EQUILIBRIUM MODEL FOR BIOMASS GASIFICATION

Anil Khadse1, Prasad Parulekar2, Preeti Aghalayam1 and Anuradda Ganesh2*

1,
Department of Chemical Engineering, IIT Bombay, Powai, Mumbai-400076
2,
Energy Systems Engineering, IIT Bombay, Powai, Mumbai-400076
*
Corresponding author, Energy Systems Engineering, IIT Bombay, Powai,
Mumbai-400076 Phone: 022-25767886, Fax: 022-25726875, e-mail:aganesh@me.iitb.ac.in

Abstract
The utilization of biomass will provide sufficient energy which can be used for electricity generation, engine
applications, etc. Gasification is the process in which biomass is converted into clean and combustible gas in the
presence of steam and air. To model gasification process in detail, knowledge of chemical reaction kinetics is
required which is not available in open literature. Thermodynamic equilibrium composition prediction is the
important step in modeling the gasification process. Here the biomass is represented as CHxOy. The biomass is
reacted with steam and air to give product gases viz. CO, CO2, H2 and CH4. The model assumes that the
principle reactions are at thermodynamic equilibrium. The model equations containing four atom balances (C,
O, H and N) and three equilibrium relations are solved for gas compositions using MATLAB. The four types of
biomasses from India are used for prediction of equilibrium gas compositions. These four samples are compared
based on gross calorific values.

Keywords: Biomass, Thermodynamic equilibrium, gasification.

1. Introduction
Biomass is a non conventional energy source. The main biomass sources are wood, saw dust, agricultural
residues, aquatic and marine biomass and wastes (Bridgwater, 1994). The utilization of biomass will provide
sufficient energy which can be used for electricity generation, engine applications, etc. Gasification is the
process in which biomass is converted into clean and combustible gas in the presence of steam and air. There
are different gasifiers like updraft, downdraft, cross draft and fluidized bed gasifiers (Khummongkol and
Arrunlaksadamrong, 1990).
The main aim of this study is to produce producer gas from biomass and use it in engine for power generation.
The experimental set up is shown in Figure 1. As shown in the Figure 1, the biomass is fed from top and is
gasified to produce producer gas.

BIOMASS TAR
GAS COOLER +
IN CRACKING GAS 800 O C STEAM GENERATOR
UNIT

UPDRAFT
GASIFIER
STEAM
+ AIR
S. I.
ENGINE
ASH AIR
BLOWER

Figure 1: Experimental set up

Equilibrium Model for Biomass Gasification 107

The tar in the outlet gases is cracked thermally in the tar cracking unit. The gases coming out of the tar cracking
unit is at 800 oC and hence need to be cooled. A heat exchanger is provided for the same and then this cooled
gas is used for engine applications. The steam generated out of the heat exchange between hot gas and cooling
water is mixed with input air to the gasifier. The addition of steam will enhance the hydrogen percentage in the
product gas and its calorific value thereby.

We assumed that updraft gasifier is at thermodynamic equilibrium. The review of various thermodynamic
equilibrium models and its applications is given by Channiwala (1992). The gasification reactions occur are at
equilibrium and thermodynamic equilibrium compositions are predicted for four biomasses. The effect of air
input, steam/air ratio is studied for each biomass. They are compared based on their calorific value.

2. Thermodynamic Equilibrium Model

2.1 Assumptions
1. Biomass is represented by the general formula C Hx Oy
2. The gasification products contain CO2, CO, H2, CH4, N2, H2O and un-burnt carbon
3. The reactions are at thermodynamic equilibrium
4. The reactions proceed adiabatically

Based on the above assumptions, the general reaction of biomass with air and steam is written as

C Hx Oy + z (p O2 + (1-p) N2)+ k H2O = a CO2 + b CO + c H2+ d CH4 + e N2 + f H2O+ g C (1)

Where, x and y are the H/C and O/C mole ratio, respectively. The moisture content of the biomass is neglected
and the product quality depends on the x and y.
The above reaction represents an overall reaction but a number of competing intermediate reactions take place
during the process. These are:
1) Oxidation
C+ O2=CO2 (2)
2) Steam gasification
C+H2O=CO+H2 (3)
3) Bouduard reaction
C+ CO2=2CO (4)
4) Methanation reaction
C+2H2=CH4 (5)
5) Water gas-shift reaction
CO+ H2O=CO2+ H2 (6)

Out of these only four reactions are independent reactions, which are chosen as oxidation, steam gasification,
bouduard reaction, and the methanation reaction. The water gas shift reaction can be considered as the
subtraction of the steam gasification and bouduard reactions. Oxidation reaction is typically assumed to be very
fast and goes to completion (Von Fredersdorff and Elliott, 1963) and three reactions namely bouduard reaction,
steam gasification and methanation are in equilibrium.

2.2. Model Equations

Taking atom balances on carbon, oxygen, hydrogen and nitrogen, we obtain,
Carbon 1=a+b+d+g (7)
Oxygen y + 2pz + k = 2a + b + f (8)
Hydrogen x + 2 k = 2c + 4d + 2f (9)
Nitrogen z (1-p) = e (10)

The three equilibrium relations for the three reactions (other than oxidation) are -
1) Bouduard reaction
y co2 Pt
K e1 = (11)
y co2
108 Advances in Energy Research (AER – 2006)

2) Steam gasification reaction

yco y H 2 Pt
K e2 = (12)
y H 2O

3) Methanation reaction
yCH 4
K e3 =
y H2 2 Pt (13)

The equilibrium constants are given by

ΔG 0
ln K e = − (14)
RT
Where, ΔG0 is the Gibb’s free energy (kJ/mol), T is the temperature in K and R is the universal gas constant in
consistent units.

The energy balance can be considered as follows -

The heat of the overall gasification reaction (1) is given by
n T
(15)
ΔH (T ) = ΔH (T ) + ∑ n ∫ C dT
R R R i pi
i =1 TR

At adiabatic condition, this heat of reaction is zero. Heat of reaction at the reference temperature is calculated
using heats of combustions of the species.

ΔH (T ) = ΔH − ΔH − ΔH − ΔH (16)
R R ccoal cCO cH 2 cCH 4

n T

Thus, 0 = ΔH (T ) + ∑ n ∫ C dT
R R i pi (17)
i =1 TR

where ΔHR is the heat of reaction, ΔHci is the heat of combustion of species ‘i’, ni is the moles of species ‘i’, Cpi
is the specific heat capacity of species ‘i’.

The eight non-linear algebraic equations (7-13 and 17) are solved simultaneously in order to determine a, b, c, d,
e, f, g (which determine the product gas composition) and the adiabatic temperature, at various pressures using
the solver FSOLVE in MATLAB. The model is simulated without energy balance. This gives us the expected
exit gas compositions at each temperature and pressure. Inclusion of energy balance will give the adiabatic
temperature along with gas compositions. Gross calorific value is calculated using the following formula

GCV=(b ΔHcCO + c ΔHcH2 + c ΔHcCH4) / (a + b + c + d+ e)

(18)

The ultimate analysis of four biomasses used in this study (Iyer et al., 2002) are tabulated in Table 1.

Table 1: Ultimate analysis of different biomass samples (Iyer et al., 2002)

Calorific value
Sr.No. Biomass sample C% H% N% O% Ash%
kcal/kg
1. Saw dust 52.28 5.2 0.47 40.85 1.2 3795
2. Bagasse (A.P.) 47 6.5 0.00 42.5 4 4200
3. Subabul 42.76 5.68 1.07 49.29 1.2 3980
4. Rice husk 36.42 4.91 0.59 35.88 22.2 3000

3. Results and Discussions

3.1. The Effect of Temperature

Figure 2 shows the product gas compositions and gross calorific value for Sawdust gasification without steam.
The CO and H2 are increases with increase in temperature. CO2, H2O and CH4 are decrease with increase in
temperature. Figure 3 shows the product gas compositions and gross calorific value for Sawdust with air and
Equilibrium Model for Biomass Gasification 109

steam (steam/air=1). It is clear that steam introduction in gasification process increases CO and H2 and gross
calorific value of the product gas. Similar results are obtained for other three biomasses. The trends are similar
for all other three biomasses. The gross calorific value (GCV) of four biomasses with temperature at air=0.1 and
steam/air ratio=8 is compared in Figure 4. The air is 0.1 and steam/air ratio is 8. These inputs are chosen based
on the maximum gross calorific value of the product gas. GCV is increased with increase in the temperature for
all samples. The GCV of bagasse is the maximum and subabul is the lowest at lower temperatures. At higher
temperatures above 1100 K, the GCV is constant and there is no significant difference in value of four
biomasses.
0.45 55
CO2
CO
0.4 50
H2
CH4
45
0.35 H2O

40
0.3
35
0.25

Gross calorific value (kcal/mol)

30
Mole fractions

0.2
25
0.15
20

0.1
15

0.05 10

0 5
600 700 800 900 1000 1100 1200 600 700 800 900 1000 1100 1200
Temperature (K) Temperature (K)

(a) (b)
Figure 2: Sawdust without steam (air=0.55) a) product gas composition b) gross calorific value
0.45 55
CO2
CO
0.4 H2 50
CH4
0.35 H2O
Gross calorific value (kcal/mol)

45
0.3
Mole fractions

0.25 40

0.2 35

0.15
30
0.1

25
0.05

0 20
700 800 900 1000 1100 1200 1300 1400 700 800 900 1000 1100 1200 1300 1400
Temperature (K) Temperature (K)

(a) (b)
Figure 3: Sawdust with steam (steam/air=1) a) product gas composition b) gross calorific value

70

65 air=0.1; steam/air=8
GCV (kcal/mol)

60

55

50

45 sawdust bagasse
subabul rice husk
40
700 900 1100 1300 1500
Temperature (K)
Figure 4: Comparisons of the gross calorific value (GCV) of four biomasses.
110 Advances in Energy Research (AER – 2006)

3.2. The Effect of Air Input

The effect of air input is studied for each sample using four different air inputs. Figure 5 shows the GCV of
sawdust for four air inputs when steam in input is zero. As air input is decreased the GCV increases with
increase in temperature. After 1100 K, GCV remains constant. This is observed for all four biomasses.

70
Effect of inlet air
60
50
GCV (kcal/mol)

40 air=0.8
30 air=0.55
air=0.3
20
air=0.1
10
0
700 900 1100 1300 1500
Temperature (K)

Figure 5: Effect of inlet air on GCV for Sawdust

3.3. The Effect of Steam/Air Ratio

The effect of steam/air ratio for sawdust is shown in Figure 6. As steam/air ratio increases at fixed air inlet, the
GCV increases. This trend is observed for all biomasses. Thus with increase in steam/air ratio favours steam
gasification reaction and H2 and CO increase in product gas increasing GCV. At higher temperature (>1100K),
GCV remains constant.

70
air=0.1
65
60
GCV (kcal/mol)

55
50
45 air=0.1; steam=0 steam/air=1
steam/air=2 steam/air=3
40 steam/air=4 steam/air=8

35
700 900 1100 1300 1500
Temperature (K)

Figure 6: Effect of inlet steam/air ratio on GCV for Sawdust

3.4. Determination of the Adiabatic Temperature

The inclusion of energy balance equation will give adiabatic gasification temperature. The compositions and
adiabatic temperature are obtained for four biomass samples with different steam to air ratios. Figure 7 shows
adiabatic temperature, GCV and carbon conversions of four biomasses with different steam/ air ratios. Adiabatic
temperature decreases with increase in steam/air ratio except for rice husk. GCV decreases with increase in
steam/air ratio except for rice husk. This is reverse trend than the trends we get without energy balance. Carbon
conversion increased with increase in steam/air ratio.

The results are compared with experimental results from literature and simulation. The results are not directly
comparable since we didn’t account for heat losses and moisture content of biomass. Our model predicts results
Equilibrium Model for Biomass Gasification 111

comparable with the experiments (Shashikantha, 1988) and simulation by Channiwala (1992). The results are
compared in Table 2.
Table 2: Comparison of results with literature

CO2 CO H2 CH4
Experiment (Shashikantha,1988) 12.17 18.24 27.65 2.06
Model Channiwala(1992) 12.85 22.72 27.91 1.58
Present model 18.72 10.46 30.90 5.93

The biomass used is Subabul wood x=1.451, y=0.697 and heating value=4780 kcal/kg. Present model predicts
more CO2, H2 and CH4 .CO is less predicted by present model. This is due to heating losses and moisture
present in biomass is not included in present model. In future model will be modified to take care of there
parameters.

750 24
Sawdust Sawdust
700 22
Adiabatic temperature (K)

Bagasse bagasse
Subabul 20 Subabul
650
Rice husk GCV (kcal/mol) Rice husk
18
600
16
550
14
500
12
450
10
400 0 0.5 1 1.5 2
0 0.5 1 1.5 2
steam/air steam/air

(a) (b)
1
0.9
0.8
Carbon conversion

0.7
0.6
0.5
Sawdust
0.4
bagasse
0.3 Subabul
0.2 Rice husk
0.1
0
0 0.5 1 1.5 2
steam/air

(c)
Figure 7: Effect of inlet steam/air ratio on a) adiabatic temperature and b) GCV c) carbon conversion for four
biomasses

4. Conclusion
The equilibrium calculations are performed for four biomasses from India. The GCV variation with temperature
suggests that as temperature increase GCV increase. At temperature greater than 1100K, GCV remains constant
for all biomasses. At air 0.1 moles and steam/air=8, all samples gives maximum GCV. The GCV of bagasse is
the highest and that of Subabul is the lowest at lower temperature (<1000K). At higher temperature is GCV
remains constant. The adiabatic temperature and GCV decrease with increase in steam/air ratio except for rice
husk. The GCV is the main criteria for engine applications. Knowing the GCV variation with various
parameters the model can be further extended for whole system including engine with inclusion of heat losses
and moisture in biomass.

References
1. Bridgwater A. V., 1994, Thermochemical Processing of Biomass, Butterworths, England.
112 Advances in Energy Research (AER – 2006)

2. Channiwala S. A., 1992, On Biomass Gasification Process and Technology Development -some Analytical
and Experimental Investigations, Ph.D. thesis, IIT Bombay, Mumbai.
3. Iyer P.V.R., T. R. Rao and P.D. Grover, 2002, Biomass Thermo-Chemical Characterization, IIT Delhi,
India.
4. Khummongkol D., and W. Arrunlaksadamrong, 1990, Performance of an Updraft Mangrove – Wood
Gasifier, Energy vol. 15, No. 9, 781-784.
5. Shashikantha, 1988, Performance evaluation of Gasifier-Engine system operating on dual fuel mode,
M.Tech. Dissertation, C.E.S.E., IIT Bombay.
6. Von Fredersdorff C. C., and M.A. Elliott, 1963, Coal Gasification, in Chemistry of Coal Utilization, H.H.
7. Lowry, ed., Wiley, New York.