grid was found to be good at temperatures >800

C.
However in pyrolysis the temperature of the sample is one of the main con-
cerns. Since only a rst approximation was made in this study, the modeling
of the sample should be improved. Also, the release of volatile species could
be incorporated in the model to model mixing behavior and possible secondary
reactions. Concluding, the main recommendations for the model are:
The relations for the thermal behavior of the pyrolysis sample should be
improved, using the work of Damartzis et al.[58] as a reference. More
details on the suggested approach can be found in chapter 3.7.
The release of volatile species could be incorporated in the model to pro-
vide a better insight in the mixing behavior and possible secondary reac-
tions. The required kinetics can be obtained form slow pyrolysis experi-
ments.
Also on the experimental part some recommendations arise from the current
study. The recommendations on this part are:
In this work, NH
3
was assumed to adsorb in the reactor. The yields were
determined indirectly, since the quantication of the adsorption was not
succesful. For future research, it is recommended to try to quantify this
amount and investigate whether other components such as H
2
O and HCN
might also adsorb.
Since the grid temperature was found to be higher than indicated by the
thermocouple, it is recommended to use the following relation to predict
the actual grid temperature: T
Grid
1.15 T
Thermocouple
To reduce the mentioned dierence in temperature between the sample
and the grid, thinner samples should be used. However the sample weight
should not be reduced, so the pill diameter should be increased. Since
the gradient in the grid at the center is limited, this does not signicantly
inuence the sample temperature.
68
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74
Appendices
75
Appendix A
Biomass properties
Table A.1: Proximate and elemental analysis of evaluated biomass residues
(% dry basis) DDGS DDGS leached PKC PKC leached
Proximate analysis
1
Moisture
2
8.9 8.5 7 9.2
Volatiles 78.2 76.2 75.5 75.1
Fixed carbon 14.7 17 18.4 19.5
Ash 7.1 6.8 6.1 5.4
Elemental analysis
1
C 49.00 48.80 49.99 47.76
H 6.34 6.32 6.01 6.05
N 4.47 4.50 2.35 2.71
S 0.43 0.44 0.53 0.38
O 32.65 33.2 36.0 37.7
HHV [MJ/kg] 19.81 20.50 17.81 18.85
Table A.2: Elemental ash analysis of evaluated biomass residues
(% dry basis) DDGS DDGS leached PKC PKC leached
Al
2
O
3
0.2 0.4 4.8 5.3
SiO
2
22.4 28.8 16.2 23.3
CaO 3.2 2.4 10.2 7.1
MgO 12.7 6.2 11.4 6.5
Fe
2
O
3
0.4 0.5 11.5 14.3
K
2
O 22.7 22.4 15.1 12.3
Na
2
O 2.8 1.8 0.4 0.1
TiO
2
0.01 0.01 0.2 0.2
SO
3
2
11.5 2.0 9.2 2.4
Cl

2.9 0.9 3.3 0

P
2
O
5
31.7 18.8 25.9 28.9
1
Performed with automatic procedure on a Carlo Erba EA 9010 manufactured by Fisons.
2
On as received basis
77
Appendix B
Quantication method
The quantication of the data obtained from the FTIR is done using the Quant
Pad software, part of the OMNIC 6.1 software package. The method quanties
the following volatile species: NH
3
, HCN, NO, H
2
O, CO, CH
4
, CO
2
, NO
2
and
HNCO.
Each species has its own characteristic peak in the infrared absorption wave-
length. Using that characteristic peak, the following wavelength windows are
used for quantication:
Table B.1: Component detection regions and windows
Component Region [cm
1
] Window [cm
1
]
NH
3
1039.6.0-1108.4
1039.6-1050.4
1061.8-1069.7
1099.1-1108.4
HCN
1584.9-1600.3
1584.9-1586.3
1596.8-1600.3
NO
1851.0-1877.0
1851.0-1855.0
1873.0-1877.0
H2O
2070.9-2137.3
2070.9-2080.0
2129.0-2137.3
CO
2286.9-2291.3
2286.9-2287.6
2290.6-2291.3
CH
4
2373.0-2381.9
2373.0-2374.1
2379.2-2380.1
2381.1-2381.9
CO
2
3044.8-3133.0
3044.8-3051.6
3117.7-3126.2
3127.8-3133.0
NO
2
3260.0-3360.0
3260.0-3280.0
3340.0-3360.0
HNCO 3884.2-3904.8
3884.2-3886.8
3898.2-3900.0
3902.8-3904.8
The following component corrections were chosen based on the available
79
calibrations:
Table B.2: Component corrections
Component x
0
x
1
x
2
Range [ppm] Avg. error [%]
NH
3
1.396768e+00 9.399489e-01 3.370036e-04 10-1000 1.16
HCN -2.302851e-01 8.035513e-01 4.120027e-04 10-1000 3.64
NO 0e+00 1.014879e+00 10-850 2.93
H
2
O 0e+00 8.460079e-01 2.254996e-04 0-7000 2.09
CO 0e+00 7.015759e-1 3.348646e-04 100-10000 3.21
CH
4
0e+00 8.812584e-01 4.094992e-04 100-20000 6.33
CO
2
-1.819956e+01 6.279380e-01 1.308933e-03 100-10000 1.13
NO
2
8.695898e+00 7.946310-01 100-10000 4.77
HNCO 0e+00 1e+00 100-1000 0
80
The calibration curves for each species are presented in the following gures.
90,0 317,5 545,0 772,5 1000,0
100,0
550,0
1000,0
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.1: NH
3
calibration line.
81
0 500 1000 1500 2000
0,0
500,0
1000,0
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.2: HCN calibration line.
0,0 250,0 500,0 750,0 1000,0
0,0
500,0
1000,0
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.3: NO calibration line.
82
1000 2250 3500 4750 6000
1000
4000
7000
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.4: H
2
O calibration line.
0 2250 4500 6750 9000
0
5000
10000
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.5: CO calibration line.
83
0 5000 10000 15000 20000
0
10000
20000
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.6: CH
4
calibration line.
1000 2000 3000 4000 5000
1000
4000
7000
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.7: CO
2
calibration line.
84
70,0 252,5 435,0 617,5 800,0
70,0
335,0
600,0
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.8: NO
2
calibration line.
400,0 425,0 450,0 475,0 500,0
300,0
400,0
500,0
Calibration Curve
Measured
A
c
t
u
a
l
Figure B.9: HNCO calibration line.
85
Appendix C
Reactor dimensions
In gure 3.2, an overview of the reactor model is presented. In the following
gures, the dimensions of the model are given in mm.
Figure C.1: 3D overview of the reactor.
87
Figure C.2: Cross section of the reactor in the x-z plane.
Figure C.3: Reactor side view in the y-z plane.
88
Figure C.4: Reactor top view in the x-y plane.
89
Appendix D
Model settings
In this appendix, the settings used in the model are presented. For all settings,
the associated menu in the COMSOL program is specied. Only data other
than default is given.
D.1 Mesh
As already was explained in the report, the subdomains were meshed one by
one, starting with the grid. This was done to be able to change element size
between the subdomains and to judge the mesh quality while creating the mesh.
The number of elements in the dierent subdomains is presented in table D.1,
while the numbering of the subdomains is shown in gure D.1.
Table D.1: Number of elements in the subdomains
Subdomain Number of elements
1 48081
2 1984
3 1179
4 2620
5 1859
6 1838
7 144
8 152
9 1861
10 1199
Total 60917
91
Figure D.1: Subdomain numbers.
D.2 Constants
These constants were specied in: Options Constants...
Table D.2: Model constants
Name Value Unit
T wall 110

C
T lid 95

C
p atm 1.013 bar
g 9.81 m/s
2
D.3 Scalar expressions
In the model, only 1 scalar expression is used. This scalar was specied in:
Options Expressions Scalar expressions...
rho he ref=mat1 rho(p atm[1/Pa],T wall[1/K])
92
D.4 General heat transfer
D.4.1 Subdomain
The settings for the dierent subdomains are given in table D.3. The helium
properties were taken from the Materials/Coecients Library Gases/Liquids
. The steel properties were not available in the used distribution of COMSOL,
this data was imported from the COMSOL 3.5 distribution material library
available on the university computers. The type of steel that was used is AISI
304. Please note that Q
d
c is the heat production by the current.
These settings are available from: Physics Subdomain settings.
Table D.3: General heat transfer subdomain settings
Subdomain k [W/(m*K)] [kg/m
3
] C
p
[J/(kg*K)] Q [W/m
3
]
Fluid k
helium
(T)
helium
(p,T) C
p,helium
(p,T) 0
Grid and electrodes k
steel
(T)
steel
(T) C
p,steel
(T) Q
dc
Thermocouple supports k
steel
(T)
steel
(T) C
p,steel
(T) 0
In the uid subdomain, convective heat transfer is enabled. The matter state
is set to Gas/Liquid, the velocity vector is specied by u,v and w. The ratio
of the specic heats is 1.66 from the helium properties. Finally, the absolute
pressure is p
a
tm.
D.4.2 Boundary settings
These settings are available from: Physics Boundary settings.
Table D.4: General heat transfer boundary equations
Boundary Setting Value
Inlet Temperature T
wall
Outlet Convective ux -
Reactor top Temperature T
lid
Other external Temperature T
wall
Internal boundaries boundaries Continuity -
The boundary settings for the grid are a bit more complicated. The bound-
ary condition is set to heat source/sink. The variables q
0
, h and T
inf
are left
zero, since convective heat transfer is calculated by the ow. The other setting
are the following:
Table D.5: Grid radiation settings
Radiation type Surface-to-ambient
0.75
T amb T wall
J
0
epsilon htgh*sigma htgh*T
4
Please note that the setting for J
0
is set by the program.
93
D.5 Conductive media
D.5.1 Subdomain settings
The for the conductivity relation, conductivity as a function of the temperature
is used. This property is also taken from the COMSOL material library.
D.5.2 Boundary settings
The boundary settings for the conductive media module are shown below. The
value of I(t) is taken from the heated grid software. The current is divided by
the electrode cross section to get the right current density.
Table D.6: Conductive media boundary settings
Boundary Setting Value
Electrode 1 Inward current ow I(t)/1.242e-5
Electrode 2 Ground -
Other boundaries Electric insulation -
D.6 Weakly compressible Navier Stokes
D.6.1 Subdomain settings
Table D.7: Fluid subdomain settings

helium
(p+p atm,T)

helium
(T)
kappa
dv
0
F
x
0
F
y
0
F
z
g*(rho he ref-rho chns)
D.6.2 Boundary settings
Table D.8: Weakly compressible Navier Stokes boundary equations
Boundary Setting Value
Inlet Velocity U
0
=0.218
Outlet Pressure, no viscous stress p
0
=0
Other boundaries No slip -
94
D.7 Solver
D.7.1 Parameters
The solver parameters are available from: Solve Solver parameters...
Please note that the used solver for the module Navier Stokes is dierent
from the other two, since this module includes non-linearities.
Table D.9: Solver parameters
Parameter Value
Analysis type Transient
Solver Time dependent segregated
General: time stepping: times range(0,0.1,t
exp
1
)
Time stepping: Method Generalized alpha
The following settings are available from: Solver Parameters General:
Segregated groups Settings...
Table D.10: Segregated groups
Module Linear Solver Preconditioner or Pre-/Postsmoother
Weakly Compressible Navier Stokes Geometric multigrid Vanka
General Heat Transfer GMRES Geometric Multigrid - SSOR
Conductive Media GMRES Geometric Multigrid - SSOR
D.7.2 Manager
From the solver manager, both the Initial valueand Values of variables not
solved for and linearization pointare set to current value for the transient anal-
ysis. In order to solve this, the model was initially solved in steady state without
specifying a current. This steady state solution gives the starting point of the
analysis, associated with the initial conditions in the experiments.
1
Where texp is the time of the experiment.
95
96
Appendix E
Devolatilization results
E.1 Inuence of the nal temperature
400 600 800 1000 1200 1400
80
85
90
95
100
105
W
e
i
g
h
t

l
o
s
s

[
w
t
%

d
.
a
.
f
.
]
400 600 800 1000 1200 1400
80
85
90
95
100
105
400 600 800 1000 1200 1400
80
85
90
95
100
Temperature [C]
W
e
i
g
h
t

l
o
s
s

[
w
t
%

d
.
a
.
f
.
]
400 600 800 1000 1200 1400
80
85
90
95
100
105
Temperature [C]
Figure E.1: Weightloss as a function of temperature
400 600 800 1000 1200 1400
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
Temperature [C]
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]


DDGS
DDGS leached
Figure E.2: NH3 yield as a function of temperature
97
400 600 800 1000 1200 1400
0
0.5
1
1.5
2
2.5
Temperature [C]
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]


DDGS
DDGS leached
PKC
PKC leached
Figure E.3: HCN yield as a function of temperature
400 600 800 1000 1200 1400
0
2
4
6
8
10
12
14
16
18
20
Temperature [C]
Y
i
e
l
d

[
w
t
%

a
.
r
.
]


DDGS
DDGS leached
PKC
PKC leached
Figure E.4: H2O yield as a function of temperature
400 600 800 1000 1200 1400
0
5
10
15
20
25
Temperature [C]
Y
i
e
l
d

[
w
t
%

d
.
b
.
]


DDGS
DDGS leached
PKC
PKC leached
Figure E.5: CO yield as a function of temperature
400 600 800 1000 1200 1400
0
2
4
6
8
10
12
14
16
18
20
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Temperature [C]


DDGS
DDGS leached
PKC
PKC leached
Figure E.6: CO2 yield as a function of temperature
98
400 600 800 1000 1200 1400
0
0.5
1
1.5
2
2.5
3
3.5
4
Y
i
e
l
d

[
w
t
%

d
.
b
.
]
Temperature [C]


DDGS
DDGS leached
PKC
PKC leached
Figure E.7: CH4 yield as a function of temperature
E.2 Inuence of the holding time
4 6 8 10 12 14 16
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.8: Weightloss as a function of the holding time
@ 500

C
4 6 8 10 12 14 16
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.9: Weight loss as a function of the holding time
@ 1300

C
99
4 6 8 10 12 14 16
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]


DDGS
DDGS leached
Figure E.10: NH3 yield as a function of the holding time
@ 1300

C
4 6 8 10 12 14 16
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.11: HCN yield as a function of the holding time
@ 500

C
4 6 8 10 12 14 16
0
1
2
3
4
5
6
7
8
9
10
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.12: HCN yield as a function of the holding time
@ 1300

C
4 6 8 10 12 14 16
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.13: H2O yield as a function of the holding time
@ 500

C
100
4 6 8 10 12 14 16
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.14: H2O yield as a function of the holding time
@ 1300

C
4 6 8 10 12 14 16
0
1
2
3
4
5
6
7
8
9
10
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.15: CO yield as a function of the holding time @
500

C
4 6 8 10 12 14 16
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.16: CO yield as a function of the holding time @
1300

C
4 6 8 10 12 14 16
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.17: CO2 yield as a function of the holding time
@ 500

C
101
4 6 8 10 12 14 16
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.18: CO2 yield as a function of the holding time
@ 1300

C
4 6 8 10 12 14 16
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.19: CH4 yield as a function of the holding time
@ 500

C
4 6 8 10 12 14 16
0
1
2
3
4
5
6
7
8
9
10
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
t[s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.20: CH4 yield as a function of the holding time @ 1300

C
102
E.3 Inuence of the heating rate
550 600 650 700 750 800 850 900 950 1000 1050
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
Heating rate [C/s]
Figure E.21: Weightloss as a function of the heating rate
@ 500

C
550 600 650 700 750 800 850 900 950 1000 1050
50
55
60
65
70
75
80
85
90
95
100
W
e
i
g
h
t

l
o
s
s

[
w
t
%

a
.
r
.
]
Heating rate [C/s]
Figure E.22: Weight loss as a function of the heating rate
@ 1300

C
550 600 650 700 750 800 850 900 950 1000 1050
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
Figure E.23: NH3 yield as a function of the heating rate
@ 1300

C
550 600 650 700 750 800 850 900 950 1000 1050
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.24: HCN yield as a function of the heating rate
@ 500

C
103
550 600 650 700 750 800 850 900 950 1000 1050
0
1
2
3
4
5
6
7
8
9
10
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.25: HCN yield as a function of the heating rate
@ 1300

C
550 600 650 700 750 800 850 900 950 1000 1050
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.26: H2O yield as a function of the heating rate
@ 500

C
550 600 650 700 750 800 850 900 950 1000 1050
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.27: H2O yield as a function of the heating rate
@ 1300

C
550 600 650 700 750 800 850 900 950 1000 1050
0
1
2
3
4
5
6
7
8
9
10
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.28: CO yield as a function of the heating rate @
500

C
104
550 600 650 700 750 800 850 900 950 1000 1050
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.29: CO yield as a function of the heating rate @
1300

C
550 600 650 700 750 800 850 900 950 1000 1050
0
1
2
3
4
5
6
7
8
9
10
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.30: CO2 yield as a function of the heating rate
@ 500

C
550 600 650 700 750 800 850 900 950 1000 1050
0
5
10
15
20
25
30
35
40
45
50
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.31: CO2 yield as a function of the heating rate
@ 1300

C
550 600 650 700 750 800 850 900 950 1000 1050
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.32: CH4 yield as a function of the heating rate
@ 500

C
105
550 600 650 700 750 800 850 900 950 1000 1050
0
1
2
3
4
5
6
7
8
9
10
Y
i
e
l
d

[
w
t
%

d
.
a
.
f
.
]
Heating rate [C/s]


DDGS
DDGS leached
PKC
PKC leached
Figure E.33: CH4 yield as a function of the heating rate @ 1300

C
106