Thermodynamic analysis of hydrogen rich synthetic gas generation from fluidized

bed gasification of rice husk
Chanchal Loha
a
, Himadri Chattopadhyay
b,
*
, Pradip K. Chatterjee
a
a
Thermal Engineering Group, Central Mechanical Engineering Research Institute (CSIR), Durgapur 713209, India
b
Department of Mechanical Engineering, Jadavpur University, S C Mallik Road, Jadavpur, Kolkata 700032, India
a r t i c l e i n f o
Article history:
Received 3 December 2010
Received in revised form
25 April 2011
Accepted 25 April 2011
Available online 26 May 2011
Keywords:
Energy
Exergy
Equilibrium model
Gasification
Biomass
Rice husk
a b s t r a c t
In the present work, the generation of hydrogen rich synthetic gas from fluidized bed steam gasification
of rice husk has been studied. An equilibrium model based on equilibrium constant and material
balance has been developed to predict the gas compositions. The equilibrium gas compositions are
compared with the experimental data of the present group as well as of available literature. The energy
and exergy analysis of the process have been carried out by varying steam to biomass ratio (j) within
the range between 0.1e1.5 and gasification temperature from 600

C to 900

C. It is observed that both
the energy and exergy efficiencies are maximum at the CBP (carbon boundary point) though the
hydrogen production increases beyond the CBP. The HHV (higher heating value) and the external energy
input both continuously increase with j. However, the hydrogen production initially increases with
increase in temperature up to 800

C and then becomes nearly asymptotic. The HHV decreases rapidly
with increase in temperature and energy input increases. Therefore, gasification in lower temperature
region is observed to be economical in terms of a trade off between external energy input and HHV
of the product gas.
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
The conservation of limited supply of fossil fuel, climate change
and the increasing concern over global warming have prompted
a search for new and cleaner methods of power generation
particularly from renewable energy sources. Amongst the different
sources of renewable energies, the most promising future energy
source is biomass [1]. India has substantial biomass resources in
the form of agricultural residues, which are currently used for
domestic energy and fuel applications mostly through combustion.
This is often, however, inefficient as well as contributing to local
pollution from inadequately controlled gaseous emissions. There-
fore, the gasification of biomass is possibly a more efficient way of
biomass utilization. Biomass gasification is the thermo chemical
conversion of solid biomass into the fuel gas which contains
mainly hydrogen, carbon monoxide, carbon dioxide, methane and
nitrogen. The product gas from the reactor also contains some
contaminants like char particle, ash and some higher hydrocarbons
or tar. A limited supply of oxygen, air, steam or a combination
of these serves as gasifying agent. Biomass gasification by using air
produces a gas with a lower Calorific Value (4e7 MJ/Nm
3
), whereas
gasification with steam and oxygen produces the gas having
medium to higher Calorific Values (10e18 MJ/Nm
3
) [2]. The gasi-
fication with oxygen is not popular due to the fact that it involves
large investment for production of oxygen. The gasificationwith air
dilutes the gas due to the presence of N
2
in the air. In recent years,
the steam gasification of biomass has become an area of growing
interest because it produces gaseous product having higher H
2
content. Besides, the steam gasification process has the following
additional advantages: it is capable of maximizing the gas product
with higher heating rate involved, advantageous residence time
characteristics, and the efficient tar and char reduction brought
about by steam reforming.
In biomass gasification, fluidized bed technology is widely used
due to its various advantages which include high heat transfer,
uniform and controllable temperature, favorable gas-solid con-
tacting etc [3]. Mansaray et al. [4] have studied the air gasification of
rice husk in a dual distributor type fluidized bed system. The effect
of varying fluidizing velocity (0.22e0.33 m/s) and equivalence ratio
(0.25e0.35) on the gasifier performance were discussed. Miccio
et al. [5] studied the biomass gasification in fluidized bed and
achieved a maximum C (carbon) post conversion of 70%. The
gasification performance of sawdust in fluidized bed reactor was
* Corresponding author. Tel.: þ91 9332151376; fax: þ91 3324146890.
E-mail addresses: chanchal.loha@gmail.com (C. Loha), chimadri@gmail.com
(H. Chattopadhyay).
Contents lists available at ScienceDirect
Energy
j ournal homepage: www. el sevi er. com/ l ocat e/ energy
0360-5442/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2011.04.042
Energy 36 (2011) 4063e4071
studied by many authors [6e8]. The effects of gasification
temperature, equivalence ratio, O/C ratio and steam-to-biomass
ratio were studied on the product gas composition and heating
value. The hydrogen yield potential was found to be the most
sensitive with equivalence ratio by Turn et al. [6], whereas the
temperature was reported to be the most important factor by Lv
et al. [7], over the range of experimental condition studied. It was
also observed by Li et al. [8] that the gas composition and heating
value depend heavily on the O/C ratio. The air gasification of wood
chips was also carried out by Lim et al. [9] in a bubbling fluidized
bed gasifier and the performance was studied in terms of thermal
output. They showed that the gas produced has an energy content
of 4.75 MJ/m
3
at a bed temperature of 733

C and equivalence ratio
of 0.23. The resulting thermal efficiency was 61.32% with a thermal
output of 355.55 kW
th
.
Fluidized bed steam gasification was studied by Rapagna et al.
[10,11] and naturally occurring catalytic substances were employed
to enhance the yield of fuel gas and reduce its tar content. The
reactions influencing the biomass steam gasification process were
studied in an atmospheric fluidized bed gasifier by Franco et al.
[12]. The effects of gasification temperature and steam/biomass
ratio were investigated on the gas composition and HHV (higher
heating value). Recently, fluidized bed gasification process with
pure steam to produce hydrogen rich gas has been reviewed by
Corella et al. [13]. It is reported that the biomass gasification with
pure steam can generates 60 vol% (dry basis) hydrogen rich gases
with tar content as lowas 0.25 g/Nm
3
.The present group of authors
[14] have also studied the fluidized bed steam gasification of
biomass experimentally and developed a correlation to predict the
hydrogen yield.
The assessment of the gasification process by analyzing the
first law(energy) efficiency and the second law(exergy) efficiency
is an effective method for design and analysis of the process. A lot
of works on energy and exergy analysis of biomass gasification in
fixed bed reactor based on equilibrium modeling have been re-
ported in the literature. Some authors have also used the
equilibrium model to describe the biomass gasification in fluid-
ized bed reactor. Equilibriummodel provides a useful design aid in
evaluating the possible limiting behavior of a complex reacting
system that is difficult or unsafe to produce experimentally or in
commercial operation [15,16] and also it is computationally
inexpensive. Pellegrini et al. [17] used chemical equilibriummodel
to present the exergetic and energetic behavior of air gasification
of sugarcane bagasse where a parametric study has been carried
out to investigate the influence of many variables such as: gasi-
fication temperature, air temperature and moisture content. The
equilibrium model was also developed by Jarungthammachote
et al. [18] to calculate the product gas composition and second law
analysis has been done for gasification of municipal solid waste in
a downdraft waste gasifier. Prins et al. [19,20] have focused their
study on the energy and exergy analysis of biomass gasification by
using chemical equilibrium model. Their Study showed that the
CBP (Carbon Boundary Point) was the optimum point of operation
with respect to exergy-based-efficiency for both gasification with
air and steam. The term CBP implies the situation where exactly
enough gasifying agent is added to obtain complete carbon
conversion. Ptasinski et al. [21] showed that the exergetic effi-
ciency of gasification also depends on the chemical composition of
biofuel used as feedstock. They showed that the exergetic effi-
ciencies of vegetable oil, straw, treated wood, untreated wood and
grass were comparable with coal, whereas the efficiencies of
sludge and manure were considerably lower. The efficiency of
biomass gasification was also analyzed by Ptasinski [22] by using
triangular CeHeO diagram, considering a biomass fuel repre-
sented as CH
1.4
O
0.59
N
0.0017
. It was observed that at the equivalence
ratio of 0.26, the chemical and the total exergy of the gas reached
maximum at CBP for an air-blown gasifier. The Exergy analysis for
biomass-to-SNG (synthetic natural gas) conversion was presented
by Jurascik et al. [23]. The analysis was made for a temperature
range from 650

C to 800

C and the pressure range from 1 to
15 bar. The results showed that the largest exergy losses take place
in the biomass gasifier, CH
4
synthesis part and CO
2
capture unit.
The exergy analysis of hydrogen production from sawdust wood
was analyzed by Abuadala et al. [24,25]. The analysis has been
done by developing an equilibrium model. The results indicated
that the hydrogen production from biomass steam gasification
depends on the operating temperature, amount of steam added
and the quality of the biomass. Kalinci et al. [26] studied the
thermodynamic performance of an integrated gasifier-boiler
power system with six different biomass fuels and showed that
the exergy contents of different biomass fuels varied from15.89 to
22.07 MJ/kg, respectively. A chemical equilibrium model has also
been developed by Karamarkovic et al. [27] to study the air gasi-
fication of biomass in different gasification temperature by
analyzing the energy and exergy associated with the process. It
was reported that the gasification process at a given gasification
temperature can be improved by the use of dry biomass and by the
carbon-boundary temperature approaching the required
temperature. A non-stoichiometric equilibrium model based on
free energy minimization was developed by Li et al. [28]. It was
showed that the gas composition and heating value vary primarily
with temperature and the relative abundance of key elements,
Nomenclature
CBP carbon boundary point
C
p
specific heat at constant pressure, kJ/kmol K
daf dry ash free
E exergy, kJ
DG
o
T
standard gibbs function of reaction
Dg
o
f ;T;i
standard gibbs function of formation, kJ/kmol
H enthalpy, kJ
H
c
heat of combustion, kJ/kmol
I Irreversibility, kJ
h
o
f
heat of formation, kJ/kmol
HHV higher heating value
K equilibrium constant
m mole of input steam
n mole of product gases
P partial pressure
Q
IN
energy input as electricity which is converted
to heat, kJ
R universal gas constant, kJ/kmol K
T, T
0
gasification and ambient temperature, K
W
IN
exergy input, which is basically work input as
electricity, kJ
x mole fraction
Greek letters
j steam-to-biomass ratio
g stoichiometric number
3
chem
standard chemical exergy
h
I
first law (energy) efficiency
h
II
second law (exergy) efficiency
D difference
C. Loha et al. / Energy 36 (2011) 4063e4071 4064
especially carbon, hydrogen and oxygen. Pressure only influences
the results significantly over a limited temperature range. The
simulation of hydrogen production from biomass gasification in
an interconnected fluidized bed was presented by Shen et al. [29].
A process simulation was conducted with Aspen plus software.
The variation of gas composition, hydrogen yield, carbon conver-
sion and available efficiencies were presented.
From the state-of the-art, it is observed that the exergetic and
energetic analysis of steam gasification of biomass in a fluidized
bed reactor is rather limited. The analysis of the gasification process
based on the newconcept of CBP is even fewer. Some authors have
discussed the effects of parameters like temperature, steam-to-
biomass ratio, moisture content, feedstock quality etc. on the
steam gasification process. But the important issue of the energy
input to the allothermal gasification process has not been discussed
in detail. Therefore, the objective of the present work is to study the
steamgasification of biomass in a fluidized bed gasifier with special
emphasis on the thermodynamic analysis involving parameters
like energy and exergy efficiency. The rice husk is used as biomass
because it cultivated in more than 75 countries in the world and
India alone generates about 22 million tones of rice husk per year
[30]. Thus rice husk would be the most natural choice for countries
like India and China and little work has been reported on the
gasification behavior of rice husk in the open literature. An equi-
librium model has been developed to predict the gas composition.
The model has been calibrated against the experimental investi-
gation described in Section 2 and also with the experimental
investigation of Rapagna et al. [11]. After calibration the model is
used to study the H
2
production, energy and exergy efficiencies,
HHV and the energy input to the system for a wide range of
temperature and S/B (steam-to-biomass ratio), particularly
focusing at CBP.
The authors envisage a twin fluidized bed gasifier where there
will be two interconnected reactor, one will act as gasifier and
another will act as combustor. The heat required for gasification,
which is supplied from the electric furnace in the present investi-
gation, will be replaced by the continuous transfer of hot bed
material from the combustor. Accordingly, the consideration of
electrical energy in the analysis does not arise. The advantages of
using two separate sections: gasification and combustion zones are
already reported in literature [31,32].
2. Process description
The gasification experiment is conducted in a laboratory scale
bubbling fluidized bed gasifier described previously [14] and pre-
sented in Fig. 1. The inner diameter of the gasifier is 50 mm and the
length is 1200 mm. The superheated steam at 200

C is introduced
at the bottom of the gasifier. The steam is used as both gasifying as
well as fluidizing agent. The rice husk is fed into the gasifier
through a water-cooled screw feeder with a variable speed drive.
The ultimate and the proximate analysis of rice husk is presented in
Table 1. Sand of size 0.3 mme0.5 mm is used as inert bed material
due to the non-granular and flaky nature of the rice husk. The
gasifier is placed inside an electric furnace to provide the heat
required for gasification. The temperatures are measured with type
R thermocouple (PlatinumeRhodium) with calibrated uncertainty
value of 2.4%. Hot gas coming out from the gasifier is cleaned and
cooled before entering into a Gas Chromatograph [Make-Chemito,
Model-GC 1000]. The Gas Chromatograph is calibrated in the
range used before analysis. The experiments are carried out for
different temperature by keeping the S/B fixed and then the S/B is
varied by keeping the temperature fixed and the product gas
compositions are analyzed.
3. Equilibrium modeling
Biomass essentially contains volatiles, fixed carbon, ash and
water. Upon heating the biomass, initially the removal of moisture
takes place up to about 120

C, followed by devolatization up to
350

C and the gasification of char occurs above 350

C [33]. In
equilibrium modeling, it is assumed that biomass, which is dry and
ash free, contains the elements C, H and O. The element of nitrogen
and sulfur are not considered because biomass contains negligible
amount of nitrogen and sulfur in comparison to carbon, hydrogen
and oxygen. Therefore, the chemical formula of the biomass is
represented as CH
x
O
y.
The steamis used as the gasifying agent here.
In general the global gasification reaction of biomass with steam as
the gasifying agent can be written as follows:
CH
x
O
y
þ mH
2
O ¼ n
H2
H
2
þ n
CO
CO þ n
CO2
CO
2
þ n
H2O
H
2
O
þ n
CH4
CH
4
þ n
c
C (1)
where, x and y are the numbers of atoms of hydrogen and oxygen
per single atom of carbon in the biomass. m is the moles of steam
added per mole of dry ash free biomass. Left hand side all are input
parameters and they are known. On the right hand side
n
H2
; n
CO
; n
CO2
; n
H2O
; n
CH4
and n
C
are the unknown number of
moles of hydrogen, carbon monoxide, carbon dioxide, steam,
methane and solid char carbon respectively present in the product.
Now to solve these unknowns equal numbers of equations are
required. Three equations are obtained fromthe material balance of
carbon, hydrogen and oxygen respectively. Carbon balance
n
CO
þ n
CO2
þ n
CH4
¼ 1 (2)
Hydrogen balance
1. Steam generator 2. Superheater 3. Screw Feeder 4. Gasifier
5. Electric Furnace 6. Cyclone Seperator 7. Gas Claning and
Cooling 8. Filter 9. Suction Pump 10. Gas Chromatograph
1
2
3
4
6
5
7
8
9
10
Fig. 1. Schematic diagram of bubbling fluidized bed biomass gasifier.
Table 1
Ultimate and proximate analysis of rice husk.
Ultimate analysis Percent Proximate analysis Percent
Carbon 38.43 Volatile matter 55.54
Hydrogen 2.97 Fixed carbon 14.99
Sulfur 0.07 Moisture 9.95
Nitrogen 0.49 Ash 19.52
Oxygen 36.36
Ash 21.68
C. Loha et al. / Energy 36 (2011) 4063e4071 4065
2n
H2
þ2n
H2O
þ4n
CH4
¼ x þ2m (3)
Oxygen balance
n
CO
þ2n
CO2
þ n
H2O
¼ y þ m (4)
Now up to the CBP, the char carbon is considered in the product
and hence six equations are needed to solve six unknowns.
Therefore, in addition to the three material balance equations
another three equations are obtained from the equilibrium
constant expression of three heterogeneous reactions as given
below.
Heterogeneous water Àgas reaction: CþH
2
O ¼ CO þ H
2
(5)
Boudouard reaction : C þ CO
2
¼ 2CO (6)
Hydrogenating gasification C þ 2H
2
¼ CH
4
(7)
The equilibrium constants are as follows
K
1
¼
P
CO
P
H2
P
H2O
¼
x
CO
x
H2
x
H2O
(8)
where,
x
j
¼
n
j

j ¼product gases
n
j
K
2
¼
ðP
CO
Þ
2
P
CO2
¼
ðx
CO
Þ
2
x
CO2
(9)
K
3
¼
P
CH4
_
P
H2
_
2
¼
x
CH4
_
x
H2
_
2
(10)
Beyond CBP, only gaseous products are considered and hence
the number of unknowns reduced to five. In that case the reaction
(5) and reaction (6) can be combined to give the homogeneous
wateregas shift reaction as given below.
Water Àgas shift reaction CO þH
2
O ¼ CO
2
þH
2
(11)
K
4
¼
P
CO2
P
H2
P
CO
P
H2O
¼
x
CO2
x
H2
x
CO
x
H2O
(12)
So, equations (10) and (12) are taken in addition to equations
(2), (3) and (4) to solve five unknowns.
The Equilibrium constant and the Gibbs free enthalpy of reac-
tion is calculated according to equations (13) and (14).
lnK ¼ À
DG
o
T
R=T
(13)
DG
o
T
¼

i
g
i
Dg
o
f ;T;i
(14)
Where R is the universal gas constant, DG
o
T
is the standard Gibbs
function of reaction and Dg
o
f ;T;i
represents the standard Gibbs func-
tion of formation at given temperature T and g is the stoichiometric
number of the gas species i. The data for h
o
f
and Gibbs function of
formation are given in Table 2 [34] for the temperature range form
800 K to 1100 K. An Arrhenius type function is fitted to calculate the
equilibrium constant in between the given temperature steps.
K ¼ k
o
exp
_
À
E
act
R=T
_
(15)
Where k
o
is the pre exponential function and E
act
is the activation
energy.
4. Energy balance
Applying the law of conservation of energy, the energy balance
for the gasification system give rise to

i ¼reactant
H
i
þ Q
IN
¼

j ¼product
H
j
(16)
where,

i ¼reactant
H
i
¼h
o
f ;biomass
þ m
_
h
o
f ;H2O
þDh
T;H2O
_
(17)
and

j ¼product
H
j
¼

j ¼product
n
j
_
h
o
f ;j
þDh
T;j
_
(18)
h
o
f
in the above equation represents the enthalpy of formation
and ∆h
T
represents the enthalpy difference between any given state
and at reference state (298 K, 1 atm). It can be represented by:
Dh
T;j
¼
_
T
To
C
p
ðTÞdT (19)
where C
p
is specific heat at constant pressure and it is temperature
dependent. The temperature dependency of C
p
can be expressed by
a polynomial function as given below.
C
p
¼ A þ BT þ CT
2
þ DT
3
(20)
The values of A, B, C and D and their range of applicability are
given in Table 3 [35].
The heat of formation of solid biomass containing only carbon,
hydrogen and oxygen can be calculated from the heat of combus-
tion of the compound (complete combustion to H
2
O and CO
2
assumed) and heat of combustion of carbon and of hydrogen. Thus
the heat of reaction
C þ
x
2
H
2
þ
y
2
O
2
/CH
x
O
y
DH
R1
¼ Àh
o
f ;biomass
DH
R1
¼ Àh
o
f ;biomass
Table 2
Heat of formation and the standard Gibbs function of formation from 800 K to
1100 K for all components.
Compound h
o
f
(kJ/kmol) Dg
o
f ;T;i
(kJ/kmol)
800 K 900 K 1000 K 1100 K
H
2
0 0 0 0 0
CO À110525 À182497 À191416 À200275 À209075
CO
2
À393509 À395586 À395748 À395866 À396001
H
2
O À241818 À203496 À198083 À192590 À187033
CH
4
À74520 À2115 8616 19492 30472
Table 3
Coefficient for specific heat for the empirical equation Cp ¼ A þ BT þ CT
2
þ DT
3
.
Compound Cp ¼ A þ BT þ CT
2
þ DT
3
(kJ/kmol K) Temperature range
A 10
2
B 10
5
C 10
9
D
H
2
20.09 À0.1916 0.4000 À0.870 273e1800
CO 27.11 0.655 À0.1000 e 273e3800
CO
2
22.24 5.979 À3.498 7.464 273e1800
H
2
O 32.22 0.1920 1.054 À3.594 273e1800
CH
4
19.87 5.021 1.268 À11.00 273e1500
C. Loha et al. / Energy 36 (2011) 4063e4071 4066
is obtained by an algebraic summation of the heats for the
reactions
C þ O
2
/CO
2
DH
R2
¼ Àh
o
f ;CO2
x
2
H
2
þ
x
4
O
2
/
x
2
H
2
ODH
R3
¼ À
x
2
h
o
f ;H2O
CH
x
O
y
þ
1
2
Â
_
2 þ
x
2
À y
_
O
2
/CO
2
þ
x
2
H
2
ODH
R4
¼ H
c;biomass
By combining the last three equations to give the first equation,
one can write
DH
R1
¼ DH
R2
þDH
R3
ÀDH
R4
or,
h
o
f ;biomass
¼ H
C;biomass
þ
_
h
o
f ;CO2
þ
x
2
h
o
f ;H2O
_
(21)
5. Exergy balance
Applying the second law of thermodynamics, qualitative
expression of law of conservation of energy to the gasification
process gives the exergy balance of the process as

IN
E þ W
IN
¼

OUT
E
k
þ I (22)
where,

IN
E
i
¼ E
biomass
þ E
steam
(23)

OUT
E
j
¼ E
dry product gas
þ E
steam
þ E
unconverted carbon
(24)
In the present system, the heat supplied to the systemis directly
from the electricity so the exergy input W
IN
(equation (22)) is
basically the work input as electricity which is converted to heat Q
IN
(equation (16)). The difference between energy and exergy balance
is that the exergy is never conserved in any irreversible process but
always decreases. Here the irreversibility term in equation (22)is
represented by I.
The exergy can be divided into two components as the chemical
exergy and the physical exergy as stated below:
E ¼ E
chem
þ E
phy
(25)
The standard chemical exergy of a pure compound is equal to
the maximum amount of energy obtained when the compound is
brought from environment state, characterized by the environ-
mental temperature and pressure, to the dead state, characterized
by the same environment condition of temperature and pressure.
The values of standard chemical exergy of pure compounds are
given in Table 4 [17]. The chemical exergy of ideal gas mixture can
be written as;
E
chem;M
¼

j
x
j
3
chem;j
þR=T
0

j
x
j
ln
_
x
j
_
(26)
where x
j
is the mole fraction and 3
, j
is the standard chemical exergy
of J
th
product respectively. It is observed from above equation that
the chemical exergy of mixture is always lower than the average
chemical exergy of the mixture, because the second term of the
above equation is always negative.
The physical exergy of a material stream can be calculated as
[36e38]:
E
phy
¼
_
T
To
C
p
dT À T
o
_
T
To
C
p
T
dT ¼ ðh À h
0
Þ À T
0
ðs À s
0
Þ (27)
Therefore, the physical exergy of ideal gas mixture can be
evaluated using mixture rule:
E
phy;M
¼
_
T
To
_
_

j
x
j
C
p;j
_
_
dT À T
o
_
T
T0
_

j
x
j
C
p;j
_
T
dT (28)
In the present work, the exergy of solid biomass was calculated
from its lower heating value using a multiplication factor
b [17,39,40] as follows:
E
biomass
¼ bLHV
biomass
(29)
where the coefficient b is given in terms of oxygen-carbon and
hydrogen-carbon ratios according to the following equation:
b ¼
1:0414 þ 0:0177½H=CŠ À0:3328½O=CŠf1 þ 0:0537½H=CŠg
1 À0:4021½O=CŠ
(30)
and the lower heating value of the biomass is given by:
LHV
biomass
¼ 0:0041868f1 þ 0:15½OŠgf7837:667½C
þ 33888:889½HŠ À ½OŠ=8Šg (31)
6. First law and second law efficiency
For the system under study, the first law efficiency can be
calculated in two different ways. The first approach is to define the
“hot gas efficiency”, is the ratio of energy of product including the
sensible energy, to the HHV of the biomass plus the energy of the
input steam plus the external energy used.
h
I; hot gas
¼
HHV
product
þ H
sensible;product
HHV
biomass
þ H
steam;input
þ Q
IN
(32)
Under the assumption of adiabatic wall condition, the hot gas
efficiency value would be 100% with no loss of energy being
considered. Therefore it is more meaningful to use so called “cold
gas efficiency”, which excludes the sensible energy of the product,
is defined as the ratio of the HHV of the product and the HHV of the
biomass plus energy of the input steam plus the external energy
used.
h
I; cold gas
¼
HHV
product
HHV
biomass
þ H
steam; input
þ Q
IN
(33)
But one of the major thermodynamical concerns is that the first
law efficiency, whether hot gas efficiency or cold gas efficiency,
does not consider the loss due to increase in entropy during the
conversion of solid fuel into gaseous products. The second law
Table 4
Chemical exergies for different components.
Component Chemical exergy (kJ/kmol)
H
2
236100
CO 275100
CO
2
19870
H
2
O 9500
CH
4
831650
C 410260
C. Loha et al. / Energy 36 (2011) 4063e4071 4067
efficiency or exergy efficiency takes care of that loss and provides
a more equitable measure of conversion efficiency [41]. However,
there are various processes of defining the exergy efficiency. The
most easiest and common definition of exergy efficiency is the sum
of the exergy of product gases divided by the total exergy input to
the system.
h
II; a
¼
E
gas
E
biomass
þ E
steam; input
þ W
IN
(34)
The unconverted carbon could also be considered as the useful
product because this could be re-introduced to the gasifier to utilize
its energy. In that case the exergy efficiency is defined as the ratio of
the exergy of the product including unconverted carbon and the
total exergy input to the system.
h
II; b
¼
E
gas
þ E
char
E
biomass
þ E
steam; input
þ W
IN
(35)
The exergy efficiency can also be defined in an alternative
manner as the sum of the chemical exergy of the product gases
divided by the total exergy input to the system.
h
II; c
¼
E
chem;gas
E
biomass
þ E
steam; input
þ W
IN
(36)
In all the above definition of the efficiency terms only the
numerator changes whereas the denominator remains same.
7. Validation
Equilibrium model is based on some assumptions like the
gasification reaction rate are fast enough and residence time is long
enough for the equilibrium state to be reached. Due to these
assumptions, equilibrium model sometimes yield greater
disagreement under certain circumstances. Therefore, a proper
calibration of the modeling results are needed with the experi-
mental values before applying the model for further analysis. Here
the computed gas compositions fromthe model are compared with
the experimental results of the present group of author reported
previously [14] as shown in Table 5. The error in this comparison is
estimated by the RMS (root-mean-square) values for each set of
data as given below
RMS ¼
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

N
j
_
Experiment
j
ÀModel
j
_
2
N
¸
¸
¸
¸
_
(37)
where N is the number of data point.
The comparison has been done for five different sets of
Temperature and S/B values. The RMS errors are calculated for each
set of data point. The maximumvalue of RMS observed is 3.197006.
The gas composition is also compared with the experimental
investigation on steamgasification of biomass reported by Rapagna
et al. [11] as shown in Table 6. Here the gas compositions are in
good agreement except for CH
4
. The reason can be attributed to the
fact that in our experiment only sand bed was used while Rapagna
et al. used sand bed with dolomite and olivine which are active for
tar destruction and increases the production of gas, but suppresses
methane reforming. Though some discrepancies arise due to the
equilibrium assumptions, still the comparison shows almost a fair
agreement of the predicted data with the experimental values.
Therefore, the calibrated accuracy of the model can be considered
to be acceptable for the analysis.
8. Results and discussion
8.1. Effect of steam-to-biomass ratio
The effect of j on the gasification of rice husk at temperature
700

C is explored through Figs. 2 and 3 and 4. The value of j can be
varied either by changing the steam flow rate and keeping the
biomass feed rate fixed or vice versa. The variation of hydrogen
production and the amount of char carbon present in the product is
shown in Fig. 2. It is observed that the amount of char carbon
present in the product decreases linearly with increase of j and
reaches to zero at j equal to 0.5, which is the carbon boundary
point (CBP) corresponding to 700

C. On the other hand the
hydrogen production increases with increase in j due the steam
reforming and gas shift reactions. The variation is linear and rela-
tively steep within the CBP. Beyond the CBP, the rate of change in H
2
yield reduces with increase of j while the curve assumes a para-
bolic shape with an asymptotic value of about 0.098. It was also
reported by Prins MJ and Ptasinski KJ [42] that the CBP was reached
at an equivalence ratio (ER) of 0.5 corresponding to the gasification
temperature of 1220

C.
The variations of h
I, cold gas
, h
II, a
, h
II, b
and h
II, c
are shown in Fig. 3.
It is observed that all efficiencies reach a maximum at CBP except
h
II, b
It is to be noted that h
II, b
considers the exergy of char carbon
present in the product which initially reduces with j and can be
distinctly observed till the CBP. However, it merges with h
II, a
after
CBP and both h
II, a
and h
II, b
becomes equal. The increase of h
I, cold gas
,
h
II, a
and h
II, c
belowthe CBP is very steep whereas the decrease after
CBP is relatively flat. It is also observed that the difference between
Table 5
Comparison of result with experimental investigation [14].
Tempe S/B Experimental Model RMS
H
2
CO CO
2
CH
4
H
2
CO CO
2
CH
4
690 1.32 50.50 14.30 26.60 8.60 48.76 12.99 31.21 7.03 2.667429
730 1.32 52.20 16.40 23.50 7.90 50.71 15.48 28.74 5.06 3.10603
750 1.00 49.50 23.70 21.20 5.60 50.37 20.59 25.01 4.02 2.619232
750 0.60 48.8 27.5 19.5 4.2 50.79 29.37 18.3 1.54 1.997783
750 1.32 52.30 17.75 22.25 7.40 51.43 16.64 27.65 4.28 3.197006
Table 6
Comparison of gas composition with published work [11].
Present Model Rapagna et al. (2000)
Case-I Case-II
(Dolomite as fluidized
bed inventory)
(Olivine as fluidized
bed inventory)
Temperature (
o
C) 770 770 770
S/B 1.0 1.0 1.0
Gas composition (Vol%)
H
2
57.98 55.50 52.20
CO 23.79 24.00 23.00
CO
2
16.70 14.10 16.90
CH
4
1.53 6.40 7.90
C. Loha et al. / Energy 36 (2011) 4063e4071 4068
energy efficiency (cold gas efficiency) and the exergy efficiencies
are a maximum at CBP. The values of h
I, cold gas
, h
II, a
and h
II, c
at the
CBP are 0.94, 0.84 and 0.81 respectively. The highest value of 0.88 is
observed for h
II, b
at the lowest j value of 0.1. It is to be noted that
the difference between first law and second law efficiency i.e.
energy and exergy efficiency is maximum at the CBP indicating
highest level of irreversibility.
The variation of HHV of the product gas and the external energy
input to the systemare also presented in Fig. 4. Initially, the HHV of
the product increases very fast with increase of j and after CBP is
reached, it increases appreciably only at very high value of j. The
external energy input also increases with increase in j and the rate
of increase is high just after CBP and then it becomes flat after j
equal to 1.1. The variation of energy input with j is somewhat flat
till the CBP and the curve is steeper just after the CBP till about an j
equal to 1.0 and then the energy input is almost at a constant level.
From the preceding analysis, it is justified to say that although
the hydrogen production increases beyond CBP, CBP is the optimum
point of gasification in terms of energy and exergy consideration.
Similar proclamation was also made by Fryda et al. [43] based on
the exergetic analysis of biomass allothermal gasification, that the
gasification should be carried out with the minimum steam
requirement to accomplish carbon conversion.
8.2. Effect of steam temperature
In the present investigation the gasification temperature is
varied form 600

C to 900

C. The effect of gasification temperature
on the hydrogen production is studied for j in the range of
0.6e1.0as shown in Fig. 5. The figure shows that the H
2
production
increased significantly with the increase of temperature from
600

C to 800

C and above 800

C it becomes nearly asymptotic.
The maximumH
2
yield achieved are 0.09, 0.085 and 0.078 kg per kg
of dry ash free biomass for J ¼ 1.0, 0.9 and 0.8 respectively. Similar
trend is also observed by Shen et al. [29] in their study. The varia-
tion of HHV and the external energy input are plotted against
temperature in Fig. 6. It depicts that at lower temperature the HHV
of the gas is more and it decreases with increase in temperature. It
is because, as temperature increases, the H
2
production increases
but CH
4
production decreases. The decrease of HHV with temper-
ature is also reported by Franco et al. [12] in their experimental
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
CBP
H
2
Char
H
2

(
k
g
/
k
g

o
f

d
a
f

b
i
o
m
a
s
s
)
0.0
0.1
0.2
0.3
0.4
C
h
a
r

(
m
o
l
e
/
m
o
l
e

o
f

d
a
f

b
i
o
m
a
s
s
)
Fig. 2. Variation of hydrogen production and unconverted char with J at a gasification
temperature of 700

C.
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
0
10
20
30
40
50
60
70
80
90
100
CBP
I,cold gas
η
η
η
E
f
f
i
c
i
e
n
c
y

(
%
)
η
II,a
II,b
II,c
Fig. 3. Variation of efficiencies with J at a gasification temperature of 700

C.
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
13.0
13.2
13.4
13.6
13.8
14.0
CBP
HHV
H
H
V

(
M
J
/
N
m
3
)
4
5
6
7
8
9
Q
I
N


(
M
J
/
k
g

o
f

b
i
o
m
a
s
s
)
)

IN
Fig. 4. Variation of HHV of the product gas and Q
IN
with J at a gasification temper-
ature of 700

C.
600 650 700 750 800 850 900
0.04
0.05
0.06
0.07
0.08
0.09
0.10
H
2

(
k
g
/
k
g

o
f

d
a
f

b
i
o
m
a
s
s
)
T (
0
C)
Ψ = 1.0
Ψ = 0.8
Ψ = 0.6
Fig. 5. Variation of hydrogen production with gasification temperature at J ¼ 1.0, 0.8
and 0.6.
C. Loha et al. / Energy 36 (2011) 4063e4071 4069
investigation. It is also observed fromFig. 6 that as the temperature
increases the external energy input increases continuously. Thus
for an economically variable operation, a trade off between HHV
and energy input is justified as the yield of H
2
is higher at higher
temperature
In Fig. 7, the steam-to-biomass ratio at CBP is also plotted
against the corresponding gasification temperature. It is illustrated
that as the gasification temperature increases, the CBP is reached at
lower value of j. For example, while the value of steam to biomass
ratio is 0.9 at 600

C, it reduces to around 0.22 when the gasification
temperature is 900

C.
9. Concluding remarks
The thermodynamic analysis can be considered as an effective
method for design and analysis of hydrogen rich synthetic gas
production formfluidized bed steam gasification of biomass. In the
present work, an equilibrium model has been developed to predict
the gas composition. The variation of hydrogen production, HHV of
the product gas, energy and exergy efficiencies and external energy
input to the gasifier are studied by varying the steam-to-biomass
ratio and gasification temperature. The H
2
production increased
continuouslywithincreaseinjandit increasedat thebeginningand
then becomes nearly asymptotic with temperature. It is also evident
form the result that all the efficiencies (h
I, cold gas
, h
II, a
and h
II, c
)
reached their maximum value at CBP except h
II, b
, which considers
theexergyof char carbon. The HHVof the product gas increasedwith
j and decreased with temperature. On the other hand, the external
energy input increased with increased in both j as well as temper-
ature. Therefore, as the energyand exergyefficiencies are maximum
at CBP and H
2
production increased beyond CBP, a designer has to
chose the range of operating parameters depending on their
requirement so that the external energy input is reasonably less as
well as theHHVof theproduct gas is intheacceptable level. It maybe
mentioned here that presence of tar in the product gas is a big
problemin fluidized bed gasification of biomass. Therefore, to crack
the tar gasification is generally done at higher temperature. Thus,
deploying catalysts for tar cracking for lowtemperature gasification
is justifiable from thermodynamic point and needs further study.
Acknowledgment
The authors expressed since gratitude to Prof (Dr.) Gautam
Biswas, Director, Central Mechanical Engineering Research Insti-
tute, Durgapur for his continuous support and encouragement. HC
acknowledges support of Department of Science and Technology
under the PURSE scheme.
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