Fuel 89 (2010) 36503661

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Fuel
journal homepage: www.elsevier.com/locate/fuel

A comprehensive mathematical model for biomass gasication in a bubbling

uidized bed reactor
Priyanka Kaushal, Jalal Abedi *, Nader Mahinpey
Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Dr. NW, Calgary, Alberta, Canada T2N 1N4

a r t i c l e i n f o a b s t r a c t

Article history: A mathematical model of biomass gasication in bubbling uidized gasier has been developed. It is a
Received 29 January 2010 one-dimensional, two-phase (bubble and emulsion), two-zone (bottom dense bed and upper freeboard),
Received in revised form 20 July 2010 steady state model. The model is based on global reaction kinetic, mass and energy balances and is capa-
Accepted 21 July 2010
ble of predicting temperature, solid hold ups and gas concentration along the reactors major axis. The
Available online 4 August 2010
overall model has sub-models to deal with biomass pyrolysis, gasication, bed hydrodynamics, material
classication and property calculation. A sub-model for tar generation and cracking is included in this
Keywords:
study. The model is capable of dealing with wide variety of biomasses and uidizing agents, i.e. air, oxy-
Chemical process
Gasication
gen, steam or a mix of these gases. Results show that during devolatilization step, gases release and mix-
Fluidization ing are sensitive and critical parameters. They have a strong inuence on the overall performance of a
Kinetics gasier. A comparison with experimental data from numerous literature works was done, which showed
Mathematical model fairly good agreement. The model can be used to study and optimize the operation of bubbling uidized
bed gasier. However, further validation with diverse data will help to ne-tune the model.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Bioenergy is expected to become one of the major energy re-
sources in the future because biomass is renewable and free from
net CO2 emissions. It is also the only sustainable source of organic
carbon [1]. Using biomass as a fuel offers certain advantages, in
terms of energy, environment, society and economy. Gasication
is one of the most important areas in the research, development
and demonstration (RD&D) of the biomass-to-energy framework.
Gasication is a promising green route for conversion of bio-
mass materials to useful Product gas that can be utilized in poly-
generartion or in production of value added chemicals (VACs).
Gasication of biomass in uidized bed has certain benets: it is
easy to scale up, it gives near isothermal condition inside bed
and it gives easy controllability of the process. However, uidized
beds are not economical for small scale application. Mathematical
models are helpful for designing, for predicting gasier behavior
and studying effect of operating parameter on gasier perfor-
mance, startup, shutdown etc. Literature focusing on coal particle
and coal gasication is in plenty [28]. However modeling work
based on biomass red uidized bed are limited. Though coal gas-
ication information is often exploited to model biomass gasica-
tion, there are some basic differences between coal and biomass.
Biomass is more reactive: it pyrolyzes fast, has more volatile and
* Corresponding author. Tel.: +1 403 2205594; fax: +1 403 2824852.
E-mail address: jabedi@ucalgary.ca (J. Abedi).
moisture, has less energy density, has little ash and sulfur content.
These differences call for a robust and detailed model for biomass
gasication; however, detailed and advanced models for bubbling
uidized bed gasication are scarce [912].
The objective of this study was the development of a compre-
hensive one-dimensional steady state model for a bubbling uid-
ized bed biomass gasication-unit. Biomass gasication below
1000 C always produces important amounts of tar whose pres-
ence in the product gas has to be estimated with a good model.
It is a common assumption to consider devolatilization to be
instantaneous because they are much faster than the gasication
process. However there are few gasication models where devola-
tilization step is modeled with a rate limiting step [1314]. In this
study, a simplied semi-kinetic approach was used to model the
devolatilization step. The devolatilization sub-model not only pre-
dicts the volatile yield but also its composition. The model is capa-
ble of predicting the concentration and distribution of gas species
and tar along the height of the gasier, the overall composition,
heating value, production rate of the product gas, and the average
temperature in the bed.
2. Biomass gasication process
There exist a number of methods for utilizing biomass potential.
A promising alternative to extract energy out of solid fuel is gasi-
cation, as gases have fundamental advantages over solid fuels
[1517]. Gasication is a high-temperature partial oxidation

0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.07.036
 P. Kaushal et al. / Fuel 89 (2010) 36503661 3651

Abbreviations

A area (cross-sectional area) [m2] Sh Sherwood Number []

Ar Archimedes number [-] T temperature [K]
a decay constant [m1] t time [s]
C concentration [mol/m3] U velocity [m/s]
Cp heat capacity [J/molK] Umf minimum uidization velocity [m/s]
CW coefcient [] V volume [m3]
D diameter of Column [m] VM volatile matter [wt/wt]
D molecular diffusivity [m2/s] w weight fraction [wt/wt]
Dia diameter [m] x distance [m]
d diameter [m]
Y correction factor []
E Activation energy [j/mol]
y mole fraction []
f volume fraction of char [m3/m3]
DG standard state Gibbs Free energy [j/mol] z height [m]
g gravity [m/s2]
H height [m] Greek
Hj enthalpy of the species j [j/mol] d fraction []
e porosity []
DH0f ;298 enthalpy of formation at 298.15 K [j/mol] /ij viscosity coefcient []
hm mass transfer coefcient [kg/barm2s] l viscosity [Pas]
k mass transfer coefcient [m/s] q density [kg/m3]
K equilibrium constant [] m atomic diffusion volume []
k cell number [] 1 single isolated []
k reaction rate constant [dependent] 1 above Transport Disengaging height []
k0 frequency factor [dependent] c stoichiometric coefcient []
M molecular weight [kg/mol]
m mass [kg] Indices
m_ mass ow rate [kg/s] B bubble
N number [] bed bed Material
n amount of substance [mol] c carbon
P pressure [Pa] E emulsion
p partial pressure [Pa] eqlm equilibrium
Q volumetric ow rate [m3/s] g gas
Q_ heat ow [j/s] j specie
q rate based on external surface [kg/m2s] max maximum
R universal gas constant [j/molK] mf minimum uidization
Re Reynolds number [] p particle
r rate of reaction [mol/m3s] t terminal
S surface area [m2]

process of a carbonaceous feedstock using a gasifying agent, such
as steam, oxygen, air or a mixture of these gases. Gasication pro-
duces a gas mixture (a mixture of hydrogen, carbon monoxide, car-
bon dioxide, methane and small hydrocarbons) that is commonly
known as product gas. Irrespective of the reactor conguration, it
is believed that gasication occurs in the sequential steps of dry-
ing, devolatilization and gasication. There are no sharp bound-
aries between the steps, and these boundaries often overlap.
Though both coal and biomass are carbonaceous feedstock, how-
ever biomass (especially wood) has more volatile. Table 1 gives
an overview of this process. It is clear from the table that devolatil-
ization is the most important step during gasication, as it takes
relatively less time and releases almost 8090% of the mass as
gas [18,19]. Unlike pyrolysis, during gasication the emphasis is
to maximizing the yield of gas. Therefore during gasication the
process/operating parameters are optimized to favors the release
of volatile present in the biomass. The progress in modeling bio-
mass gasication and pyrolysis has recently been reviewed [20].
whole gasication process is divided into three sub-models: kinet-
ics, hydrodynamics and streams (material classication and prop-
erties). These sub-models are further divided into classes (shown
in Fig. 1) in order to have a realistic approach toward the overall
gasication process. Out of various regimes of uidization, this
study focuses on bubbling regime. The Kinetic sub-model has sep-
arate subroutines to take care of drying, devolatilization and gasi-
cation. The streams that ow in and out of control volume are
described in material sub-model (as solid liquid or gas). The vari-
ous thermodynamic properties of these streams are calculated in
this sub-model. It can be seen in the Fig. 1 that the information
can ow both ways among the sub-models. The boundary of the
investigated system is shown in Fig. 2. Bed geometry, temperature,
pressure, composition and ow rate of the incoming streams are
the inputs of the model. It is assumed that the cyclone instanta-
neously separates the gas from the solids and no reaction takes
place in the cyclone.

Table 1
Overview of gasication steps.[59,87] *Depends on moisture present in feed (wood).
3. Model development
Gasication step Reaction time(seconds) Mass released

The objective of this modeling was to couple the kinetics of dry- Drying 140220 0.10.5*
Devolatilization 250660 0.780.9
ing, devolatilization, gasication and the reactor hydrodynamic, in
Gasication t>3000 0.10.2
order to study the performance of a uidized bed gasier. The
3652 P. Kaushal et al. / Fuel 89 (2010) 36503661

Main overestimation [2223]. According to the interpretation adopted

by different studies, it is clear that the fraction of the total ow
in the dense phase can vary considerably (Table 2). The range of
Hydro dynamic

the emulsion phase ow is between 14% and 59% of the total gas
Sub-Model

Bubbling
Dense Freeboard ow. In this study, the bottom dense zone is modeled according
to the modied two-phase theory [24]. The mathematical repre-
Hidden layers

sentation for the visible bubble ow rate is estimated as

Kinetic Drying Devolatilization Gasification
Sub-Model Q B YU 0  U mf A 1

Material A correction factor Y is introduced to cap the amount of gas

Sub-Model Solid, Liquid, Gas owing into bubble phase. Y is always below unity and usually
in the range from 0.7 to 0.8. In case of OTPT, most of the gas pass
or slip through the reactor un-reacted as bubbles where as the
Results
emulsion phase, which is rich in solid (i.e. reactive biomass), has
Fig. 1. Simplied structure of model.
gas deciency. Hence the modied division of gas ow between
phases is more favorable for gassolid reactions. Bubbles and their
behavior play a major role in gassolid uidization. Bubbles are
Product gas responsible for features that differentiate the xed bed from the
uidized bed. They modify the gas ow in the system and cause
particle movement, which results in rapid and extensive particle
mixing. One crucial factors that affect the velocity of the bubble
are the viscosity of the gas and the size and density of the solid par-
ticles (both these parameters also affect the minimum uidization
Additional stream

velocity). The higher the minimum uidization velocity, the lower

(if any)

will be the velocity of the rising bubble. Accordingly, the ndings

Freeboard

of Davidson and Harrison [25] were adapted. The following equa-

tion has been used to calculate the rising velocity of the bubbles:

U B U B;1 U o  U mf 2
Biomass Feed

U B;1 is the rise velocity of a single isolated bubble of radius rB [26].

Dense Based on the two-phase theory, a signicant part of the gas ows in
bed
the bubble phase. Thus, the inter-phase mass transfer between the
blow down bubble and emulsion phases is essential for the gassolid reactions
(Fig. 3). A number of correlations can be found for inter-phase mass
Gasifying agent
transfer [2729]. However, in this model the interchange (mass
Fig. 2. Modeling boundary for the gasication process. transfer) coefcient kB,E (Eq. (3)), is based on the surface area

1 dNj;B dC j;B SB;E

 U B kB;E C j;B  C j;E 3
3.1. Hydrodynamic sub-model V B dt dx VB
Table 3 lists the equations used for the hydrodynamic calcula-
As explained above, this model deals with the bubbling regime tion and are detailed elsewhere [30].
of uidization. The bubbling bed is divided into two-zones, i.e.
dense and freeboard (Fig. 2). Each of these zones is divided into 3.1.2. Freeboard zone
cells where the local variables (hydrodynamic, kinetic and thermo- A plug ow model is assumed for the ow of gas through the
dynamic) are evaluated. Cells are solved sequentially with the out- freeboard zone; and, although the freeboard zone is assumed to
put of the Nth cell considered as the input for the (N + 1)th cell. All be free of solids, the catalytic activities of the char and bed material
hydrodynamic parameters are based on the properties of the bed are considered for calculating the gas phase reaction kinetics [31].
material. For simplication, an average particle diameter is used.

3.2. Kinetic sub-model (process modeling)

3.1.1. Dense zone
The description of the expansion of a bubbling uidized bed is Gasication involves the breakdown of large and heavy mole-
derived from the two-phase theory of uidization by Tommey cules of hydrocarbons into lighter ones. The process is a series of
and Johnstone [21]. However, in Original Two-Phase Theory steps, as shown in Fig. 4. For this modeling study, drying, devolatil-
(OTPT), the amount of gas owing through the bed as bubbles is ization and gasication are the three steps/processes considered. It
overestimated. Modications have been made to account for the is assumed that these processes take place sequentially.

Table 2
Flow assumed in various version of two-phase theory [24].

Theory VFB IFB TFB FDP TF

1 Two-phase U  U mf A 0 U  U mf A U mf A UA
2 Total decit GB 0 GB UA  GB UA
3 Through ow GB U mf dB A GB U mf dB A AU  U mf dB  GB UA
4 ntype GB U mf 1 ndB A AU  U mf 1  dB AU mf 1  dB UA

VFB, visible ow in bubble phase; IFB, invisible ow in bubble phase (through ow); TFB, total ow in bubble phase; FDP, ow in dense phase; TF, total ow.
 P. Kaushal et al. / Fuel 89 (2010) 36503661 3653

Gas out bubble Gas out emulsion 2 2

phase phase 4 2
2

z+z o Steam
100-200 C

1
Mass

EMULSION
BUBBLE
200-500oC
Exchange
z
500-950oC
Cracking, reforming

z
Gas in bubble Gas in emulsion
phase phase
Fig. 4. Simplied representation of gasication steps.

Fig. 3. Mass exchange between the bubble and emulsion phases.

3.2.1. Drying
Typically, the moisture content of freshly cut wood ranges from
30% to 60%. However, most gasication systems use dry biomass
with moisture contents of 1020%, in order to generate a high
heating value product gas. In this study, a simplied approach is
formulated to model drying. It is assumed that the loosely bound
water (moisture) present in the biomass irreversibly and instanta-
neously changes its phase from liquid to gas at a temperature
above 100 C, as in Eq. (4)
_ Bio jLiquid wm m
wm m _ Bio jGas
3.2.2. Devolatilization
Devolatilization is an extremely complex phenomenon due to
the large number of chemical and physical transformation
occurring rapidly and simultaneously. In general, when the
dried fuel is heated in the range of 200500 C in absence of
oxygen (or any other oxidizing agent), it decomposes into solid
char and volatiles (condensable hydrocarbon or tar and gases).
This process is called devolatilization. The relative yields of
gas and solid depend mostly on the heating-rate and the aver-
age temperature. The devolatilization product then reacts with
the gasifying medium (air, oxygen or steam) to produce carbon
monoxide (CO), carbon dioxide (CO2), hydrogen (H2) and lighter
hydrocarbons.
With respect to coal, thermal treatment of biomass is a recent
development. Though biomass differs from coal, analogies from
coal are often drawn for better understanding of biomass gasica-
tion process. The coal-devolatilization models available in litera-
ture focus on the amount of volatile release (kg/s) and are based
on: kinetic approach with Arrhenius terms, particle size, mass
and heat transfer, etc. [3237].
However not much is said about the approaches to calculate the
composition (yj) of the volatiles released [3841]. Majority of the
approaches are based on the fuel analysis and assumption that vol-
atile is made up of C, H, O, N, S and HC species and the nal volatile
has CO, CO2, NO, SO2, H2, H2O and light or heavy HC (if any). Such
4 approach is good for preliminary guess but is not recommended for
modeling processes, especially when the model is predictive in
nature. Although a lot of effort has been made to model devolatil-
ization step, majority of the gasication-models have their own
pitfalls. For e.g. a major drawback of these model was to assume
that devolatilization was instantaneous and producer gas was free
of tar [4244]. Gmez-Barea and Leckner has recently reviewed the
existing models with their strength and weaknesses [45]. The tar
fraction in the product-gas exiting a gasication-unit is lower then
the product-gas exiting from a pyrolysis-unit. However, it is not to
forget that, production of primary tar, Tar1 (Fig. 4) is measurable;
however gasiers are designed to promote tar cracking and
reforming reactions. High temperature, high residence time, cata-
lyst-bed, an oxidizing agent, etc. are to promote cracking and
reforming reactions. Therefore tar fraction T2 (Fig. 4) is lower in
the nal product gas.

Table 3
List of primary equations used in hydrodynamic model.

Name Expression
q
Correction factor for modied two-phase theory Y
0:260:7 exp0:0033dp
4 NAor 0:4
z
0:15U U mf 0:33
q
Bubble diameter dB 0:54U  U mf 0:4 z 4 NAor 0:8 g 0:2
Maximum bubble diameter dB;max
2U 2t
g
p
Velocity of single bubble U B;1 0:71 gdB
Bubble fraction dB
YU 0 U mf
UB
q
Mass transfer coefcient U mf 4emf DU B
K BE 4 B pd
l
p
Minimum uidization velocity U mf q dg p 27:22 0:0408Ar  27:2
g

Porosity at minimum uidization emf 0:478Ar0:018 ; 177 < Ar < 4030

Archimedes number 3
dp qg qp qg g
Ar l2g
r n
Terminal velocity q q d g 24 24 4
U t 43 pq g Cpw C w RT ; Ret < 1 Re p
Ret
0:4; 1 < Ret < 30000:43; Ret > 3000 ;
g

Diffusivity DA;B p1:43T

1:75107

P 1=3 P 1=3 2
p M A;B v A
v B
 
Viscosity Pn 1=2 1=4 2

lm j1 Pyn j lyj / ; /ji j i i 1=2j

1 l =l M =M

i1 i ji 81Mj =Mi 
3654 P. Kaushal et al. / Fuel 89 (2010) 36503661

The devolatilization step of the biomass is a source of high
uncertainty. Nevertheless unlike the popular instantaneous devol-
atilization assumption, in this study a simplied semi-kinetic ap-
proach is used to model devolatilization process. This study deals
with bubbling uidized bed gasication i.e. small particle size, high
temperature, near isothermal condition. At high temperature,
small particle devolatilization is independent of heating-rate.
Therefore Arrhenius type kinetic model is used to dene devolatil-
ized-gas composition.
Global decomposition of the wood is coupled to the ultimate
and proximate analysis of the biomass feed to calculate the yield
and composition of the devolatilization product. The three compet-
ing reactions that represent the devolatilization step are shown in
Fig. 5. The char produced post-devolatilization is a model parame-
ter. However, by default, it takes the value of xed carbon
(proximate analysis). The sum of Tar1 and gases is equal to the vol-
atile matter (proximate analysis). Additionally it is also assumed:
that the entire hydrogen and oxygen content of the biomass is re-
leased during the devolatilization process, and the volatile matter
released, Eq. (5), is a mixture of CO, CO2, H2, water (H2O),methane
(CH4) and primary tar (Tar1).
VM wCO CO wCO2 CO2 wH2 H2 wH2 O H2 O wCH4 CH4
wTar1 Tar1
The composition of devolatilized-gas is estimated from the rate
equations as shown in Eqs. (7 and 8). The kinetic constant for the
rates are reported in Table 4 and are valid for temperature range
of 200 C < T < 950 C.
wCO : wCO2 : wH2 : wH2 O : wCH4 : wtar1 r CO : rCO2 : rH2 : r H2 O
: rCH4 : rtar1
Ej 
rj kj exp RT
Ej1 
r j1
kj1 exp RT
a challenge for a 1 D model. Unlike coal, devolatilization of biomass
has a strong inuence on the overall gasication process because
the volatile fraction in biomass is approximately 67 times more
than coal. Therefore in this study the steam and gas released dur-
ing drying and devolatilization are not added instantaneously to
the gas stream. They are added in a predened pattern along the
height of the gasier, as shown in Fig. 6. The prole gas distribution
is to deal with the mixing problem of gas. By default equal distri-
bution of gas along the height of the gasier is assumed. Because
of the high devolatilization rates, the gasifying agent can not reach
the particle surface, since gas diffusion to the particle is much
slower [52]. Therefore a progressive conversion model (PCM) is
implemented for the drying and devolatilization of the solid bio-
mass. In PCM, it is assumed that the diameter of the particle stays
constant, whereas the density decreases, as in Eq. (8).
Dmbio
Dqbio 8
V
3.2.3. Gasication
Char, is the product of the preliminary drying and devolatiliza-
tion step. Char is often modeled as carbon. However, hydrogen and
oxygen fractions in char are reported [53]. This is because char
5 composition is strongly dependent on the devolatilization step.
Char gasication too is a complex process due to the combination
of different mechanisms like mass transfer, chemical reaction and
heat transfer. The net carbon (char) after devolatilization is in-
volved in a number of heterogeneous gasication reactions, as
listed in Table 5. Data reveals that with 10% addition of raw wood
ash in the gasier, at temperature of 800 C, the reactivity of wood
has increased nearly 6 times [54,55]. Hence the catalytic activity of
6
7
Height (or cells of dense zone)

i
While modeling gasication, another popular simplication is d
to assume devolatilization as instantaneous [4551]. Considering p
the fact that devolatilization is much faster than gasication it
seems correct from rst principle. The gas released during devola-
tilization has to mix with the other up-owing gas stream (e.g. gas- k+1
ifying agent and the gas released from char gasication). However,
k
if all the devolatilized-gas is mixed at one point it will affect the
e
equilibrium and bed hydrodynamics and hence will inuence the
nal gas composition. Gas mixing, is a sensitive parameter and is

Gas
Qgas
Volatile
matter Fig. 6. Gas mixing prole along the height. i: increasing; d: decreasing; e: equal; p:
wood Tar1 1st increases then decreases.

Fixed
Char carbon
Table 5
List of gasication reaction present in model.
Fig. 5. Simplied model for volatilization.
Name Reaction Reaction rate
Heterogeneous:
Table 4 Steam C H2 O ! CO H2 [90]
Kinetics of primary devolatilization [88,89]. Dry C CO2 ! 2CO [58]
Hydro C 2H2 ! CH4 [91]
Component kj (1/s) Ej (kj/mol)
Oxygen 1 bC 1 b=2O2 ! bCO CO2 [92]
CO 9.00  1009 111.0 Homogeneous
CO2 5.23  1009 105.0 Shift CO H2 O $ CO2 H2 [31]
H2 4.73  1004 92.5 General CO 1=2O2 $ CO2 [93]
H2O 3.68  1013 149.5 General CH4 3=2O2 $ CO 2H2 [93]
CH4 1.09  1005 71.3 General 2H2 O2 $ 2H2 O [93]
Tar1 2.09  1010 112.7 Reforming CH4 H2 O $ CO 3H2 [94]
 P. Kaushal et al. / Fuel 89 (2010) 36503661 3655

the ash which plays an important role in steam assisted char con-
version is considered.
The Boudouard reaction or dry gasication has been studied
extensively, as the products do not enter into side reactions. How-
ever, the activation energy for this reaction is strongly inuenced
1=3
by the type of carbon [5657]. The methane formation by hydro-
gasication is important, especially for air and oxygen gasication,
because the energy content of the synthesis gas is increased due to
the presence of methane. The oxygen necessary for gasication is
also reduced because of the heat released in methane formation.
The heterogeneous reaction kinetics parameters for different bio-
mass feeds have been listed by Barrio and Hustard [58]. Chen
and Gunkel studied the effect of char particle size and temperature,
on gasication [59]. They found that, with ne particle at high tem-
perature, the particle temperature (on surface and inside) is con-
stant. So isothermal condition within the char particle is a fair
assumption, however if the particle size is more than 1040 mm,
isothermal-particle is a false assumption. They also report that
for bulk temperature up to 1000 K reaction kinetics control the
reaction, but at higher bulk temperature gas diffusion can not be
neglected. Based on their nding the char gasication is modeled
in this study. It is assumed that, during gasication, the gasifying
agent from the bulk gas stream is transported to the char surface,
where it reacts heterogeneously with the carbon in a thin layer
without any ash formation. The gasication rate, in terms of mass
transfer through the gas lm, is described as:
q hm pg  ps 9 a mixture of non-condensable gases and light hydrocarbons. Eq.
Mc ShDg
hm 10
dchar RT m
where pg and ps are the partial pressure of gasifying agent in bulk
gas and char surface respectively. hm is the mass transfer coef-
cient. Dg is the molecular diffusivity of gasifying agent through
the gas lm. dp is the instantaneous diameter of the char particle.
Tm is the average gas lm temperature. The chemical reaction rate
of char with gasifying agent per unit time per unit external surface
area of the particle is:
q kchar;s pns 11
Above equations, Eqs. (9 and 11) were solved under steady state
assumption i.e.
q kchar;s pns hm pg  ps 12
For the cases, where gasication reaction is rst order, Eq. (12),
was solved analytically
Char conversion is modeled as shrinking particle model where it
is assumed that the diameter of the char particle decreases, while
the density of the char remains constant. In this work the shrink-
age is simply assumed to be mass-proportional [61]
3 mchar
r 16
4 pqchar
The homogeneous reactions (gas or vapor phase reactions only)
are modeled as non-elementary (global) reaction where the rate
expression follows a power law expression in the concentrations,
Eq. (17)
dC j
r j kC j n 17
dt
The pre-exponential factor and the activation energy for each of
the reactions have to be supplied as inputs to the model. For
reversible reactions, the rate of the reverse reaction is calculated
using thermodynamic data [62].
kfor
K eqlm 18
kback
DG0
K eqlm exp 19
RT
The primary tar (Tar1) that was produced during the devolatil-
ization step undergoes cracking in the gasication step to produce
(20) represents the tar cracking step. The coefcients c for Eq.
(20) are reported in Table 6.
tar ! cCO COg cCO2 CO2 g cCH4 CH4 g cH2 H2 g
ctarinert tar inert 20
For the tar cracking rate (kg/kg/s), the kinetic model by Boroson
and Howard [63] was used.
rjcrack cj 104:98 Exp93:37=RT wtar qg 21
where wtar qg is the amount of tar in gas phase. From Table 6, it is
evident that only 78% of the primary tar is cracked, and the rest
(22%) remains unchanged. However, studies show that operating
parameters, such as uidizing agent, temperature, residence time,
certain bed materials, and additives have catalytic effect on tar
cracking [64]. Tar yield as low as 6% has been reported [65]. Hence,
to deal with this situation, a correction factor, g, is introduced, the
value of which is 0:5 6 g 6 1: The remaining yield, in such a case, is
loaded on H2 and CO2 [66].

1 3.3. Balances
q p 13
1
hm
k1 g
char A model is a mathematical representation of a process. The pri-
For other cases where n1; Eq. (12), was solved numerically to mary purpose of modeling is to understand some existing process
estimate the value of ps. Also, the temperature dependency of the and to describe the concept mathematically. The elemental mass
rate constant was given by Arrhenius expression. Experimental balances inside each cell are checked by the stoichiometry of the
data were tted to the Arrhenius expression via minimization of homogeneous and heterogeneous reaction formulations. The glo-
root-of-mean-square-deviation method and the constants (k0 and bal balance, Eq. (22) for char is applied across each zone.
E) were estimated [60]: m _ charout m
_ charin  m _ charreact 0 22
Eap
RT
kchar;s k0 exp p 14
At any given time, char undergoes four heterogeneous gasica- Table 6
tion reactions simultaneously (Table 5). Therefore Eq. (15), is the Relative yield of tar cracking product [63].
sum of char gasied due to steam, carbon di oxide, hydrogen and
Species (j) cj Species (j) cj
oxygen as gasifying agents. Each of these four char gasication
reaction is modeled as per Eqs. (912). CO 0.78  0.72222 CH4 0.78  0.11334
CO2 0.78  0.14222 Tar1 1.00000
qnet qst qdry qhydro qoxy 15 H2 0.78  0.02222 Tar2 0.22 x g
3656 P. Kaushal et al. / Fuel 89 (2010) 36503661

X
N
  enthalpy balance across a zone delivers the average temperature of
_ Charreact
m dmchari =dt 23 the zone. The simplied energy balance equation is:
i1
X
N  X
N 
where dmChari =dt is the amount of char reacted (or gasied) in the Q_ add nj Hj TIn Q_ loss nj Hj TOut 25
j1 j1
control volume and is linked to the char fraction in the bed or zone.
The char fraction in the zone is iterated until the global mass bal-
ance, Eq. (24) is satised.
X X 850 (a) Measured Model
_ in
m _ out
m 24
800

Temparature (C)
The energy conservation equation is solved across the entire zone,
and it is assumed that, within a zone, the temperature is uniform.
750
This assumption is based on efcient solid mixing and the domi-
nance of the solids heat capacity within a uidized bed. The overall
700

START 650
T1 T2 T3 T4 T5 T6 T7 T8 T9
25700 Test Run

Read input file 20 (b)

Predicted (Vol%)
Provide 15
Is P over bed No
height of CH4
provided? dense bed 10
Yes
5
Iterate height of dense bed
0
0 5 10 15 20 25
40
Average temparature
(c) T9
35 T7 T
H2
Predicted (Vol%)

T5
Fraction of char in zone T4T6
30 T3
T2
25
Drying
l cell
Loca tion
la
calcu 20 T1
Devolatilization
15
15 20 25 30 35 40
40
Gas mixing (d) T1
35 T7
Predicted (Vol%)

CO2 T3T5
Thermo T6 T9 T2
Bed Reaction Elemental T4
dynamic hydrodynamic kinetics 30
balance
25 T8
Data transfer to next cell
20
Last cell ? No
15
15 20 25 30 35 40
Yes 40
No Iterate char T1
Mass balance ? fraction (e)
35 T2 T8
Predicted (Vol%)

Yes CO T4
T3 T6
Iterate No Energy balance ? 30 T7
Temperature
Yes T5
25 T9
Write output file
20

Last Zone ? No Data transfer to

15
next zone 15 20 25 30 35 40
Yes
Experimental (Vol%)
STOP
Fig. 8. Comparison of model predictions with the measured data of Campoy et al.
Fig. 7. Model algorithm for the dense zone (bottom bed). [73].
 P. Kaushal et al. / Fuel 89 (2010) 36503661 3657

Table 7
Model input, data extracted from tables in reference [73].

Model input
Bed Diameter 0.15 m Fuel Wood Pellets
Freeboard Diameter 0.25 m Fuel Flow Rate 1021.6 kg/h
Freeboard Height 2.15 m Gasication Agent Air + Oxygen + Steam
Bed Material Ote [67] Operation Temperature 755840 C

Operational condition Test run

T1 T2 T3 T4 T5 T6 T7 T8 T9
Biomass feed (kg/hr) 11.5 12.2 12.2 15 15 12.4 10 16.2 12.0
Air (Nm3/hr) 17 17 17 17 17 11.9 9.1 10.6 7.7
Oxygen (Nm3/hr) 0 0 0 0 0 1.5 1.2 1.4 1.0
Steam (Nm3/hr) 0 2.5 5.1 3.2 6 3.7 5.6 4.7 6.5

Z T
Hj T DH0f ;298;j C P;j T  dT
298:15K
The enthalpy of the gas mixtures and the solid bed material are cal-
culated using the 4th-order NASA polynomials [67] and data re-
ported by Barin [68], respectively. Fig. 7 gives an overview of the
model algorithm for the bottom dense bed. For freeboard, which
is nothing but a plug ow reactor a global energy balance similar
to Eq. (25) is applied to get an average temperature of the zone.
4. Results and discussion
There are some extensive models that exist today [9,6972], but
it is difcult to check their robustness. Most of them are very spe-
cic and are formulated to study a particular case. It is hard to gen-
eralize these models, because most of the key information or data
required are not published. An effort has been made here to vali-
date this model with as diverse data as possible. Fig. 8 is based
on the study of Campoy et al. [73]. They used wood pallets with
empirical formula CH1.4O0.64 (dry, ash free basis). The moisture
and ash content were 6.3% and 0.5% (wt basis). The test rig is de-
tailed elsewhere [74]. The operating mode for all the tests in the
pilot-scale FBG was auto-thermal and adiabatic. Also, the temper-
ature of the gasication agent was xed at 400 C for all tests. The
mode of operation they used for conducting the tests, for wood
pellets, consisted of four variables that could be independently var-
26
ied: the ow rates of biomass, air, steam and oxygen. The ow
rates of air and oxygen determined the oxygen content in the en-
riched air. The experimental program comprised tests with air
oxygensteam mixtures in different proportions i.e. to tests vary-
ing stoichiometric ratio (SR), steam-to-biomass ratio (SBR), and
the oxygen percentage of the enriched air (OP). For their study,
they varied SR, SBR and OP (between the indicated ranges: SR from
0.24 to 0.38, SBR from 0 to 0.63 and OP from 21% to 40%) to explore
the effects of these variables on the quality and composition of the
produced gas. Table 7 lists the key operating parameters for Fig. 8.
The details of the model inputs and operating parameters can be
found elsewhere [7576]. It can be seen in Fig. 8 that the model
predictions are in good agreement with the measured values: all
the predictions are within 5% of the measured value. During each
of the test runs, many of the operating parameters (stoichiometric
ratio, steam-to-biomass ratio, temperature, etc.) were changed.
Therefore, it is not easy to nd the exact cause for the observed
change in gas composition among the test runs. However, the
authors [73] have tried to give a detailed explanation.
In Fig. 8, both model predictions and measured data show that
the percentage of hydrogen varied widely (1935%), while the
methane fraction in the produced gas was almost constant

70 CO CO2
45 16 H2 CH4 Schuster et al. [77]

Predicted Measured 60 Model prediction

14
40 Low Temperature High Temperature
H2
12 50

35
Volume %
Predicted (Vol %)

10
Predicted (Vol %)

40
CO
30 8
(secondary axis)

30

6
25 20 CO2

4
20 10 CH4
2
0
15 0 700 750 800 850 900
CO CO2 H2 CH4
Temperature (C)
Fig. 9. Effect of different gas-mixing patterns on the gas composition for test run T1
of Table 7. Fig. 10. Comparison of model prediction for steam as the gasifying medium..
3658 P. Kaushal et al. / Fuel 89 (2010) 36503661

Table 8 (911%). This suggests that hydrogen production was sensitive to

Model input parameters (*: 15% of total carbon present in biomass). the uidizing medium and its ratio to biomass fed while methane
Column: Minimum Dia. 0.67 m is relatively insensitive to these parameters.
Total Height 6 m The reason to have small variation in methane percentage could
Pressure drop (gasier) 0.15 bar possibly be: (a) the main source of methane in the product gas is
Bed material quartz sand
Char Carbon*
via devolatilization, which is primarily a function of temperature,
Fuel composition: (by weight) and is practically independent of gasifying medium; (b) also as gas-
C 48.26 Ultimate analysis ication is nothing put partial oxidation in under-stoichiometric
H 05.82 condition the reactive species, H2 and CO, react with the most of
O 45.67
the gasifying agent. Another observation made during this study
Volatile 80 Proximate analysis
Moisture 25 is that the model was sensitive to the gas-mixing pattern. Fig. 9
Temperature: shows the predicted gas composition for the same operating con-
Biomass 20 C ditions (T1 of Table 7), but with the different mixing patterns de-
Steam 400 C ned in Fig. 6. It can be seen that the difference between the
Heat loss 5% (of input)
Steam ow rate 500 kg/hr
predicted and measured compositions was more than 10%. There-
Biomass ow rate 2900 kg/hr fore, proper selection of the mixing pattern is very important, in or-
der to get close to practical experiences.
All the typical uidizing/gasifying agents normally used for gas-
ication were studied and are presented in Fig. 8.
Table 9 Steam, as the only gasifying agent, is presented in Fig. 10.
Model input parameters [79].
Schuster et al. [77] developed a Dual Fluidized Bed (DFB) model
Internal Dia. 6 cm for the steam gasication of biomass. It is an allothermal unit. Un-
Operating temperature 800 C like auto-thermal gasier where a part of the biomass is com-
Biomass throughput 260 kg/hr m2
busted inside the gasier to generate heat in situ, in allothermal
Moisture in feed 2 5%
Bed particle size 400 micron unit heat is transferred to the gasier to sustain the endothermic
Height of dense bed 20 cm gasication reactions. In DFB unit, heat is generated by combusting
Biomass feed rate 9 g/min the spent char, exiting the gasier, in a separate uidized bed com-
Bio feed (dry basis) Saw dust C4O2.7 H5.8 N0.02 bustor. Circulating bed material acts as a heat bridge between the
Gas velocity 19 (2Umf) cm/s
Gasifying agent Air
two uidized beds. The details of the DFB gasier could be found in
Bed material Silica sand reference [78]. Separating the biomass gasication from char-com-
bustion has an added advantage of generating clean and high

25

20 Experimental data [79]

Model
Tar yield (g/Nm3)

15

10 close fit of the

experimental data

0
700 720 740 760 780 800 820 840

Temperature (C)

Fig. 11. Comparison of predicted tar yield to measured value..

 P. Kaushal et al. / Fuel 89 (2010) 36503661
heating value product gas. However modeling a circulating bed is
complex. The gasier is in bubbling regime, where as the combus-
tor is in fast uidization regime. Fast uidized DFB combustion
model is provided elsewhere [30]. The combustor and the gasier
models are linked to generate the result. Table 8 provides the mod-
el parameter. The effect of average bed temperature on gas compo-
sition is simulated in Fig. 10. Similar trends were observed in both
studies. With the increase in the average temperature of the bed,
the production of CO and H2 were increased, while CO2 and CH4
were decreased [7981]. It can be seen in the Fig. 10 that the
change in concentration, in comparison to higher temperature, is
more prominent in the lower temperature range (700 C <
T < 800 C). It brings to notice that at high temperature char-gasi-
cation rate is no longer controlled by surface reaction kinetics [59].
Similar trends were observed in both studies. At an enhanced level,
the differences at individual points are indispensable. The possible
reason may arise from the fact that tar formation was not consid-
ered and equilibrium was assumed to be the dominant mode in
their model [77]. These could be the possible reasons for the min-
imal production of methane in their study as well. However there
are no measured data to validate either of these simulation results.
While modeling a gasication process, it is common to neglect
tar [8283]; however, incorporating the formation of tar is an
essential step towards commercialization of the process [84].
Narvaez et al. carried out experiments in a small scale bubbling
uidized bed gasier [79]. They used special tar and gas sampling
device to measure tar and gas amount and composition. Their re-
ported data were used to check the models tar handling feature.
Input data are reported in Table 9. However additional details like
experimental set ups and operating parameters could be found in
the literature [79]. In this study, tar was handled explicitly as a
separate subroutine (or object). In Fig. 11, the effect of temperature
on the tar yield is plotted. In accordance with popular observation,
the tar yield decreased with the increase in the average tempera-
ture of the gasier [8586]. This may arise from the facts that tar
cracking is favored by high temperature and increased residence
time (due to the added height of the freeboard zone). Measured
data for this particular case are also shown in Fig. 11.
As seen in Fig. 11, for a temperature of approximately 800 C,
three values of tar yield were observed for the same operating con-
ditions. This is because of the fact that the model predicts the aver-
age value while the point from where the gas sample is collected
and analyzed is the local value. It also suggests that, in addition
to the axial gradient, there is a strong radial gradient. This supports
the above-mentioned claim that the gas mixing is a sensitive
parameter and has a strong inuence on the overall performance
of the gasier. Also, instantaneous gas release and mixing is not
a fair assumption to model devolatilization step of gasication.
5. Conclusions
The presented gasication model is a one-dimensional, steady
state, two-phase model which allows mass transfer between
phases. The model developed is robust and considers all the
key parameters for a bubbling uidized bed gasier. The bottom
dense bed is modeled in accordance with the modied two-
phase theory. The gasier freeboard is assumed to be free of so-
lid, however the catalytic activity of ne char particle on gas
phase reactions were considered in freeboard. In the model, the
char-gasication rate was controlled by a mixed resistance of
reaction kinetics and bulk gas diffusion. Heterogeneous reactions
were assumed to take place on char surface and shrinking parti-
cle model (SPM) was formulated to model the solid particles.
During devolatilization around 80% of mass is released and is a
very critical step. Unlike, common assumption devolatilization
3659
step was not modeled as instantaneous and tar free. A partly ki-
netic, partly mass balance scheme was adapted to model the
step. Tar, released during devolatilization, was represented by a
combination of model compounds. The mass and energy balances
were performed to get solid hold ups and average temperature,
respectively.
Reactor geometry, mass ow rate, composition and tempera-
ture of incoming streams were the model inputs. The model is
capable of predicting the bed temperature, tar yield, product gas
composition, heating value and production rate. To check the
robustness of the model, an effort was made to validate this model
with as diverse data as possible. The model had shown good qual-
itative and quantitative agreement with other bubbling bed gasi-
cation models. A preliminary validation with some experimental
data from the literature was conducted. Results show that the
model is capable of dealing with air, oxygen, steam or a mix of
these gases as the gasifying medium.
The model performance could have been improved, if more de-
tailed design and experimental data were available. Efforts are in
progress to generate data in-house for the purpose of additional
modeling studies with parameter variation.
Acknowledgements
The nancial support of the Alberta Agricultural Research Insti-
tute (AARI), Institute for Sustainable Energy Environment and
Economy (ISEEE) and Natural Sciences and Engineering Research
Council of Canada (NSERC) are acknowledged.
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