Fuel 280 (2020) 118582

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Full Length Article

Kinetic modeling of biomass gasification and tar formation in a fluidized bed T

gasifier using equivalent reactor network (ERN)
⁎
Bijoy Das, Atmadeep Bhattacharya1, Amitava Datta
Department of Power Engineering, Jadavpur University, Salt Lake Campus, Kolkata 700098, India

A R T I C LE I N FO A B S T R A C T

Keywords: A chemical kinetic based simulation model of a bubbling fluidized bed biomass gasifier has been developed using
Biomass gasification an Equivalent Reactor Network (ERN). The pyrolysis zone is modeled using a thermodynamic equilibrium model
Pyrolysis and a kinetic-controlled perfectly stirred reactor (PSR) placed in succession. The gasification zone and the
Kinetic modeling freeboard are simulated as perfectly stirred reactor (PSR) and plug flow reactor (PFR), respectively. A detailed
Tar
chemical reaction mechanism is used to describe the chemistry of reaction during devolatilization and gasifi-
Equivalent reactor network
cation stages. The formation and evolution of gaseous and tar species in different zones of the gasifier are
estimated and the major reaction paths have been identified. The influence of equivalence ratio (ER) on the
gasifier performance and tar species formation has been studied. Out of the three ERs considered (0.27, 0.24 and
0.19), the best performance of the gasifier is exhibited at ER = 0.24 in terms of cold gas efficiency.

1. Introduction
Biomass is a widely available, carbon–neutral energy resource that
currently accounts for more than 10% of the world's total energy con-
sumption [1]. One convenient way of extracting energy from the bio-
mass is through its gasification and then using the resultant fuel gas
either in internal combustion engine or in gas turbine engine to produce
electricity. However, as the energy content and density of the biomass
feedstock are low, the cost of the biomass transportation should be
considered in the economic assessment of biomass conversion tech-
nologies [2]. Therefore, the power generation from gasification of
biomass in small scale decentralized units is often a more economical
option than that in a large scale centralized plant [3,4]. Furthermore,
the emission indices of carbon monoxide (CO) and soot from a gasifier-
engine combined system operating on woody biomass remains negli-
gibly small [5]. Besides the gasifier and reciprocating internal com-
bustion engine couplings, there are a few works available in the lit-
erature on the gasifier and gas turbine combinations as well. Such
combinations may also be used in conjunction with steam turbines in
the integrated gasification combined cycle (IGCC) plants. A detailed
review of the usefulness of the IGCC technology involving biomass can
be found in Parraga et al. [6]. It has been identified in this review that
the biomass gasification process is quite complex and therefore its
modeling is a challenging task.
The fuel gas (named producer gas or syngas), produced through
gasification of biomass in air, contains hydrogen (H2), carbon monoxide
(CO) and methane (CH4) as the combustible components; in addition to
the other non-combustible components like carbon dioxide (CO2) and
nitrogen (N2). The syngas composition varies significantly with the
biomass feedstock, gasifier type and gasifier operating parameters [6].
It is an established fact that the performance of both the IC engine and
the IGCC plant depends strongly on the quality of the fuel gas produced
from biomass gasification [7,8]. The producer gas also contains tar,
which is a complex mixture of hydrocarbons heavier than benzene [9].
Tar is produced in the gasifier primarily during the pyrolysis of bio-
mass; and then it is subjected to secondary reactions. Different com-
pounds present in tar have been listed by Milne et al. [10] following the
work of Evans and Milne [11]. Tar is an unwanted constituent of the
producer gas, which adversely affects the quality of the fuel for its use
in engines and turbines. The tar constituents may condense to block the
fuel lines and particle filters in engines. They also result in the increased
emission of soot and UHC (unburned hydrocarbon) in the exhaust.
Therefore, reduction of tar in the producer gas remains an important
objective in the design and development of the biomass gasifier unit. A
recent review by Islam [12] has listed numerous catalytic materials that
are being researched upon for the tar removal process in biomass ga-
sification.
Another method of reducing the quantity of tar in the producer gas

⁎
Corresponding author.
E-mail address: amdatta_ju@yahoo.com (A. Datta).
1
Presently at Department of Mechanical Engineering, Aalto University, Finland.

https://doi.org/10.1016/j.fuel.2020.118582
Received 6 April 2020; Received in revised form 31 May 2020; Accepted 29 June 2020
Available online 11 July 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
B. Das, et al.
is by in-situ control of tar formation through appropriate choices of the
gasifier type and operating parameters [13,14]. Several gasification
parameters, like the type of biomass feedstock, gasification agent and
equivalence ratio in the gasifier, gasification temperature and pressure,
are found to influence the formation of tar during biomass gasification.
The fluidized bed gasification (FBG) process leads to efficient tar
cracking due to high gasifier temperature causing a reduction in the
quantity of tar in the gas [15]. At the same time, bubbling fluidized bed
gasifiers are among the simplest (in terms of scalability and controll-
ability) and the most cost-effective technology of gasification with
flexibility towards a wide variety of biomass feedstock [16,17].
Experimental determination of tar in producer gas is a resource
intensive exercise that necessitates successful sampling and highly re-
liable measurement [18,19]. On the other hand, a suitable model of tar
can predict the formation and transformation of tar compounds in
different zones of the gasifier and also evaluate the composition in the
final producer gas. The model can also be used to optimize the oper-
ating parameters for controlling the tar quantity in the fuel. However, it
is necessary to couple the tar formation model with the overall model of
the gasifier, which will predict the composition of the producer gas
formed in gasification.
Tar is a complex mixture of condensable hydrocarbon compounds,
classified as primary, secondary and tertiary, according to the appear-
ance of the molecules and based on its evolution according to tem-
peratures [20]. Many researchers have represented tar by an equivalent
single hydrocarbon (like CHpOq) to simplify the modeling of its for-
mation [21,22]. Such assumption enables to include tar in the equili-
brium modeling of the gasification process [23]. However, the equili-
brium models have the limitations in over-predicting the gas
production, tar content and the concentration of the combustible gas-
eous components in the producer gas [24,25]. An improved modeling of
tar formation and destruction considers tar to be composed of a few
lumps of hydrocarbons involving a set of kinetic equations [26]. Palma
[27] proposed a brief chemical kinetic model on tar formation from
lignin in a fluidized bed gasifier. This model successfully gave quali-
tative chemical insights into the tar formation process. In another work,
the same author [13] has reviewed detailed kinetic mechanisms for tar
formation and evolution in biomass gasification comprising large
number of elementary reaction steps. Moreover, the need for better
understanding of detailed chemical kinetics of the tar formation me-
chanism has been highlighted in this review work.
The use of computational fluid dynamics (CFD) in the simulation of
a fluidized bed gasifier can provide a deeper insight into the transport
processes, predicting the distributions of the velocity, pressure, tem-
perature, species concentrations and other hydrodynamic parameters
inside the gasifier. Ismail et al. [28] adopted the Eulerian–Eulerian 2D
CFD model to simulate the fluidized bed biomass gasification and in-
vestigated the concentrations of individual species and cold gas effi-
ciency at different equivalence ratio and biomass moisture content. As
an alternative to this approach, Ku et al. [29] simulated the gas phase
by Eulerian method and the particle phase by discrete element method
(DEM), thereby tracing the individual particles to accurately predict the
microscopic information like the particle trajectories, particle–particle
interactions, particle entrainments, and particle reactions. During the
CFD simulation in the reactor, the associated chemical kinetic me-
chanism consumes the major part of the computational resources [30].
Therefore, it is a common practice to use global reactions in CFD si-
mulations in order to minimize the computational cost [31]. However,
the detailed chemical reaction path from the input biomass to the
product gas is missing in the global reaction pathway. Simplistic global
mechanisms fail to evaluate the tar composition correctly and cannot
predict the component-wise distribution of tar [32].
To overcome the shortcomings of the equilibrium modeling and
global mechanism based CFD simulation, Lee et al. [33] combined
thermodynamic and kinetic based models for the pyrolysis of biomass.
They applied two computational codes – HSC Chemistry for
2
Fuel 280 (2020) 118582
thermodynamics and Sandia PSR [34] for kinetic simulations – for the
precise prediction of the biomass pyrolysis products. It was demon-
strated in this work that the combination of thermodynamic equili-
brium model in HSC chemistry and PSR can successfully predict the
pyrolysis products. Dupont et al. [35] incorporated only the kinetic
processes to model the biomass-steam gasification considering the
biomass transformation process to occur in two successive steps – (i)
pyrolysis of biomass and (ii) steam gasification of solid residue. They
observed that the gasification process is controlled by the chemical
kinetics of reactions. They further compared the time scales of different
processes involved in gasification and showed that the pyrolysis time is
much less than the gasification reaction time and the relative time
scales depend on the gasification temperature. Hafner et al. [36] used a
detailed reaction mechanism for high temperature gasification of
ethylene glycol produced by fast pyrolysis of biomass in an entrained
bed gasifier. They validated their simulation results using experimental
data from the literature for concentration profile, laminar flame speeds,
ignition delay times as well as gasification result in complex turbulent
reactive flow. A multi-physics model by Qiao et al. [37], considering
detailed gas phase chemistry and particle phase reactions, simulated the
gasification processes in a well-stirred reactor. They studied the effects
of particle size, pressure, porous structure, O2 concentration, radiative
heat transfer and H2 addition on gasification performance. Another
detailed kinetic model for bio-oil gasification was developed by Khan-
shan and West [38] using separate plug flow (PFR) and continuous
stirred tank (CSTR) reactors. They used the sensitivity analysis to
identify the most valuable information for improving the mechanism
predictions. A reactor network modeling (RNM), comprising a CSTR
and PFR, was adopted by Stark et al. [32] for air-blown gasification in
fluidized bed gasifier. The biomass mechanism developed by the CRECK
group was adopted in the model to simulate the chemical reactions. The
concentrations of major gaseous species and tar compounds, produced
during biomass gasification, were predicted and validated. It was found
that the RNM model can predict the major syngas species and one-ring
aromatic tars as well as heterocyclic aromatic tars with good accuracy.
It has also been shown in the work that the char conversion following
pyrolysis is mostly by elutriation from the bed and carbon conversion
through char gasification and oxidation plays insignificant role.
It is clear from the above-mentioned literature survey that accurate
prediction of tar species with detailed chemical kinetics in the biomass
gasification process needs more attention. The transformation of bio-
mass in a gasifier takes place through two successive steps – pyrolysis
and gasification, and chemical kinetics play an important role in both of
them. In a fluidized bed gasifier, the vigorous mixing due to movements
of bubbles and bed solids creates an environment of uniform tem-
perature and concentrations. Thus, the continuously stirred reactor
model applies well within the bed. To the best of our knowledge, no
work has been reported in the literature encompassing, successively,
the detailed kinetic model both for the pyrolysis and gasification pro-
cesses. Therefore, the present work deals with the chemical kinetic
analysis of the fluidized bed gasification process in an equivalent re-
actor network (ERN) that can physically describe the transport pro-
cesses in the gasifier. This approach will require relatively small com-
putational demands of mathematical model with large chemical
reaction mechanism. The chemical kinetic mechanism has been opti-
mized in the parametric range under consideration using sensitivity
analysis. The mechanism has been validated using the experimental
data from the literature. The tar formation and destruction pathways
have been analyzed and the concentrations of important tar compo-
nents in different zones of the gasifier and finally in the producer gas
have been reported at various operating conditions.
2. Simulation methodology
The present analysis deals with the fluidized bed gasification of dry
and ash free woody biomass in a stream of air. Fig. 1(a) shows the
B. Das, et al.
Fig.1. Schematic diagram of (a) the bubbling fluidized bed biomass gasifier showing different zones in it; (b) Equivalent reactor network for the gasifier.
schematic of a bubbling fluidized bed biomass gasifier with the biomass
feedstock fed from the top and the gasification air introduced from the
bottom. Such a scheme has been adopted in the present work from the
experimental study of Kim et al. [39]. It may be mentioned in this re-
gard that similar fuel and oxidizer feeding strategies in bubbling flui-
dized bed biomass gasifiers are quite commonly reported in the lit-
erature [40–42]. The air, which is sub-stoichiometric in quantity,
maintains fluidization of the bed in the bubbly flow regime, where
vigorous bubble movement inside the bed ensures good mixing. The
oxygen in air gets fully consumed in the chemical reactions occurring in
the bed. The biomass, entering the gasifier, gets pyrolyzed due to the
high temperature and in absence of oxygen, forming the gaseous
components, tar and char. Further gasification reactions continue in the
fluidized bed and finally in the freeboard above the bed, as shown in
Fig. 1(a). In order to compute the composition of the output gas, and
concentration of tar components an equivalent reactor network (ERN)
has been formed (Fig. 1 (b)) considering three zones – i.e. pyrolysis
zone, gasification zone and freeboard zone. The following assumptions
have been made in developing the model:
3
Fuel 280 (2020) 118582
1. Pyrolysis zone has been modeled as a combination of thermo-
dynamic equilibrium model and kinetic model [33]. The position of
the pyrolysis zone is adjacent to the fuel entry region (Fig. 1 (a)).
The oxygen present in air fed from bottom of the gasifier does not
reach the fuel entry point due to the sub-stoichiometric environment
inside the reactor.
2. The volume of the pyrolysis zone has been assumed as 2% of the
total gasifier volume from a scale analysis considering the fact that
the pyrolysis takes place within a very short time upon entry of the
biomass into the gasifier [43,35,27]. Devolatilization occurs in-
stantaneously during pyrolysis so that the thermodynamic equili-
brium exists among the product gases from the devolatilization
process. The devolatilization products further react among them-
selves following a kinetic scheme within the pyrolysis zone. During
such reactions, the homogeneous gaseous interaction is much faster
than the heterogeneous surface reaction [32]. The small volume of
the pyrolysis zone and the turbulence in the flow results in a well
stirred situation during the kinetic reaction which has been modeled
using a perfectly stirred reactor (PSR).
3. The gasification reactions occur in the fluidized bed which is
B. Das, et al. Fuel 280 (2020) 118582

approximated as a perfectly stirred reactor (PSR) considering the

Fixed bed gasification involving

very high rate of mixing due to the hydrodynamics of the bed.
4. The freeboard is modeled as a plug flow reactor (PFR) due to little

Detailed chemical kinetics

Detailed chemical kinetics

axial mixing or negligible mass diffusion in the flow direction

Sommariva et al. [49]

5. As the model predictions are validated against the experimental
results of Kim et al. [39], the temperatures at different zones of the
gasifier are assumed to be the same as those in the experiments. The

solid fuels
temperature values of different zones were set by averaging the
experimental thermocouple readings of Kim et al. [39] in the re-
spective zones.
6. The walls of the gasifier are considered as non-catalytic. All gaseous
species are assumed to be ideal with variable specific heat.

Devolatilization and gas phase reactions in

The thermodynamic equilibrium calculation for the simulation of
initial part of the pyrolysis process has been done with the HSC
Chemistry 6.0 tool [44]. The biomass entering the pyrolysis zone has

Detailed chemical kinetics

elements C (51.02%), H (7.16%), O (41.73%), N (0.09%) and S
(0.004%), following the ultimate analysis of the feedstock [39]. During
the evaluation of equilibrium species composition, the Gibbs free en-

biomass pyrolysis
Ranzi et al. [48]
ergy has been minimized for the mixture. The species considered during
the equilibrium calculation are H, H2, C, CO, CO2, CH4, HCN, NH3,
C2H2, C2H6, C2H4, C3H8, N, N2, NO, N2O, O, O2, H2O, H2O2, HO2, NO2,

——
NO3. However, as the hydrocarbons heavier than CH4 are not ther-
modynamically stable species, their existence in the pyrolyzed gas
cannot be predicted from the equilibrium calculation [45]. Therefore,

Thermodynamic equilibrium and well-stirred reactor using

the thermodynamic equilibrium calculation returns only H2, C, CO,
CO2, CH4 and H2O in significant concentrations. The components from
the HSC calculation are further reacted in a perfectly stirred reactor
(PSR1 in Fig. 1(b)), which is also a part of the pyrolysis process, ac-
counting the kinetic rates of chemical reactions.
Table 1 summarizes the simulation methodologies adopted in the
present work for the modeling of pyrolysis and gasification zones in a
biomass gasifier and comparing them with methodologies adopted by
skeletal GRI-Mech mechanism

other researchers. It may be seen from the table that Lee et al. [33] used
similar strategy to predict the gaseous products from biomass pyrolysis.
However, the present treatment of biomass pyrolysis differs from the
Biomass pyrolysis

work of Lee et al. in the following respects. The carbon (C) in the
Lee et al. [33]

equilibrium products from HSC calculation represents both volatile and

solid phase carbon with the relative amount dependent on temperature.
Description of pyrolysis and gasifier models adopted in the present work from literature.

For the pyrolysis temperature considered in the present work, the solid
——

carbon in the equilibrium product is found to be 65–68% of the total

carbon. The solid phase carbon remains as charcoal. Lee et al. [33]
Thermodynamic equilibrium and well-stirred reactor using

Well-stirred and plug flow reactor using detailed chemical

eliminated the solid phase carbon from the equilibrium product mixture
and considered only the pyrolyzed gas components and the volatile
carbon to react in the PSR through kinetic reactions. However, the
charcoal formed after devolatilization of woody biomass is a micro-
Bubbling fluidized bed biomass gasification

porous solid with a very high surface area per unit volume. Therefore,
without neglecting the solid phase carbon from further reaction, we
have assumed it to react homogeneously over the whole volume of the
charcoal, with access of gaseous components through the large number
of micropores and mesopores. Thus, the entire carbon obtained from
detailed chemical kinetics

the equilibrium calculation continues to react in the PSR1 of the pyr-

olysis zone. Moreover, as mentioned in Table 1, Lee et al. [33] con-
sidered the GRI-Mech chemical mechanism and the associated kinetic
Present Work

parameters to solve the chemistry in the perfectly stirred reactor during

pyrolysis. GRI-Mech was developed for the oxidation of natural gas and
kinetics

does not employ well for the reactions involving higher hydrocarbons.
So, it will not be able to correctly account the wide variety of com-
pounds in the biomass tar formed on pyrolysis. We, therefore, adopted a
Investigated phenomenon

chemical mechanism more suited for biomass devolatilization and

pyrolysis.
Pyrolysis model

The pyrolysis is followed up by the gasification process, modeled

Gasifier model

using a perfectly stirred reactor (PSR2), occurring in the fluidized bed

(Fig. 1(b)), with the admission of fluidization air of sub-stoichiometric
Table 1

quantity. The PSR is characterized by the volume of the reactor, mass

flow rate of fluid through the reactor, inlet conditions (temperature and

4
B. Das, et al.
composition) and temperature of the reactor. In the PSR, the mixing
rates are considered to be very fast and the chemical conversions from
the reactants to the products are controlled by the rates of kinetics of
reactions. The Modeling of both PSR1 and PSR2 has been done by
solving a system of nonlinear algebraic equations using Chemkin-Pro
package to evaluate the species concentrations within the reactor
(which are equal to those at the outlet) considering homogeneous re-
actions in the gas phase. The equations are solved by the damped
modified Newtown algorithm. The mathematical details of the perfectly
stirred reactors used in the present work may be found in [34,46].
It may be seen from Fig. 1 (b) that the products of PSR2 enter the
freeboard zone above the bed. Low solid concentration, perfect mixing,
uniform properties in the radial direction and change of concentration
along the axis of flow make the freeboard zone to be suitably modeled
as PFR. A set of ordinary differential equation is solved for conservation
of mass, energy and momentum for a differential slice in the flow di-
rection to solve the PFR model. The relevant equations pertaining to the
PFR in the freeboard zone has been solved using Senkin program [47]
in the Chemkin-Pro package. The mathematical details of PFR used in
this simulation are available in [46].
The kinetic model of multistep chemical reactions focusses on the
pyrolysis reactions forming gaseous species, tars and solid carbon,
secondary gas phase reactions of the gaseous and tar species, and re-
action of the char with the gaseous species. Ranzi and his coworkers at
the CRECK modeling group have done a lot of work and proposed
chemical mechanisms with kinetic parameters for the simulation of
pyrolysis and gasification reactions of biomass [48,49]. It is shown in
Table 1 that the detailed chemical kinetic model has been adopted in
the present work for the gas phase reactions in both the pyrolysis and
gasification zone. However, in the present work, we have optimized the
detailed CRECK mechanism containing 451 species and 17,848 reac-
tions (version 1412, available at the website http://creckmodeling.
chem.polimi.it/) through sensitivity analysis [30] to generate a me-
chanism to predict the formation of the major gaseous and tar con-
stituents in the producer gas in the parametric range suitable for flui-
dized bed gasification. The sensitivity analysis has been performed on
the mole fractions of the four major constituent species (H2, CO, CO2
and CH4) pertaining to the producer gas at the gasifier outlet one at a
time. Finally, 42 reactions that led to the wrong prediction of the target
species have been identified and removed from the initial mechanism.
The mechanism with the remaining 17,806 reactions has been used in
the work. Appendix A of the supplementary material lists the excluded
reactions in the present work.
The model predictions have been validated against the experimental
data from Kim et al. [39]. The total height and the internal diameter of
the gasifier are 3.8 m and 0.4 m, respectively. In the model, the bed
region is considered to extend up to 2 m height above which the free-
board zone has the height of 1.8 m. The corresponding volumes are
used for the PSR2 and PFR zones. The simulations have been done for
three different equivalence ratios (ER = Actual air–fuel ratio/ Stoi-
chiometric air–fuel ratio) of 0.27, 0.24 and 0.19. The details of biomass
and air feeding rates at different equivalence ration are shown in
Table 2. The values in the table correspond to those in the experimental
work of Kim et al. [39]. As seen from the table, the simulation of the
pyrolysis zone has been performed at atmospheric pressure and tem-
peratures of 650 °C, 681 °C and 660 °C for ER 0.27, 0.24 and 0.19,
respectively. The modeling of the gasification zone has also been done
Table 2
The gasifier conditions used in simulation for comparison with experimental results [39] in Fig. 2 (a-d). All simulations are done at atmospheric pressure.
Case ER Biomass feeding rate (kg/hr) Air flow rate (Nm3/hr)
Case I 0.27 34 37
Case II 0.24 55 54
Case III 0.19 55 43
5
Fuel 280 (2020) 118582
at atmospheric pressure. The temperatures during gasification have
been considered as 769 °C, 765 °C and 739 °C for the 0.27, 0.24 and
0.19, respectively. All these temperatures correspond to the average
experimental temperature data given in Kim et al. [39].
3. Results and discussion
3.1. Analysis of syngas production
The developed model is used to simulate the gasification of woody
biomass in a bubbling fluidized bed gasifier and predict the composi-
tion of gaseous constituents and tar in the producer gas. A comparison
of the mole fractions of the major gaseous constituents, like H2, CO, CO2
and CH4, in the producer gas predicted from the model against those
reported from the experiments [39], at different ER, is shown in
Fig. 2(a-d) at identical pressures, temperatures, equivalence ratios and
biomass feed rates (Table 2). However, the experimental data on tar
quantity at the gasifier outlet has not been provided by Kim et al. [39].
Therefore, the tar concentration in the producer gas predicted using the
present model has been compared with the experimental data from
Campoy et al. [50] for the same biomass fuel and equivalence ratios
(ER = 0.27 and 0.19) at atmospheric pressure. In the present work, the
tar species considered at the gasifier outlet are styrene, naphthalene,
phenylacetylene, anthracene, 7,12-dimethylbenz(a)anthracene and its
isomers, corannulene and its isomers, pyrene and its isomers, biphenyl,
phenol, toluene, napthol, acenaphthylene and its isomers, indene and
xylene. It may be noted in this context that while the simulated gasifier
conditions are according to Table 2, the experimental conditions in
Campoy et al. [50] are the following: biomass feeding rate 15 kg/hr,
gasifier bed temperature 805 °C (for ER = 0.27) and biomass feeding
rate 20.5 kg/hr, gasifier bed temperature 780 °C (for ER = 0.19).
It is observed from the model predictions that the mole fraction (in
percentage) of H2 in the producer gas increases monotonically from
13.44% to 16.26% (Fig. 2a) and that of CO from 13.67% to 16.32%
(Fig. 2b) as the ER is decreased from 0.27 to 0.19. On the other hand,
the mole fraction of CH4 increases marginally from 4.88% to 5.35%
(Fig. 2c) with the corresponding change of ER. The concentration of
CO2 first decreases from 16.70% to 15.44% with ER changing from 0.27
to 0.24 and then increases to 16.26% as ER decreases further to 0.19
(Fig. 2d). The simulation results demonstrate a good agreement with
the experimental result of Kim at al. [39] as observed from the figures.
The prediction of CO shows a maximum deviation of 5.15% at ER of
0.24 and a minimum of −0.94% at ER of 0.27 from the corresponding
experimental results. Likewise, the deviations for all other species and
at all three ERs remain well within ± 10%. On a similar note, it may
be observed from Fig. 2e that the present model predicts the tar content
quite accurately as well. One reason of the deviation between the ex-
perimental data and the numerical prediction, whatever is observed in
the figure, is the difference in operating conditions between the ex-
periments and simulation.
It is seen from Fig. 2 that the mole fractions of CO and H2 increase
continually with the decrease in equivalence ratio. At a lower equiva-
lence ratio, as the environment within the gasifier becomes less oxi-
dizing, more incomplete combustion products, like CO and H2, remain
in the product gas. Similar trends in the variations of syngas composi-
tion with the change in ER were observed by earlier researchers [23,51]
in their gasification studies. The opposing trend in the variation of CO2
Pyrolysis Temperature (°C) Gasification Temperature (°C)
650 769
681 765
660 739
B. Das, et al. Fuel 280 (2020) 118582

(a) (b)
H2 (Present Simulation) CO (Present Simulation)
20 20
H2 (Experiment [39]) CO (Experiment [39])

H2 Mole Fraction (dry vol.%)

CO Mole Fraction (dry vol.%)

15 15

10 10

5 5

0 0
Case I Case II Case III Case I Case II Case III

(c) (d) CH4(Present Simulation)

20 CO2 (Present Simulation)
8
CO2 (Experiment [39]) CH4 (Experiment [39])

CH4 Mole Fraction (dry vol.%)

CO2 Mole Fraction (dry vol.%)

15 6

10 4

5 2

0 0
Case I Case II Case III Case I Case II Case III

(e) 40 Tar (Present Simulation)

Tar (Experiment [50])
Tar Concentration (g/Nm3)

30

20

10

0
ER 0.27 ER 0.19
Fig. 2. Comparions of the predicted mole fractions of syngas components from the present model with the experimental data from the literature [39]; (a) H2, (b) CO,
(c) CO2, (d) CH4 and (e) tar for different equivalence ratios as in table 1.

mole fraction with the change in ER from 0.19 to 0.24 and then from
0.24 to 0.27, observed in the present work, is also in line with the re-
sults of biomass gasification reported earlier by Lv et al. [52]. Gasifi-
cation temperature along with the ER influences the chemical reactions
to alter the concentrations of the components in the producer gas.
In order to understand the chemical conversion paths enabling the
formation of the major combustible components of the syngas (H2 and
CO), the rate of production (ROP) analysis has been done in the flui-
dized bed zone of the gasifier (i.e. in PSR2) for H2 and CO. The rate of
production of H2 and CO in the major reaction steps, at ER = 0.19, are
shown in Fig. 3(a) and 3(b), respectively. It is to be noted that in the
reaction zone, there can be a host of reactions involving a particular
species. Out of them, some reactions produce the particular species
resulting in a positive rate of production while, other reactions consume
it causing a negative rate of production. We have shown six most sig-
nificant reactions, for each of H2 and CO, in terms of the absolute value
of rate of production in Fig. 3. It is observed that the reaction of for-
maldehyde (CH2O) with the H radical is the most dominant path in the
formation of H2, contributing to its maximum rate of production
(Fig. 3(a)). On the other hand, the reaction of H2 with phenyl (C6H5),
vinyl (C2H3) and methoxy (CH3O) radicals are significant in the con-
sumption of H2. The reaction of cyclopentadiene (CYC5H6) with H ra-
dical also has a positive reaction rate for the generation of hydrogen,
although to a much lesser extent. Similarly, the reaction of hydrogen
with styrene radical (C6H5C2H2) consumes H2 to some extent. The
formation of CO mostly takes place through the oxidation of formyl
radical (HCO), showing the maximum rate of production of CO
(Fig. 3(b)). Reactions of benzene (C6H6), acetyl radical (CH3CO) and
cyclopentadienyl radical (CYC5H5) with other radicals also produce CO,
though to a much lesser extent. The reactions of CO with hydroperoxyl
radical (HO2) and hydroxyl radical (OH) are significant for CO de-
struction. Both these reaction steps lead to the formation of CO2 in the
bed. All the results show the dominating effects of different radicals
towards the production of H2 and CO in the syngas. The temperature
existing in the gasifier plays an important role in controlling the ki-
netics of the reactions and influencing the formation of the syngas
constituents. In the present simulation, the temperature has been set in
agreement with the experiment. These results indicate the inadequacy

6
B. Das, et al.
(a) ROP H2
-0.4 -0.2 0 0.2 0.4 0.6 0.8
Rate of Production (mole/cm3-s)×107
(b) ROP CO
-3.00 -2.00 -1.00 0.00 1.00 2.00
Rate of Production (mole/cm3-s)×107
Fig. 3. Rate of Production for (a) H2 and (b) CO at 739.4° C gasifier temperature and 0.19 ER.
of equilibrium model in simulating the gasifier operation.
3.2. Analysis of tar production
The most important contribution of the present work is the evolu-
tion and prediction of tar components in different parts of the gasifier
and finally in the producer gas. A significant amount of tar components
is formed in the pyrolysis products following the decomposition of the
biomass. The tar produced during pyrolysis further undergo cracking in
the gasification zone and produce a mixture of non-condensable gases,
light hydrocarbons and unconverted tar fractions. The formation of the
tar components depends on the gasifier operating parameters such as
pressure, temperature, equivalence ratio and also on the residence time
over which the chemical reactions occur. It has been observed in the
literature that for the operating temperature range of the gasifier, as
considered in this work, the predominant tar species are the aromatics
[14].
3.2.1. Identification of main tar forming reactions
Benzene (C6H6) is the aromatic species with single aromatic ring
formed during the pyrolysis of biomass. Other aromatic species are
formed from it through a sequence of reactions. Among a host of dif-
ferent hydrocarbon species in the chemical mechanism, we have iden-
tified five species, namely benzene, toluene, styrene, xylene and
naphthalene, [13,27] and plotted their concentrations in the pyrolysis,
gasification and freeboard regions to show the evolution of the tar
species in the gasifier (Fig. 4(a)-(e)). All the results of Fig. 4 are for
ER = 0.19 and with the corresponding flow rates listed in Table 2.
Moreover, to understand the evolution path of the tar species, we have
also plotted the most significant reaction steps in the pyrolysis and
gasification zones causing the formation or destruction of each of the
five tar species as mentioned above (Fig. 5) at the same ER.
The mole fractions of the species, shown in Fig. 4, indicate that the
concentrations of the tar species remain the highest in the pyrolysis
Fuel 280 (2020) 118582
6. C6H5C2H2+H2=>C6H5C2H3+H
5. H+CYC5H6=>H2+CYC5H5
4. H+CH3OH<=>H2+CH3O
3. C2H3+H2=>C2H4+H
2. H+C6H6<=>H2+C6H5
1. H+CH2O<=>H2+HCO
1 1.2
6. HO2+CYC5H5=>C4H5+CO+OH
5. CH3CO+M<=>CH3+CO+M
4. OH+C6H6=>CYC5H6+CO+H
3. CO+OH<=>CO2+H
2. CO+HO2<=>CO2+OH
1. O2+HCO<=>HO2+CO
3.00 4.00
zone. This is due to the release of the hydrocarbon species during the
devolatilization of biomass and subsequent reactions among them in
the pyrolysis zone. Such observations have been made previously
during biomass pyrolysis studies [53–55]. The concentrations of the tar
species decrease in the gasification zone through various cracking re-
actions [56,57]. Thereafter, not much change in the concentrations has
been found to occur in the freeboard region. Fig. 4 shows that benzene
is having much higher concentrations than any of the other four species
plotted in the figure. This observation is in line with the experimental
observation made by Dufour et al. [58] for the pyrolysis of solid bio-
mass. The mole fraction of benzene in the pyrolysis zone is 4.8%, which
drops down to 2.3% during the gasification (Fig. 4(a)). Styrene is the
second most significant species having mole fraction of 0.75% in the
pyrolysis zone (Fig. 4(c)). The concentrations of toluene (Fig. 4(b)) and
naphthalene (Fig. 4(e)) in the pyrolysis zone remains at 0.13% and
0.17%, respectively, while xylene has mole fraction less than 0.03%
during the pyrolysis (Fig. 4(d)). The mole fractions of styrene, naph-
thalene, toluene and xylene are 0.17%, 0.07%, 0.025% and 12 ppm,
respectively, after gasification. Finally, not much change in the con-
centrations of the species occur in the freeboard and the mole fractions
of the tar components in the final producer gas remain only slightly
lower than those in the gasifier. The near constant major species con-
centration along the freeboard zone of a bubbling fluidized bed gasifier
has been previously reported in the experimental study by Radmanesh
et al. [43] as well.
The detailed chemical mechanism considered in different zones of
the gasifier enables to identify the major reaction steps through which
the important tar species are formed or consumed. As the freeboard
zone does not contribute in changing the concentrations of the tar
species to any significant extent, only the pyrolysis and gasification
reactions have been focused upon in the present work. Fig. 5(a) and
5(b) show the ten most significant reactions involving benzene during
the pyrolysis and gasification, respectively, on the basis of the magni-
tude of the rate of production of benzene. The formation of benzene in
7
B. Das, et al. Fuel 280 (2020) 118582

6 0.15
(a) Benzene (b) Toluene
5

Mole Fraction (%)

Mole Fraction (%)

4 0.1

2 0.05

0 0
Pyrolysis Gasification Freeboard Pyrolysis Gasification Freeboard

1 0.032
(c) Styrene (d) Xylene
0.8
0.024
Mole Fraction (%)

Mole Fraction (%)

0.6
0.016
0.4

0.008
0.2

0 0
Pyrolysis Gasification Freeboard Pyrolysis Gasification Freeboard

0.2

(e) Napthalene
0.15
Mole Fraction (%)

0.1

0.05

0
Pyrolysis Gasification Freeboard
Fig. 4. Predicted mole fractions of (a) benzene, (b) toluene , (c) styrene, (d) xylene and (e) napthalene at the outlets of different zones in the gasifier at bed
temperature of 739.4° C and ER 0.19.

the pyrolysis zone is mainly contributed by the reactions
C2H3 + C4H4= > C6H6 + H, H + LC6H6 < = > C6H6 + H and
C6H5 + CH2CO= > C6H6 + HCCO, having production rates of
11.26 × 10-7 mol/cm3-s, 10.14 × 10-7 mol/cm3-s and 9.34 × 10-7 mol/
cm3-s, respectively (Fig. 5(a)). Colket [59] identified the first of the
above three reactions, between vinyl radical (C2H3) and vinylacetylene
(C4H4), as the main route to the formation of benzene during pyrolysis
in the prescribed temperature range. The importance of H radical in the
reactions of benzene is evident from the list of reactions in Fig. 5(a). H
radical reacts with toluene (C7H8) to form benzene by separating a
methyl radical (Reaction 5). Another significant reaction in benzene
formation (Reaction 6) is the acetylene (C2H2) addition to n-butadienyl
(C4H5) followed by cyclization and hydrogen loss as suggested by Cole
et al. [60]. On the other hand, consumption of benzene occurs during
pyrolysis to form naphthalene (C10H8) through reactions 4, 8 and 10;
styrene (C6H5C2H3) through reaction 7 and methane (CH4) through
reaction 9.
In the gasification zone of the fluidized bed, the mole fraction of
benzene drops down considerably compared to that in the pyrolysis
zone. The analysis of the rate of production of benzene in the gasifi-
cation zone (Fig. 5(b)) indicates the most significant reaction to be that
between phenyl group and hydrogen gas to form benzene (Reaction 1).
However, the production rate of benzene in the above reaction is sub-
sided by the two main consumption reactions in which CO and CH4 are
formed (Reactions 2 and 3). While the rate of production of benzene in
reaction 1 occurs at a rate of 0.22 × 10-7 mol/cm3-s, the consumption of
benzene through the next two reactions occurs at a cumulative rate of
0.27 × 10-7 mol/cm3-s. Likewise, considering the whole set of reactions
of benzene in the gasification zone, the net rate of production is ne-
gative, lowering the concentration of benzene from its value in the
pyrolysis zone. The volumetric rate of production of benzene plotted in
Fig. 5(a) and 5(b) for the pyrolysis and gasification zones, respectively,
show a two order of magnitude difference in their values. This is be-
cause of the shorter volume of the pyrolysis zone in which the reactions
get completed indicating the fast rate of reaction occurring there. Si-
milar order variation in the rates of production of other species has also
been observed between the pyrolysis and gasification zones.
The ten important reactions involving toluene in the pyrolysis and

8
B. Das, et al. Fuel 280 (2020) 118582

(a) Pyrolysis 10. C4H3+C6H6=>C10H8+H

9. CH3+C6H6=>CH4+C6H5
8. CH2C3H5+C6H6=>2H2+H+C10H8
7. H+C6H5C2H3<=>C6H6+C2H3
6. C4H5+C2H2<=>C6H6+H
5. H+C7H8<=>C6H6+CH3
4. C4H5+C6H6=>C10H8+H2+H
3. C6H5+CH2CO=>C6H6+HCCO
2. H+LC6H6<=>C6H6+H
1. C2H3+C4H4=>C6H6+H

-10.00 -5.00 0.00 5.00 10.00 15.00

Rate of Production (mole/cm3-s)×107

(b) Gasification 10. C6H5+CH2O=>C6H6+HCO

9. HO2+C6H6=>H2O2+C6H5
8. H+LC6H6<=>C6H6+H
7. C2H3+C4H4=>C6H6+H
6. C6H5+CH4=>C6H6+CH3
5. H+C6H5OH<=>C6H6+OH
4. C4H5+C6H6=>C10H8+H2+H
3. CH3+C6H6=>CH4+C6H5
2. OH+C6H6=>CYC5H6+CO+H
1. H+C6H6<=>H2+C6H5

-0.15 -0.10 -0.05 0.00 0.05 0.10 0.15 0.20 0.25

Rate of Production (mole/cm3-s)×107

(c) Pyrolysis 10. C7H8<=>CH3+C6H5

9. C2H3+C7H8=>C2H4+C7H7
8. C6H4CH3+H2=>C7H8+H
7. CH3+C7H8<=>CH4+C7H7
6. H+C7H8=>H2+C6H4CH3
5. H+XYLENE<=>C7H8+CH3
4. 2SC4H7=>CH3+H+C7H8+H2
3. H+C7H8=>H2+C7H7
2. H+C7H8<=>C6H6+CH3
1. C7H8<=>C7H7+H

-8.00 -6.00 -4.00 -2.00 0.00 2.00 4.00 6.00 8.00

Rate of Production (mole/cm3-s)×107
Fig. 5. Rate of production in the pyrolysis and gasification zone for major tar components; (a) & (b) benzene (c) & (d) toluene, (e) & (f) styrene, (g) & (h) xylene and
(i) & (j) naphthalene at bed temperature of 739.4° C and ER 0.19.

gasification zones, in terms of the magnitude of rate of production, are
shown in Fig. 5(c) and 5(d), respectively. It is observed that the first
reaction in the pyrolysis zone produces toluene while the next two
important reactions consume toluene (Fig. 5(c)). Reactions 4 and 5 of
the pyrolysis zone again produce toluene. The net contribution of the
ten significant toluene reactions in the pyrolysis zone is a rate of pro-
duction of 1.09 × 10-7 mol/cm3-s, while the other reactions are even
less contributing. This rate of production is much smaller in comparison
to that of benzene for which the net rate of production of the ten im-
portant reactions in the pyrolysis zone is 21.18 × 10-7 mol/cm3-s. As a
result, the toluene concentration never increases to a very high value in
the pyrolysis zone and the toluene mole fraction at the exit of the
pyrolysis zone remains at 0.13%. The mole fraction of toluene drops
considerably (by 82%) in the gasification zone as toluene reacts with
different radicals like H, CH3, OH and HO2. H-abstraction reactions are
found to play important role in many of the destruction reactions of
toluene with the radicals. The cracking reactions of toluene in the ga-
sification zone results in the formation of CH4 and H2 as in reactions 2
and 3, respectively, (Fig. 5(d)).
The formation of styrene (C6H5C2H3) in the pyrolysis zone mainly
occurs through the reaction of benzene with vinyl radical (C2H3)
marked as shown in reaction 1 of Fig. 5(e). The reactions

9
B. Das, et al. Fuel 280 (2020) 118582

(d) Gasification 10. OH+C7H8=>C6H4CH3+H2O

9. H+C7H8=>H2+C6H4CH3
8. C7H8<=>C7H7+H
7. H+C7H8<=>C6H6+CH3
6. HO2+C7H8=>H2O2+C7H7
5. OH+C7H8=>C7H7+H2O
4. C6H4CH3+H2=>C7H8+H
3. H+C7H8=>H2+C7H7
2. CH3+C7H8<=>CH4+C7H7
1. O2+C7H8<=>HO2+C7H7

-0.02 -0.01 -0.01 0.00 0.01 0.01 0.02

Rate of Production (mole/cm3-s)×107

(e) Pyrolysis 5. C2H3+C6H5C2H3=>C2H4+C6H5C2H2

4. C6H5C2H2+CH2CO=>C6H5C2H3+HCCO
3. C4H5+C4H4=>C6H5C2H3+H
2. H+C6H5C2H3=>H2+C6H5C2H2
1. H+C6H5C2H3<=>C6H6+C2H3

-2.00 -1.00 0.00 1.00 2.00 3.00 4.00 5.00

Rate of Production (mole/cm3-s)×107

(f) Gasification 5. CH3+C6H5C2H3=>CH4+C6H5C2H2

4. C6H5C2H2+C6H6=>C6H5C2H3+C6H5
3. HO2+C10H7OH=>C6H5C2H3+2CO+OH
2. C6H5C2H2+H2=>C6H5C2H3+H
1. OH+C6H5C2H3=>H2O+C6H5C2H2

-0.16 -0.12 -0.08 -0.04 0.00 0.04 0.08

Rate of Production (mole/cm3-s)×107

(g) Pyrolysis 5. CH3+XYLENE=>CH4+RXYLENE

4. H+XYLENE<=>C7H8+CH3
3. 2SC4H7=>2H+XYLENE+H2
2. H+XYLENE=>H2+RXYLENE
1. XYLENE<=>RXYLENE+H

-6.00 -4.00 -2.00 0.00 2.00 4.00 6.00 8.00

Rate of Production (mole/cm3-s)×107
Fig. 5. (continued)

C4H5 + C4H4= > C6H5C2H3 + H and
C6H5C2H2 + CH2CO= > C6H5C2H3 + HCCO also contribute towards
the formation of styrene, though to a lesser extent than the first reac-
tion. Styrene is consumed in the pyrolysis zone through its reaction
with H-radical (reaction 2) and vinyl radical (reaction 5). However, the
rate of consumption of styrene in these reactions remains far less than
its rate of generation in reaction 1. Thus, the styrene concentration in
the pyrolyzed product remains at 0.75%, which is higher than toluene
and naphthalene. Styrene mole fraction drops down to 0.17% in the
gasification zone mainly due to its reaction with OH radical producing
water vapour and C6H5C2H2 (Fig. 5(f)). The consumption rate of
styrene in this reaction far outweighs the formation of rate of styrene in
other reactions for which the styrene concentration falls considerably in
the gasification zone.
The formation rate of xylene in the pyrolysis zone is low and most of
the xylene formed there is cracked in the gasification zone by H, OH
and CH3 radicals (Fig. 5(g) and 5(h)). Only 3% of the xylene produced
in the pyrolysis, is present at the gasifier outlet. Naphthalene is another
important tar compound formed in the pyrolysis zone mainly from the
single ring aromatic benzene (Fig. 5(i)) and also from tetralin and
naphthalene radicals. Naphthalene also gets consumed through the
reaction with H radical in this zone. Combination of all these reactions
leaves the pyrolyzed gas with 0.16% naphthalene, which drops down in
the gasification zone to near about 0.06%. The important cracking

10
B. Das, et al. Fuel 280 (2020) 118582

(h) Gasification 5. CH3+XYLENE=>CH4+RXYLENE

4. H+XYLENE<=>C7H8+CH3
3. O2+XYLENE<=>HO2+RXYLENE
2. OH+XYLENE=>H2O+RXYLENE
1. H+XYLENE=>H2+RXYLENE

-4.00 -3.00 -2.00 -1.00 0.00 1.00 2.00 3.00

Rate of Production (mole/cm3-s)×1010

(i) Pyrolysis 10. C2H3+C6H5C2H=>C10H8+H

9. C10H7+CH2CO=>C10H8+HCCO
8. H+C10H8=>H2+C10H7
7. C4H3+C6H6=>C10H8+H
6. CH2C3H5+C6H6=>2H2+H+C10H8
5. C10H7+H2=>C10H8+H
4. RTETRALIN=>C10H8+H2+H
3. C4H5+C6H6=>C10H8+H2+H
2. H+C10H8=>0.5RTETRALIN+0.5C10H7
1. H+C10H8=>C6H5+C4H4

-15.00 -10.00 -5.00 0.00 5.00 10.00

Rate of Production (mole/cm3-s)×107

(j) Gasification 10. C4H3+C6H6=>C10H8+H

9. C4H2+C6H6=>C10H8
8. H+C10H8=>H2+C10H7
7. O2+C14H9=>C10H8+2CO+C2H
6. OH+BIN1A=>0.4H2+0.2C10H8+0.85BIN1A+HCO
5. C10H7+H2=>C10H8+H
4. C4H5+C6H6=>C10H8+H2+H
3. RTETRALIN=>C10H8+H2+H
2. H+C10H8=>0.5RTETRALIN+0.5C10H7
1. H+C10H8=>C6H5+C4H4

-0.06 -0.04 -0.02 0.00 0.02 0.04

Rate of Production (mole/cm3-s)×107
Fig. 5. (continued)

reactions contributing to the fall in naphthalene concentration in the alone. The gasifier temperatures have been maintained in line with the
gasification zone are again affected by H radicals (Fig. 5(j)). experiments of Kim et al. [39] and are fixed at 769.3 °C, 765 °C and
739.4 °C, respectively, for ER = 0.27, 0.24 and 0.19. It is observed from
the figure that with the decrease in equivalence ratio, as the gasifier
3.2.2. Effects of equivalence ratio on tar species
environment becomes richer in fuel, the mole fractions of most of the
The effect of equivalence ratio on the concentration of selected tar
tar species increase. This happens due to less availability of oxygen to
species in the producer gas formed in the gasification of woody biomass
react with the tar compounds inside the gasifier. The mole fraction of
in a bubbling fluidized bed gasifier is shown in Fig. 6(a)- (f). The mole
benzene far exceeds the other hydrocarbons in the producer gas as
fractions of benzene, toluene, xylene, styrene, naphthalene, a few 2–3
observed from the figure. The mole fraction of benzene in the producer
rings aromatics, and a few other 4–7 rings aromatics are plotted in the
gas at ER = 0.27 is 1.8%, while at ER = 0.19 the mole fraction of it
figure for three equivalence ratio values (ER = 0.27, 0.24 and 0.19).
goes up to 2.3%. Styrene and naphthalene are two most abundant
For the comparative study, the equivalence ratio is varied only by
species after benzene. While styrene mole fraction at ER = 0.19 is
changing the air flow rate while keeping a constant biomass feeding
0.16% that of naphthalene at the corresponding condition is 0.07%.
rate of 55 kg/hr. Thus, the operating conditions for the results in Fig. 6
Toluene is found to have a low concentration. Interestingly, some of the
do not fully agree with those in Table 2, where for the ER = 0.27 case,
2–3 ring and 4–7 ring tar components show a decrease in their mole
the biomass feeding rate is different. We have done this as biomass feed
fractions when the ER is changed from 0.27 to 0.24; but their con-
rate is also an influencing parameter on tar formation and varying it
centrations increase when the environment in the gasifier is made
along with the equivalence ratio will not indicate the effect of the latter

11
B. Das, et al. Fuel 280 (2020) 118582

3.00 0.2
(a) Benzene (b) Styrene

1- Ring Tar Mole Fraction (%)

Benzene Mole Fraction(%)
2.50 Toluene
0.16
2.00
0.12
1.50
0.08
1.00

0.50 0.04

0.00 0
ER 0.27 ER 0.24 ER 0.19 ER 0.27 ER 0.24 ER 0.19

3.0E-4 0.1
(c) (d) Napthalene

2-3 Ring Tar Mole Fraction (%)

Xylene Phenanthrene and anthracene
2.5E-4
Xylene Mole Fraction (%)

0.08 Biphenyl
2.0E-4
1.5E-4 0.06

1.0E-4 0.04
5.0E-5
0.02
5.0E-19
ER 0.27 ER 0.24 ER 0.19
-5.0E-5 0
ER 0.27 ER 0.24 ER 0.19

0.01 0.06
(e) Acenaphthalene and isomers (f) Corannulene and isomers
4-7 Ring Tar Mole Fraction (%)
2-3 Ring Tar Mole Fraction (%)

Fluorene
0.008 0.05 7,12-Dimethylbenz[a]anthracene
Diphenylmethane
and isomers
0.04 Pyrene and isomers
0.006
0.03
0.004
0.02
0.002
0.01

0 0
ER 0.27 ER 0.24 ER 0.19 ER 0.27 ER 0.24 ER 0.19
Fig. 6. Predicted mole fraction of tars; (a) benzene, (b) styrene & toluene, (c) xylene, (d) &(e) 2–3 ring tars, and (f) 4–7 ring tars at different equivalence ratios with
fixed biomass flow rate of 55 kg/hr and gasifier temperature of 769.3 °C, 765 °C and 739.4 °C for ER of 0.27, 0.24 and 0.19 respectively.

richer with ER = 0.19. This trend is similar to that of CO2 in the pro-
ducer gas with the variation in ER and can be attributed to the re-
sidence time and oxidizing atmosphere within the gasification zone of
the reactor. It is to be mentioned here that in the present computation
the temperature of the gasifier has been defined in each case without
computing the value from the energy conservation equation at the
corresponding ER. The gasification air flow rate through the bed is
lower at lower ER, maintaining a less oxidizing (i.e. richer) environ-
ment in the bed. The kinetic rates of reactions change accordingly due
to the change in concentrations of the reacting species. At the same
time, the reduced flow rate of air through the bed increases the re-
sidence time of the species within the bed enabling them to participate
in chemical reactions over longer duration. The combined effect of
these two results in non-monotonic variation of the mole fraction of
certain tar species with the change in ER. Similar trends in the results
were earlier reported from the fluidized bed gasification study of
sawdust biomass by Horvat et al. [61].
The total tar concentration formed in the gas (g/Nm3) has been
computed for the three ER values to observe the variation. The aromatic
species with heavier molecular weight than benzene have been con-
sidered in the total quantity of tar due to the ability of benzene to retain
its gaseous form at the exit of the gasifier [27]. The tar species con-
sidered here are the same as in Fig. 2 (e). The tar concentration in the
gas at ER = 0.19 is found to be 29.6 g/Nm3. However, the corre-
sponding values at ER = 0.24 and 0.27 are evaluated as 18.97 g/Nm3
and 18.76 g/Nm3, respectively. This nature of variation of the total tar
with ER is consistent with the experimental results of Kinoshita et al.
[62].
3.3. Overall gasifier performance
Table 3 gives a general description of the important performance
characteristics of the gasification process predicted from the model. The
experimental data from Kim et al. [39] have also been shown for
comparison at ER = 0.24 and 0.19 and good agreements are observed.
The results of ER = 0.27 have not been compared as it has already been

12
B. Das, et al.
Table 3
Gasifier performance at different equivalence ratios (ER) for biomass flow rate of 55 kg/hr and bed temperature of 769.3 °C, 765 °C and 739.4 °C for ER of 0.27, 0.24
and 0.19 respectively. The experimental data [39] at identical conditions is shown for comparison at ER = 0.24 and 0.19.
Parameter ER 0.27 ER 0.24
Present simulation Present simulation
CO (Volume %, dry) 13.97 15.77
CO2 (Volume %, dry) 16.10 15.44
H2 (Volume %, dry) 13.97 15.56
CH4 (Volume %, dry) 4.48 4.79
Tar (gm/Nm3) 18.77 18.97
LHV (MJ/Nm3) 5.33 5.88
Dry gas production (Nm3/kg fuel) 2.18 2.09
CCE (%) 82.06 82.57
CGE (%) 64.62 68.42
mentioned in Section 3.2.2 that the biomass feeding rate for this con-
dition has been changed from that of Kim et al. [39]. The results show
that the combustible gaseous components in the producer gas, namely
CO, H2 and CH4, increase with the decrease in the ER. On the other
hand, the tar concentration in the producer gas increases considerably
at ER = 0.19, compared to the other two cases. Lower Heating Value
(LHV) of the producer gas is an important indicator of the quality of the
fuel produced. It is observed from the results in Table 3 that the LHV of
the fuel increases with lower ER, due to increased concentration of the
combustible components in the gas. On the contrary, lower ER leads to
lower rate of dry producer gas generation. The carbon conversion ef-
ficiency (CCE), representing the fraction of the number of carbon moles
in the biomass feedstock which has been transferred to the gaseous
components of the producer gas, decreases at ER = 0.19. It is to be
mentioned here that in calculating the carbon conversion efficiency we
have considered the carbon in CO, CO2, CH4, C2H4 and C2H6 in the
producer gas from the carbon in biomass. The reduction in carbon
conversion efficiency at ER = 0.19 is due to the carbon transferred in
the increased quantities of tar compounds.
Cold gas efficiency (CGE = dry gas generation, Nm3/kg fuel × LHV
of producer gas, MJ/Nm3/LHV of Biomass feedstock, MJ/kg) defines
the fraction of the stored energy in the biomass which is transferred to
the producer gas fuel on gasification. The results show that among the
three ER values considered, the maximum cold gas efficiency is ob-
tained at the middle value of ER = 0.24. It shows that there is an op-
timum equivalence ratio of operation of the gasifier which will give the
most efficient energy conversion performance. It may be mentioned in
this regard, that the presence of optimum equivalence ratio in the
context of cold gas efficiency of bubbling fluidized bed gasifiers has
been reported before in both theoretical [63] and experimental [64]
studies.
It may be summarized from the above results that the detailed
chemical kinetic analysis of biomass gasification process in bubbling
fluidized bed reactors brings about the identification of important re-
action pathways leading to the prediction of syngas composition.
Therefore, the present study provides accurately validated explanations
on the formation and destruction routes of major pyrolysis and gasifi-
cation products like H2, CO and tar. The approach developed in this
work is the first of its kind and is expected to provide more accurate
chemical information on tar formation in bubbling fluidized bed bio-
mass gasifiers. Moreover, as an additional advantage, the proposed
approach demands very little amount of computational resource due to
the exclusion of detailed fluid dynamic analysis.
4. Conclusions
A kinetic model of fluidized bed gasifier has been developed based
on an Equivalent Reactor Network (ERN). The gasifier is divided into
three zones – pyrolysis zone, gasification zone in the bed and freeboad
zone. Pyrolysis of the biomass is modeled with a thermodynamic
equilibrium model followed by a kinetic model applied in a perfectly
13
Fuel 280 (2020) 118582
ER 0.19
Kim et al. [39] Present simulation Kim et al. [39]
15 16.32 16.1
16 15.93 16.4
16.1 16.26 16.5
4.6 5.35 5.3
– 29.60 –
5.3 6.26 5.7
– 1.84 –
– 76.24 –
– 64.02 –
stirred reactor (PSR1). Subsequently, the gasification zone and free-
board have been modeled using a second perfectly stirred reator (PSR2)
and a plug flow reactor (PFR). The kinetic scheme of biomass proposed
by the CRECK group has been used after eliminating 42 reactions
identified through a sensitivity analysis. The composition of the pro-
ducer gas has been compared against the experimental data from the
literature and a good agreement has been reached.
The following conclusions can be drawn from the study.
• Active radicals play an important role in determining the rates of
different gasification reactions in the fluidized bed. Kinetic para-
meters of the reaction equations decide the composition of the
producer gas mixture.
• Hydrocarbon species of tar are formed in the pyrolysis zone and
have their highest concentration there. Thereafter, the tar con-
centrations fall in the gasification zone of the fluidized bed. Not
much change in the concentrations of species is observed in the
freeboard zone of the gasifier.
• Benzene is having the maximum concentrations among different
aromatic hydrocarbons. Styrene and naphthalene are the next two
significant hydrocarbons. The concentrations of different hydro-
carbons depend on their formation and destruction rates in various
zones. The rate of reaction in the pyrolysis zone is significantly
larger than that in the gasification zone.
• For most of the tar species, the concentrations decrease continually
with the increase in ER. The oxidizing atmosphere created at higher
ER reduces the concentration of the hydrocarbons.
• However, for some 4–7 ring aromatic species (such as pyrene and its
isomers, corannulene and its isomers and 7,12-dimethylbenz(a)an-
thracene), the concentration becomes the minimum at an optimum
ER in between. Such a non-monotonic trend with ER originates from
the combined effects of changes in chemical kinetics and residence
time inside the reactor.
• The tar concentration in the producer gas drops considerably with
the increase in ER from 0.19 to 024. However, with further increase
in ER to 0.27, the drop in tar concentration is only marginal.
• Increase in ER from 0.19 to 0.27 decreases the LHV of the producer
gas due to less concentrations of the combustible components, like
H2, CO and CH4, in the oxidizing environment of the gasifier.
However, the dry gas production rate increases as the ER is in-
creased. The cold gas efficiency is found to be the maximum at
ER = 0.24 indicating it to be the optimum equivalence ratio leading
to the best performance of the gasifier.
• Finally, the proposed modelling approach provides accurate and
computationally inexpensive way of evaluating major products like
H2, CO and tar constituents in the fluidized bed biomass gasification
process.
CRediT authorship contribution statement
Bijoy Das: Methodology, Software, Formal analysis, Validation,
B. Das, et al.
Writing - original draft. Atmadeep Bhattacharya: Methodology,
Resources, Data curation, Writing - original draft. Amitava Datta:
Conceptualization, Writing - review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.118582.
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