Solar Energy Vol. 51, No. 1, pp. 19-25.

1993
Printed in the U.S.A.

0038~392X/93 $6.00 + .00

Copyright ~) 1993 Pergamon Press Ltd.

KINETIC MODEL OF BIOMASS GASIFICATION

Y. WANG and C. M. KINOSHITA
Hawaii Natural Energy Institute, University of Hawaii at Manoa, 2540 Dole Street, Holmes Hall 246,
Honolulu, HI 96822, U.S.A.
Abstract--A kinetic model for biomass gasification is developed based on the mechanism of surface reactions.
The apparent rate constants are computed by minimizing the differences between experimental data and
theoretical results for different residence times and different temperatures. The kinetic model is validated
by comparing experimental data with the theoretical results for different equivalence ratios; the simulations
agree well with the experimental data. Simulations modeling the influence of char particle size on the time
required to achieve 90% carbon conversion agree with the results of tests performed by other investigators.
Simulations are performed to evaluate the effects of the following parameters on biomass gasification: (a)
type of oxidant, (b) residence time, (c) char particle size, (d) temperature, (e) pressure, (f) equivalence
ratio, and (g) moisture.

1. I N T R O D U C T I O N

Biomass gasification processes in downdrafl gasifiers

and fluidized bed gasifiers are quite similar--the biomass undergoes a series of thermochemical conversion
processes: pyrolysis, combustion, and reduction. It is
believed that each of these processes takes place in different reaction zones. For example, flaming pyrolysis
( F P ) , char reduction ( C R ) , and inert char zones have
been identified in stratified downdraft gasifiers[6]. The
combustion reaction in the FP zone is much faster
than the gasification reaction in the CR zone [ 7 ] ; thus,
the overall biomass gasification rate is controlled by
kinetics in the CR zone.

The primary goal of biomass gasification for energy

refinement is the conversion of the chemical energy in
biomass into chemical energy in the product gas. Understanding the kinetic mechanism of biomass gasification is crucial to designing and operating biomass
gasification systems, and achieving optimal energy
conversion.
Several attempts have been made to predict the
equilibrium compositions of product gases[I,2,3 ]. A
kinetic model has been developed for pyrolysis of single
particles of biomass [ 4 ]. This model has classified the
pyrolysis products into only two components: volatiles
and char (the composition of the volatile matter was
not predicted due to the complex nature of the pyrolysis
process). A nonisothermal model, based on empirical
rate equations of C-CO2 and C-H20 reactions, has been
developed for gasification of single char particles[ 5 ].
This model ignored methane reactions and assumed
that the water-gas shift reaction was in equilibrium all
time.
The above mentioned models were based on simplified gasification processes. Comparisons of equilibrium and actual gas compositions indicate that substantial differences between the actual gas composition
and theoretical predictions exist [ 2 ]. The kinetic formulation presented here attempts to more accurately
model biomass gasification based on the kinetics of
surface reactions.

2.1 Initial conditions

Biomass enters the high temperature FP zone where

it is converted into char and volatiles. Combustion
takes place when the volatiles react with oxidant. The
pyrolysis-combustion process in the FP zone is dominated by exothermic reactions where biomass is converted into char, CO2, and H20. It is assumed that
part of the volatiles are cracked into methane in the
FP zone. The products from the FP zone then move
into the C R zone, where endothermic reactions dominate and the thermal energy generated by the pyrolysiscombustion process is transformed into chemical energy in combustible gas species such as H2 and CO.
The concentrations of the products exiting the FP zone
become the initial concentrations of the reactants in
the CR zone. Thus, in the CR zone, the initial amounts
of H2 and CO are zero and the amount of nitrogen
remains constant.
Continuity dictates that at t = 0 (i.e., when the
reactants enter the CR zone):

2. PRINCIPLES OF COMPUTATION
A general equation for biomass gasification is
C H l O e + yO2 + zN2 + w H 2 0 = x~C + x2H2

x2,0 = 0:

+ x3CO + x4H20 + x5CO2 + xrCH4 + x7N2

where CH~O~ is the chemical representation of biomass, and y, z, w, and x~ are the molar numbers of
various components. The subscripts a and 13 are determined from the ultimate analysis of the biomass
feedstock (e.g., a = 1.4 and fl = 0.59 for wood).

x3,0 = 0;

x7,0= z

XI,0 + XS,0 + 3('6,0 = 1

( 1)

2A'4,0 + 4X6,0 = a q- 2 W

(2)

x4.0 + 2X5.o = 2 y + 13 + w

(3)

where X~,ois the initial a m o u n t of species i in the C R

zone; y is a function of equivalence ratio ( E R ) ; and w
19

Y. WANGand C. M. KINOSHITA

20

can be calculated from the moisture:biomass ratio (dry

basis) wt. An additional relationship is needed to solve
eqns ( 1-3 ); the following is assumed,
x4.0 = XXs,o + w

(4)

where X denotes the water vapor:carbon dioxide formation ratio. ), = 1.0 for all computations in this study
based on the assumption that the same amounts of
CO2 and H20 (in addition to that from moisture in
the feedstock and injected steam w) are produced in
the FP zone.
2.2 Chemical reactions in the char reduction zone
Temperature in the CR zone ranges from 700900C. At temperatures below 900C, mass transfer
and pore diffusion are much faster than chemical reactions; thus, the rate-controlling factor is chemical
kinetics [ 6,7 ]. In the CR zone, the following reactions
take place.
1. C + C O 2 -~ 2C0
2. C + H 2 0 = H2 + C O
3. C + 2 H 2 = C H 4
4. H 2 0 + CH4 = C O + 3H2.
Substantial research has been conducted on the
surface kinetics of the C-CO2 reaction [ 8-13 ]. Different
kinetic mechanisms for the C-CO2 reaction have been
suggested by different investigators. For example,
Standish and Tanjung found that, at temperatures
900C and above, gasification occurs primarily on the
outer shell of the char particle, with the interior of the
char remaining largely unreacted, and that the overall
process was well represented by a shrinking corereaction control model [ 10].
Binford and Eyring studied the C-H20 reaction and
found that the water-gas shift reaction (H20 + CO
= H2 + CO2) does not participate in the reactions[14].
The kinetic study of methane thermal decomposition
suggested a very complicated chain reaction on the
carbon surface [ 15 ].
At the beginning of the present study, the watergas shift reaction was included in the model, but later
was eliminated because sensitivity analyses indicated
that the model was not sensitive to the apparent rate
constant for that reaction in the investigated range of
moisture:biomass ratio (w, < 0.2).
Surface reactions 1 and 2 involve single gas molecules. The Langmuir-Hinshelwood mechanism is applied [ 16 ],
A + S ~ A. S

A. S --,- products

(fast)
(slow)

where A denotes a gas molecule, S an active surface

site, and A. S an adsorbed molecule. Two molecules
are involved in surface reactions 3 and 4. The Langmuir-Rideal mechanism is applied [ 16 ],
A + S ~ A. S

A- S + B ~ products

(fast)
(slow)

where B denotes another gas molecule which reacts

with the adsorbed molecule A . S . Since several gas
species are involved in those surface reactions, competitive adsorption occurs [ 16 ]. The rate equation for
reaction 1 can be formulated based on the LangmuirHinshelwood mechanism:
-V+j = kIKsCTPs/(I + ~ KiPi)

(5)

where
~_, giPi = K2p2 + gaP3 "Jr g4P4
+ g s p 5 -t- K6P6 + gTP7.
v+~ is the reaction rate for reaction 1 in the forward
direction, p~ the partial pressure of gas species i, K~the
adsorption constant for species i, Cr the total active
sites of the char surface, and k~ the rate constant for
reaction 1 in the forward direction.
The net reaction rate can be obtained by extending
eqn (5) to include the reverse reaction rate in accordance with chemical equilibrium. The net rate for reaction 1, v,, can thereby be expressed as
-vl =

klKsCT(p 5 - p2 / Kpl )
1 + F, K~p~

(6)

where Kpl is the equilibrium constant for reaction 1.

The partial pressure of gas species i, p,, can be determined from
p, = x,/Px

(7)

where
1

Px = - ~ xi
P i=2
and p is the pressure in the gasifier. It is assumed that
the char panicles in the CR zone are spheres of uniform
size, and all of the char spheres shrink at the same rate
during the char reduction process. The active sites of
the char surface are proportional to the surface
area[12,14]and they can be determined from the following equation:
72ks [ X,o] 1/3

Xl

(8)

where o is char density, ks is the number of moles of

active sites per unit char surface area, and dp is the
initial diameter of the char sphere. Inserting eqns (7)
and (8) into eqn (6) gives:

- v , ( X ) = ko,

x. -

?I-;-Z

(x,.ol,-

x, /

x,

(9)

where k,~ = 72ksk~K5 is the apparent rate constant,

and Vl is written as v~(X) to emphasize its dependence
on X = (x~, x 2 , . . . , x7).

21

Kinetic model of biomass gasification

dx 5

Similarly, rate equations for reactions 2, 3, and 4

become

dt

-- ~)1 ( X )

(18)

-"---e= - v 3 ( X ) + v4(X).
dt

(19)

(10)

-- u3(X)

ka3 P ; ~ ?g---~ 1-~X i \ X, ]

It can be deduced from the above equations that

the composition of the product gas depends on the
pressure and temperature of the gasifier p and T, the
moisture:biomass ratio w~ (including the moisture in
the feedstock and the injected steam), equivalence ratio
(ER), the amount of nitrogen in the oxidant z, the
particle size of char dp, and the residence time t, i.e.,

,Ddp
(11)

X4X6- x3x3/(p2xK,,l) (Xl..o] 1/3 xi

(12)

X = f ( p , T, w,, ER, z, dp, t).

where v~(X) is the net reaction rate, Kp~is the equilibrium constant, and ka~ is the apparent rate constant
for reaction i. The apparent rate constant is the product
ofa pre-exponential factor Ai and an exponential factor,
according to the Arrhenius equation,

kai

3. EVALUATION OF PARAMETERS AND VALIDATION

OF MODEL

The simulation parameters include four equilibrium

constants Kpi, four apparent rate constants kai, and six
adsorption constants K~. The equilibrium constants are
determined from JANAF thermochemical data. The
adsorption constants should be independent of pressure, origin, porosity, crystallinity, and particle size of
carbon; however, they should depend on temperature [ 9 ]. The adsorption constants used in this model
are based on previous research [ 7 ] and are fixed due to
insufficient information on their dependence on ternperature.
The six unknowns x~ (i = 1, 2 . . . . . 6), for given
gasification conditions, can be determined by solving
six differential equations, eqns (14-19), simultaneously. A computer program (SCoP) was used to solve
the above differential equations [ 17 ].
The apparent rate constants were obtained by minimizing the differences between the test data and theoretical computations for different residence times at a
fixed temperature.

(13)

= AiEXP(-Eai/RT)

where R is the universal gas constant, Eat is the activation energy for reaction i, and T is the absolute temperature in the CR zone.
The following differential equations apply to the
reactions in the CR zone.

dxi

= l ) l ( X ) + 1)2(X ) + u 3 ( X )

(14)

dx2
- - = - l ) 2 ( X ) + 2t~3(X) - 3 u 4 ( X )

(15)

dx3
dt

(16)

--

dt

dt

2 v l ( X ) - v 2 ( X ) - v4(X)

dx4

( 17 )

d t = v2(X) + v4(X)

50'
40'
i

H2

30

[] CO
CH4

~ 20,
"~

o CO2

10.

0
0

CH~ --~=-

(20)

Cs

!
I

4 5 6 7 8
Residence Time (s)

10

Fig. 1. Residence time vs. species concentration ( Cs solid carbon is defined as the mass ratio of char residue:
biomass).

22

Y. WANGand C. M. KINOSHITA

"'o~ 5 0 ~ . ~
c

40

,-

30

co

o
0

20

"~

10

CO

n
H2

CO

'

* CH4

o C02
A Cs

if)

650

700

750

800

850

900

950

T e m p e r a t u r e (C)
Fig. 2. Temperature vs. species concentration.

Minf(kal, ka2, ka3, ka,) = Min ~ ~ (x 0 -

Xexp,tj)

j=] i=]

where Xexp,~jis the measured concentration of species i

at residence time tj, and x~j denotes the computational
value of species i at residence time tj. The test data
were obtained from a bench-scale indirectly heated,
fluidized bed gasifier operating at atmospheric pressure,
using saw dust as feedstock [ 18 ].
The theoretical results, based on the evaluated kai,
are compared with the test data for T = 800C in Fig.
1. The theoretical results fit the test data very well. ka~
can be evaluated for different temperatures in a similar
manner. The computational results (using the evaluated k~) are compared with the test data for different
temperatures in Fig. 2.
According to eqn ( 13):
In k~i = in Ai

for different equivalence ratios. The theoretical results

for CO and CH4 agree very well with the experimental
data; the theoretical results for CO2 compare reasonably
well with the test data. Slight differences between the
theoretical and actual data exist for H2; however, the
trends are the same.

4. S I M U L A T I O N S - - R E S U L T S AND DISCUSSION

The kinetic model, with the evaluated rate constants, was used to analyze the influences of the various
parameters on conversion ratio (the conversion ratio
of a species is defined as its yield in molar n u m b e r per
mole ofbiomass feed; CHI.400.59). The conversion ratio
for H20 is not discussed below, since only dry product
gas is of interest to most researchers. Unless noted otherwise, pure oxygen is the oxidant for the computational results presented below.

-- Eai/RZ.

4.1 Residence time

Regressions for kai are presented in Fig. 3. Ai and Ea~
are calculated according to the regressions. The regression results for the apparent constants are presented
in Table 1.
The kinetic model is validated in Fig. 4 by comparing the theoretical results with the experimental data

Computational simulations for varying residence

time are presented in Fig. 5. The results indicate that
the chemical reactions proceed very rapidly (i.e., conversion ratios for all species change significantly) during
the first 20 s. From 20-40 s, the chemical reactions
proceed relatively slowly. This occurs for the following
reasons: (a) concentrations of gaseous reactants decrease, (b) the total char surface area decreases due to
carbon consumption, and (c) the surface reactions become inhibited as more carbon surface is covered by
H2 and CO. The species do not change significantly

A_
m

Table 1. Regression results of the apparent rate constants

2
1[
8.5

,"

8.8

9.1

9.4

9.7

Reaction
i

I
10.0

10.3

104/T

Fig. 3. Arrhenius plot of apparent rate constants.

1
2
3
4

A~
( 1/s)
3.616
1.517
4.189 X
7.301 X

101
104
10-3

10-2

E~j
(KJ/tool)

R value
(%)

77.39
121.62
19.21
36.15

99.8
99.9
99.1
96.2

Kinetic model of biomass gasification

23

50
c

40

. CO

H2

2o

"~

10.

D.

= CO

*CH4
CO2

CH4"
0
0.15

a Cs

&

0.20

0.25

0,30

0.35

0.40

0.45

Equivalence Ratio
Fig. 4. Equivalence ratio vs. species concentration.

4.2 Char particle size

Chemical reaction rates are influenced by char particle size through the overall surface area of char. For
a fixed amount of char, increased particle size corresponds to decreased total char surface area, which reduces the surface reaction rate; thus, longer residence
time is needed to achieve the same conversion ratio.
Computations indicate that the residence time required
to achieve 90% carbon conversion efficiency, tc=o.~,
increases almost linearly with char particle size dp, (Fig.
6); this agrees with the results of tests performed by
Standish and Tanjung[10]. Conversion ratios of H2,
CO, CO2, and C H 4 for different dp are the same as
those shown in Fig. 5 (at tc~o., = 15 s), as long as the
residence time reaches tc=o.j.

for t > 40 s. All species approach equilibrium at long

residence time. Carbon conversion efficiency reaches
90% at tc=o.~ = 15 s for oxygen gasification and at tc=o.
= 20 s for air gasification. H2 and CO increase, and
carbon, CO2, and CH4 decrease, with increasing residence time.
Nitrogen is inert; however, it influences conversion
ratio in biomass gasification in the following respects:
(a) nitrogen dilutes reactant concentrations, which decreases reaction rates; (b) nitrogen molecules may
cover some active sites on the char surface, which inhibits the reaction; and (c) nitrogen in the reactants
reduces the residence time. The first two factors cause
a time lag for air gasification compared with oxygen
gasification. However, the time lag eventually disappears at sufficiently long residence time (t > 80 s). The
third factor may cause significant differences in conversion ratios between air gasification and oxygen gasification when t < 40 s. At equilibrium, the conversion
ratios for air gasification are the same as those for oxygen gasification.

4.3 Temperature
In biomass gasification, temperature influences rate
constants, equilibrium constants, and residence time.
Residence time is a function of the height of the gasifier
Lg, equivalence ratio (ER), moisture in the reactants

c iiiiiiiiiiiiiill
Oxygen

0.8

=
. o,

.......

u)

0.5
0.4

>
=
0
O

0.3
0.2 ~ F ~, ', C
,
C

"
.o

Air ......

.............

0.1

.c.9_2

............

10

20

30

40

Residence

-. . . . . . . . . . . . . . .

CH4
i

.... ,..... .

50 60

70

Time

(s)

i:"

80

"i

90 100

Fig. 5. Residence time vs. conversion ratio ( T = 800C, p = I arm, ER = 0.3, wt = 0, d p = 1 m m ) .

24

Y. WANG and C. M. YONOSH]TA

300
250 ~
200
150
100

*-

160
~ 12014~
1
.

50
0

60
40
20

0 2 4 6 8 I0 12 14 16 18
CharParticleSize(mm)

700

750

800

850

900

Temperature(C)

Fig. 6. Influence of particle size on tc=o.~(T = 800C,p = 1

atm, ER = 0.3, wt = 0).

Fig. 8. Influence of temeprature on tc=o.~ (p = arm, ER

= 0.3, wt = 0, dp = 1 mm).

wt; feedstock feed rate Gt, pressure p, and temperature

T, as given in the following equation:

creasing pressure, due to increased residence time (see

eqn [21]) and to reaction rates having greater effect
on conversion ratio at lower pressures. Pressures above
3 atm result in more CO2 and carbon, and less CO and
n2. CH4 behaves like CO2 and carbon, but reaches a
m i n i m u m at p = 6 atm.

t =

kt lpL~

(21)

G T ( k , 2 E R + w,)

where ktl and kt2 are conversion factors used to convert

the different units in eqn (21) into time. The computational results for varying temperature are presented
in Fig. 7. Residence time decreases slightly with increasing temperature. CO and H2 increase significantly
as temperature increases, even though residence time
decreases. Carbon decreases substantially, and CH4 and
CO2 decrease slightly, as temperature increases. The
residence time requied to achieve 90% carbon conversion efficiency decreases significantly with increasing
temperature (Fig. 8).
4.4 Pressure
The advantages of increased pressure are higher reaction rate due to increased partial pressure of each
species, and longer residence time due to reduced volumetric flow. The disadvantages of increased pressure
are higher yields of carbon and methane, and lower
yields of H2 and CO, due to a shift in equilibrium[ 2].
The computational results for varying pressure are
presented in Fig. 9. In the range 1 to 3 atm, CO and
H2 increase, and CO2 and carbon decrease, with in-

,12

0.7

11
10

4.6 Moisture
Simulations varying moisture:biomass ratio from
0 to 0.24, were performed to examine the effect of
moisture:biomass ratio of conversion ratio. Moisture
has little effect on conversion ratio in the range of
computation. This is caused by a balance between decreasing residence time (see eqn [ 21 ]) and increasing
H 2 0 reactant as moisture increases---decreasing residence time tends to convert less carbon into gaseous
species while increasing reactant tends to convert more
carbon into gaseous species.

0.7-

o6

g
.~

4.5 Equivalence ratio

The computational results for varying equivalence
ratio are presented in Fig. 10. Carbon, H2, and CO
decrease, and CO2 increases almost linearly, as ER increases due to increased oxygen in the reactants.
Methane increases with increasing ER for E R < 0.27
due to decreased residence time (see eqn [21 ]), and
decreases with increasing ER for E R > 0.3 as the combustion reaction becomes more prevalent.

- 240

=.o 0.0

r-o~ i 0.40.5.

o
650

700

750

800

850

900

950

.~

0.2.

iv-

0.1-

Temperature(C)
Fig. 7. Temperature vs. conversion ratio and residence time
(p = 1 atm, ER = 0.3, wt = 0, dp = I mm).

~"

- 160

- 120

0.30.1

.2oo
so

CH4

0.0
1

13

17

0
21

Pressure(atm)
Fig. 9. Pressure vs. conversion ratio and residence time (T
= 800C, ER = 0.3, wt = 0, dp = 1 mm).

Kinetic model of biomass gasification

-20
-18
-16

0.6"

":m
_ 0.50.4~

0.3.

-14
-12

-108

"~-~

0.2.
0

O.t.

0.0
0.15

I
0.20

I
0.25

I
0.30

I
0.35

I
0.40

~,

cc

0.45

Equivalence Ratio
Fig. 10. Equivalence ratio vs. conversion ratio and residence
time ( T = 800C,p = 1 atm, wt = 0, dp = 1 mm).
5. SUMMARY AND CONCLUSIONS

A kinetic model for biomass gasification was developed based on the mechanism of surface reactions.
The apparent rate constants were computed by minimizing the differences between the experimental data
and theoretical results for different residence times and
different temperatures. The kinetic model was validated
by comparing experimental data with the theoretical
results for different equivalence ratios; the simulations
agree well with the experimental data. Simulations
modeling the influence of char particle size on the residence time required to achieve 90% carbon conversion
agree with the results of tests performed by other investigators. Simulations were performed to evaluate
the effects of the following parameters on biomass gasification: (a) type of oxidant, (b) residence time, (c)
char particle size, (d) temperature, (e) pressure, (f)
equivalence ratio, and (g) moisture.

Acknowledgments--The authors thank the U.S. Department

of Energy, the National Renewable Energy Laboratory, and
the State of Hawaii for supporting this work.
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25

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