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Energy Sources, Part A: Recovery,
Utilization, and Environmental Effects
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Modeling the Steam Gasification
Reactions for Reactor Design
D. K. Sharma
a
a
Center for Energy Studies, Indian Institute of Technology , Delhi ,
New Delhi , India
Published online: 05 Oct 2010.
To cite this article: D. K. Sharma (2010) Modeling the Steam Gasification Reactions for Reactor
Design, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 33:1, 57-71, DOI:
10.1080/15567030902967819
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Energy Sources, Part A, 33:5771, 2011
Copyright Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567030902967819
Modeling the Steam Gasication Reactions
for Reactor Design
D. K. SHARMA
1
1
Center for Energy Studies, Indian Institute of Technology, Delhi,
New Delhi, India
Abstract Gasication of coal is important for hydrogen generation and also for the
integrated gasication combined cycle power generation. Modeling of the gasication
reaction is important for the reactor design and operation. Different models suggested
for the gasication of coals and chars have been reviewed. The author and his research
group have carried out studies on the steam gasication of coal after organo-rening
and steam pyrolysis. Based on the studies of the author and his research group on
the steam gasication of coal, preextracted coal residues and their chars, a modied
model for the steam gasication of coal, has been suggested. This model is based on
the shrinking core model and this incorporates the surface and chemical reactivities
of coal along with adsorption equations and residual volatile matter.
Keywords active surface area, exposure of mineral matter, factors affecting gasi-
cation, fuel cells, H
2
generation, integrated gasication combined cycle, modeling,
organo-rening, steam gasication, steam pyrolysis
Introduction
Direct use of coal results in environmental pollution. However, coal can be gasied to
generate hydrogen or produce synthesis gas for the integrated gasication combined cycle
(IGCC) power generation as well as fuel cells (Sharma, 2008). Extensive work has been
carried out on gasication of coals and chars (Elliot, 1981).
Commercial/demonstration plants based on gasication of coal are either running or
are in the stage of commissioning. However, neither the structure of coal nor the exact
mechanism of gasication of coal is clear. It is important to understand the mechanism
of gasication for designing the reactors for the gasication of coals. Modeling of
gasication reactions is also important for the reactor design. One of the problems in
the coal gasication is the short life span of refractories. Advancement in modeling may
avoid the costly replacement of refractory lining by properly understanding some of the
important factors. The author and his research group have extended research work on
the gasication of coal through organo-rening and steam pyrolysis of coals. Kasaoka
et al. (1987) have reported the effect of carbonization conditions on the steam gasication
of coal.
In the present work, the aim was to rst review the different models of steam
gasication of coal and then suggest a modied model based on the present authors
studies as reported in the previous papers (Sharma and Singh, 1993; Sharma et al., in
press; Sharma, 2010).
Address correspondence to D. K. Sharma, Center for Energy Studies, Indian Institute of
Technology, Delhi, New Delhi 110016, India. E-mail: sharmadk28ces@gmail.com
57
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58 D. K. Sharma
Modeling of Gasication Reactions
Rational design of a coal gasier requires the best possible understanding of the funda-
mental chemical and physical processes that occurs during the subsequent gasication of
the coal char itself. Liu et al. (2000) have reported the mathematical modeling of coal
gasication at high pressure and temperature. Kuo (1984) has reported the activation
energies for the different gasication reactions. Different models have been proposed
for the gasication reactions that involve different rate constants, k
1
. k
2
. . . . . k
n
, etc., of
different reactions taking place at different stages (Elliot, 1981).
Smoot and Smith (1985) have described the initial kinetic modeling of coal char
gasication reactions as follows:
Modeling of char oxidation with O
2
2C CO
2
K
!2CO
1 D T( CTT)
D 1.68 10
2
ms
1
K
1
T D 1.32 10
6
ms
1
K
2
Char oxidation with CO
2
C CCO
2
K
!2CO
1 D T
n
e
E=RT
n D 1.0
D 4.40 ms
1
K
1
1 D 38.7 kcal mol
1
Char oxidation with H
2
O
C CH
2
O
K
!CO CH
2
1 D T
n
e
E=RT
n D 1.0
D 1.33 ms
1
K
1
T D 35.1 kcal mol
1
Complicated and complex reactions taking place during gasication of coal and coal
char require in-depth computations, which may be possible by using super computers.
However, in any event, mathematical modeling of complex coal conversion systems,
including the direct combustion or gasication reactions, involve many physical and
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Modeling the Steam Gasication Reactions for Reactor Design 59
chemical processes that are not fully understood. Even the organic chemical structure
and physicochemical constitution of coal and coal char is not understood yet.
Different models include the mathematical modeling where different reaction rate
constants have been taken together in equations to derive the overall rate constants (Elliot,
1981; Kuo, 1984; Liu et al., 2000). Damkhler, Biot, and Piclet numbers are also used.
Molina and Mondragon (1998) have reviewed some of these models. Models that do
not consider structural changes during reaction are most simple (Molina and Mondragon,
1998), otherwise the treatment becomes too complex, where a large number of rate
constants of several reactions are included in equations. In fact, several other workers
have also reported the modeling and simulation work on the uidized bed and entrained
ow gasication of coals or chars (Ni and Williams, 1995; Vamvuka et al., 1995; Yan
et al., 1999; Yan and Zhang, 2000; Kim et al., 2000; Ross et al., 2005). However, a few
general gasication models have been considered presently. Steam is more reactive than
CO
2
and this can be attributed to the weak hydrogen bonds present in water molecules
compared to the double bonds present in the CO
2
. This involves structural factors.
Shrinking Core Model
The size of coal char particles decrease during steam gasication reactions; therefore,
the shrinking core model has been suggested for the steam gasication of coals/chars, on
the same lines as this has been suggested for combustion (Levenspiel, 1992), pyrolysis
(Sharma et al., 1994), and organo-rening of coal (Giri and Sharma, 2000).
The low porosity of coal char, which restricts diffusion of reactants into the internal
structure of the coal char particle, causes the reactions to occur on the surface of the
shrinking core. For this model, the structure factor depends on the initial surface area,
porosity and if chemical reaction is the controlling step, reactivity expressions are:
. D b1 (1 kt )
3
c.
J.
Jt
D 3k(1 .)
2=3
.
where k is reaction kinetics constant and . is the conversion. The present author has
modied this model further as described later in the text based on his studies.
Homogeneous Model
This model assumes that the gas (steam or CO
2
) is reacting with coal/char in all possible
places and the reaction is like a homogeneous system where the particle is (almost) totally
accessible for reaction with gases:
. D 1 e
kt
.
J.
Jt
D k(1 .).
This is a simple model. Ahmaruzzaman and Sharma (2007a, 2007b) have recently used
this for kinetic studies on coprocessing of coal with plastics, vacuum residue, and biomass.
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60 D. K. Sharma
Random Pore Model
In this model, the random overlapping of pores surface is considered, which reduced
the area available for reaction (Molina and Mondragon, 1998):
. D 1 e
2t .A
o
t C2A
1
t /
.
J.
Jt
D 4(1 .)
_

2
1
C
o
ln(1 .).
where
o
and
1
are empirical constants. This model has been modied to include
active surface intrinsic reactivity. Everson et al. (2006) have further modied this model
as described later in the text.
Johnsons Model
Johnsons model is as follows (Molina and Mondragon, 1998):
J.
Jt
D
1
k
1
(1 .)
2
3
e
x
2
.
where
1
is the relative reactive factor depending on char type and temperature, k
1
is a
kinetic constant depending on partial pressure of gases reacting, and .
2
represents the
relative inuence of the effective surface area. This model gets transformed to a simple
model depending on value.
van Heek et al. (1987) have extended extensive research work on the kinetics of
gasication of coal. Johnson (1981) has reviewed the fundamental aspects of gasication
of coals where rates of several steps are important. However, if D 0, this model becomes
the non-reacting shrinking core model and if D 1, this becomes a homogeneous model
for conversions below 0.75. This model seems to be a modication of the other models
to include different factors affecting the char reactivity.
Dutta and Wen Model
This model has introduced the factor a, which is the ratio of the pore surface available
per unit weight to the initial one:
J.
Jt
D akC
g
(1 .).
This is relatively a simpler model. In fact, it is the active surface area within pores,
which is an important factor in the gasication, though volatile matter also inuences the
reactivity of coal or char.
Modied Volumetric Model
This is a modication of the homogeneous model where a time factor (i.e., order b of
the reaction) has been added as follows:
. D 1 e
at
b
.
J.
Jt
D a
1=b
b(1 .)ln(1 .)|
.b1/=b
.
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Modeling the Steam Gasication Reactions for Reactor Design 61
where a and b are empirical constants. This is a modication to include homogeneous and
random pore model expressions. This model takes into account the kinetics parameter,
i.e., the order of the reactions.
Adshiri and Furusawa Model
Here, S
x
, the surface area has been included for low porosity, i.e., <0.5 chars (Molina
and Modragon, 1998):
J.
Jt
D S
x
k k(1 .).
This is also a simple model for the complex gasication reactions. The percolation model
involves pore behavior and fragmentation (Goler et al., 2009).
Unication Theory Model
This is based on the shrinking core model having order m for gas:
J.
Jt
D 1
CO
(1 .)
m
1
"
D
0.38
t 1
2
1
"
D
_
t
0
_
J.
Jt
_
J.
and
t 1
2
1
"
D 1
u
.
This model takes into account the order of the reactions and half-time of reactions as
has been reported by Miura et al. (1989) and the present author (Sharma et al., in press;
Sharma, 2010). Molina and Mondragon (1998) have reported this in detail.
Liliedahl and Sgostorem Model
This model includes active sites and free chars:
. D cosh(kk
1
)e
kt
.
. D (1 Ckk
1
t )e
k.k
1
C1/t
.
where k and k
1
are kinetic constants that depend on the nature and pressure of the
gasifying agent. Molina and Mondragon (1998) have described this in detail. In fact,
complexities of gasication may require an in-depth and detailed approach for modeling
these reactions (Elliot, 1981; Liu et al., 2000; Johnson, 1981). Most of these models are
useful for approximate calculations.
Modied volumetric model and unication theory model may be mostly used if
the object is to compare the reactivity of different coals. The homogeneous model and
shrinking core model are good to describe a relation between time and conversion. If
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62 D. K. Sharma
one sees large and a lot of different smaller size char particles in ash from the gasier
then the shrinking core model may be used. However, when one sees small, irregularly
broken or fused and cracked particles, the application of homogeneous model may be
better. However, due consideration should be given to active surface areas in coals/chars.
Kasaoka et al. (1987) have reported the following equation:
1 D 0.719 [FC(Coal)]
0:75
[C(char)]
0:59
where FC (Coal) is the xed carbon in coal and C is the moisture holding capacity of
the char in g water/g of dry solid char prepared at temperatures above 900

C.
Coats and Redfern Model
The author has used the Coats and Redfern model (Sharma et al., in press) for the studies
of nonisothermal kinetics of steam gasication of coal and char. In fact, Lee and Beck
(1984) have also reported a modied model for the nonisothermal kinetic studies.
For n D 1
LnLn(1 .),T
2
| D Ln
__
1
a1
__
1
21T
1
__
1,1T
n 1
Ln1 (1 .)
1n
,(1 n)T
2
| D Ln
__
1
a1
__
1
21T
1
__
1,1T
where
. D Fractional weight loss of coal in steam
T D Temperature
D Frequency factor
1 D Gas constant
a D Heating rate
1 D Activation energy of the gasication reaction
Ahmaruzzaman and Sharma (2005a, 2005b, 2007b, 2007c) have also employed this model
for co-processing of coal with plastics, vacuum residue, and biomass recently.
Lee and Beck Model
Lee and Beck have reported that their model represents more accuracy than the Coats
and Redfern model. The Lee and Beck model is as follows:
_
!
!
0
Jo
(o)
D

_
_
_
_
_
1T
2
1
_
exp
_

1
1T
_
_
1 C
21T
1
_
_
1T
2
1
_
exp
_

1
1T
_
_
1 C
21T
0
1
_
_

_
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Modeling the Steam Gasication Reactions for Reactor Design 63
For rst order reaction,
(o) D (1 o)
_
!
!
0
Jo
(o)
D ln(1 o
0
) ln(1 o)
For nth order reaction,
(o) D (1 o)
n
_
!
!
0
Jo
(o)
D
_
1
1 n
_
(1 o
0
)
1n
(1 o)
1n
|
For 0th order reaction,
(o) D 1
_
!
!
0
Jo
(o)
D o o
0
where
D Arrhenius frequency factor, s
1
1 D Activation energy, KJ/mol
1 D Gas constant (8.314J/mol.K)
T D Final temperature, K
D Heating rate, K/s
o
0
D Initial weight
o D Fraction of solid gasied at time t
T
0
D Initial temperature
(o) D Function of o
Recent Models
Everson et al. (2006) have stated that the low porosity of the coal char, which restricts
diffusion of reactants into the internal structure of coal char particle, causes the reactions
to occur on the surface of a shrinking core. These authors have included the structure
factor that depends on the initial surface area, porosity, and the conversion into the
shrinking core model. The respective structure factor is the following:
(.) D
S
o
(1 .)
2
3
1 c
o
.
J.
Jt
1
(1 .)
2
3
D r
S
o
1 c
o
t.
with
J(.) D
_
x
0
J.
(.)
.
Thus, a linear plot of (.) versus t for constant partial pressure of the gas is a suitable
test for the validity of the shrinking core model (Everson et al., 2006).
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64 D. K. Sharma
It was found that the shrinking unreacted core model with a controlling surface
reaction together with Langmuir-Hinshelwood intrinsic reaction kinetics was applicable.
The shrinking external surface area of a particle is a determining structural property.
Factors Affecting Modeling of Gasication of Coal
At low temperatures, steam gasication reaction (kinetics) is controlled by (chemical
reaction) kinetics and later on at high temperatures rst by pore diffusion and then by
lm diffusion (van Heek and Muehlen, 1985). Pressure has no effect on gasication
of coal/char and surface area in chars passes through maximum between 650850

C
of pyrolysis and then drops (van Heek and Muehlen, 1985). At low temperatures the
chemical reactions are slow in steam gasication and pores are accessible, whereas at
high temperatures, the chemical reactions become faster and pores with smaller volumes
are no longer accessible. Activation energy of pore diffusion is 50% of that of chemical
reaction controlled.
Activation energy of coal chars for steam gasication is close to 120250 KJ/mol
as reported in the literature (Everson et al., 2006). Miura et al. (1989) have reported that
gasication rates in thermogravimetric analysis (TGA) are same as in the gasication
reactor; therefore, kinetic modeling based on TGA studies would be valid for the gasi-
cation reactors. Earlier studies of the authors research group have shown that factors, such
as volatile matter, chemical reactivity, chemical pretreatment (such as organo-rening),
steam pyrolysis, availability of mineral matter (MM) as catalysts and promoters, active
surface area, etc., are important for the gasication of coal (Sharma and Singh, 1993;
Sharma et al., 1991; Sharma et al., in press; Sharma, 2010).
Modeling the Steam Gasication of Residual Coals Obtained
after Organo-rening and Their Chars (Authors Model)
In the previous paper (Sharma et al., in press; Sharma, 2010) the development of a
stepwise coal conversion process has been reported. Talcher coal, a bituminous coal, was
subjected to stepwise organo-rening (solvent extraction) using anthracene oil (AO) fol-
lowed by liquid parafn (LP) extraction. The residual coals (RC) obtained were pyrolyzed
and the steam gasication kinetics of these samples were studied in a gasication reactor
as well as in TGA apparatus under nonisothermal conditions. In fact, TGA provides
a semi-quantitative understanding under well-controlled laboratory conditions. The use
of ne particles and small sample sizes would minimize the phenomenon related to
transport problems and may simulate the uidized bed conditions. This would improve
the validity of steam gasication data for kinetic analysis and modeling. The advantages
of nonisothermal (dynamic) mode of TGA are that the kinetics can be probed over the
entire temperature range of interest in a continuous manner. The disadvantages of the
changes in the sample when it is being raised to a temperature of interest are avoided.
Presently, the Coats and Redfern model was used for the kinetics analysis even though a
modied Coats and Redfern model is also available and may be used further if required
(Lee and Beck, 1984). The steam gasication reactions were found to be diffusion-
controlled mostly for the residual coals as well as for the chars of the residual coals
obtained (Sharma et al., in press; Sharma, 2010). Everson et al. (2008) have used a
power equation to use the random pore model and Zhang et al. (2010) have modied the
same for use on catalytic gasication of coal.
The aforementioned discussion on the factors effecting the steam gasication of coal
has revealed that the steam gasication reactivity mainly depends upon the rank (C %)
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Modeling the Steam Gasication Reactions for Reactor Design 65
of coal, H/C, O/C atomic ratio, active surface area (i.e., active sites associated with
heteroatoms, side chains, strained rings, etc.), nascent sites, dangling carbon atoms or
side chains, sterical strained functional groups, edge carbon atoms containing structures,
reactive functional groups generated (e.g., epoxide, CH
2
OH, CHO, etc.), amount of
mineral matter, their dispersion in coal/char and exposure or availability, pores holding
moisture and chemisorbed O
2
, volatile matter or residual volatile matter, fuel ratio,
VM/FC (ratio), pyrolysis conditions for preparing chars, system pressure, reactive gas
concentration, temperature, aromaticity, degree of condensation of aromatic rings or cross-
linking, etc. Research work in some of these areas has been performed (Sharma et al.,
1986a, 1986b, 1986c; Sharma and Singh, 1995; Sharma and Singh, 1993; Pande and
Sharma, 2001, 2002; Sharma et. al., 1991; Sharma et al., 1994; Sharma, 1992).
In the present work, attempts were made to enhance the steam gasication reactivity
of Talcher coal, where mineral matter is nely dispersed in the organic matter of coal.
Talcher coal was rst subjected to the solvent extraction by using anthracene oil at 250
300

C. This resulted in swelling of the coal followed by penetration of the solvent in

the coal to break the three-dimensional cross-linked gel structure of coal. The extraction
of organic matter from coal results in removing not only the trapped molecules but this
also benecially disrupts and degrades coal macromolecules by breaking noncovalent
and covalent interactions. This results in the following modications of coal (Sharma
and Giri, 1994): (1) Reduction of size grading and increase of surface area (Giri, 1995);
(2) Generation of active and nascent sites in coal by creating channels, worm hole-type
pores, or ssures and cracks (Ahmaruzzaman and Sharma, 2005b); (3) Widening pores
and creating more meso, micro, and macropores, by generating active sites whereby
moisture holding capacity and O
2
chemisorption capacity would be enhanced; (4) De-
ploymerizing the coal and creating active functional groups having enhanced reactivities;
(5) Increasing proportion of MM and exposing more and more mineral matter, which
becomes available and acts as catalysts; (6) Increasing the VM/FC fuel ratio; (7) Recov-
ering the volatile components from coal, which would have generated tar in the gaseous
products; (8) Oxidation of MM to act as catalysts; (9) Generation of quinonoids, phenols,
acids, avonoids, epoxide, aldehydes, etc. type reactive structures; and (10) Generation
of nanoparticles with very large surface areas and special reactivity properties, etc.
Similar effects would be offered by the next step of extraction of the residual coal
(RC) with liquid parafn. Further, the next step was the steam gasication of the RCs
obtained. The benecial effects of using steam in pyrolysis at 650

C would generate
reactive char from the RCs (Sharma and Singh, 1995). The oil tar products and pyrolysis
gases may be recovered. The char obtained would contain sufcient active sites with
an increased active surface area. However, the residual volatile matter (RVM) may be
reduced, but the char surface area was modied sufciently for the steam gasication
to react properly; therefore, in the present work it is proposed to suggest a modied
shrinking core model as follows:
J(.) D
J.
Jt
D 3koS
u
(1 .)
2
3
.
where S
u
takes into account the active surface area (Ahmaruzzaman and Sharma, 2005b)
and o is related to the thermochemical degradation/depolymerization of coal/char macro-
molecules, as shown:
J(.) D S
u
o
(1 .)
2
3
1 c
o
.
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66 D. K. Sharma
In fact, o is related to the chemical reactivity/thermochemical reactivity of coal, which
may be dened approximately as VM/FC (or RVM/FC only) and precisely as the ratio of
aliphatic, i.e., naphthenic or hydroaromatic functionality/aromaticC (from the solid state
13
CNMR spectral analysis). Pretreatments, such as organo-rening and steam pyrolysis,
afford sufcient RVM in the treated coal to render it reactive for the steam gasication
reactions as described earlier (Sharma et al., in press; Sharma, 2010).
Coal moisture holding capacity (C) is related to micropores volume, and active
surface area (ASA) is related to the amount of O
2
chemisorbed. Therefore, ASA and C
are more related to the number of active sites on coals (Miura et al., 1989).
1
H
2
O
D Steam gasication reactivity
D
0.5
t
0:5
.
where t
0:5
is the time for 50% gasication of coal.
The 1
H
2
O
values obtained by applying this formula are shown in the Table 1. 1
H
2
O
showed the following trend (Table 1):
OTC D AO-C > AO-LP-C > OTC > AO-LP-C-C > AO-C-C
(supporting the effect of organo-rening)
This trend almost correlated well with the amount of RVM in coal/char or with RVM/FC
ratio (Table 1).
Atomic H/C ratio of OTC, AO-C, and AO-LP-C was found to be 0.935, 0.765, and
0.611, respectively. The atomic H/C ratio of OTC-C, AO-C-C, AO-LP-C-C was observed
to be 0.339, 0.025, and 0.026, respectively.
Almost the same trend was followed in swelling ratio in quinoline, which is a measure
of the degree of reduction of cross-linking density in the three-dimensional cross-linked
network gel structure of coals/chars (Pande and Sharma, 2001, 2002).
These studies showed that organo-rening (i.e., solvent extraction) is a benecial
treatment for the stream gasication of coal. This has also been supported by the
Table 1
Steam gasication reactivities of treated coals and chars
Sample
t
0:5
,
min 1
H
2
O
D
0:5

0:5
Swelling in
quinoline
RVM,
% 1
H
2
O
, min
1
OTC 82.5 0.0060 2.0 38 6.0 10
3
AO-C 87.0 0.0057 2.2 34 6.0 10
3
AO-LP-C 92.0 0.0054 1.3 27 5.7 10
3
OTC-C 92.5 0.0052 1.2 14 5.4 10
3
AO-C-C 95.0 0.0054 1.3 27 5.2 10
3
AO-LP-C-C 94.0 0.0053 1.1 18 5.3 10
3
OTC D Original Talcher coal; AO-C DAO extracted/treated (residual) coal; AO-LP-C D AO-LP
successively extracted/treated (residual) coal; OTC-C D Original Talcher coal char; AO-C-C D AO
extracted residual coal char; AO-LP-C-C D AO-LP extracted residual coal char; RVM D Residual
volatile matter.
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Modeling the Steam Gasication Reactions for Reactor Design 67
differential gravimetric analysis studies of the rate of gasication reactions of treated
coal samples at different temperatures (Sharma and Singh, 1993; Sharma et al., in press).
The reason could be the following: (1) Reduction of degree of cross linking of the
coal; (2) Creation of surface active sites, coal pores, cracks, etc. by solvent diffusion,
swelling, and leaching (Pande and Sharma, 2001, 2002); (3) Increase of proportion of
MM and exposing and availability of MM as a result of the leaching and consequent
removal of organic matter from coal (Sharma and Mirza, 1983); (4) Modication of coal
by solvent extraction, where coal is benecially disrupted to generate active functional
groups, such as side chains on reconguration after solvent removal or desorption;
(5) Depolymerization and degradation of coal macromolecules during organo-rening.
The following reactive chemical moieties may be generated for further reactions as
shown below.
Extraction would recover some of the trapped and loosely held molecules of coal
thus, this would lead to reduction of tar, phenolic compounds, oil, etc. in the gaseous
products, and, therefore, this may help in avoiding the step of gas clean-up in the IGCC
power generation.
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68 D. K. Sharma
The factor o, in the presently suggested model, represents VM/FC or RVM/FC in
coal or char in an approximate sense,
a
(C) or C-aromaticity of coal based on NMR
spectroscopy in a chemical sense, and H/C atomic ratio if NMR spectral analysis is
not available. Dependence of steam gasication reactivity on RVM presently, validates
inclusion of o in the model suggested for the steam gasication of coal presently. Thus,
present studies along with previous studies (Sharma et al., in press; Sharma, 2010) render
a support to the present model suggested for the steam gasication of coal, which takes
into account not only shrinking core-random pore model (including chemical reactivity
of coals and chars and Langmuir and Hinshelwood equations) and modied chemical
reactivity at the surface of coal and chars as a result of pretreatments and modication
etc. for boosting the reactivity. Presently, the following model based on the chemical
reactivity of coal and char has been suggested as follows:
(X) D
S
r
o(1 X)
2
3
1 c
o
.
JX
Jt
1
(1 X)
2
3
D r
S
r
1 c
o
o.
along with Langmuir and Hinshelwood equations and S
u
based on absorption studies on
residual coal by Ahmaruzzaman and Sharma (2005b):
(X) D r
s
r
o
1 c
o
t.
with J(X) D
_
X
0
dX
f.X/
.
Gasication models can be used for the reactor design, process control, operation,
trouble shooting, and for prolonging the life of the gasication liner.
Conclusions
The organic chemical structure and physical constitution of coal are still not clearly
understood. Gasication reactions of coal involve a complex chemistry that makes it
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Modeling the Steam Gasication Reactions for Reactor Design 69
difcult to model the gasication reactions. Presently, several models reported on the
gasication of coal and char have been reviewed. Attempts have been made to suggest a
model for the gasication of coal and char, which may incorporate the chemical reactivity
of coals and char along with surface reactions, based on the shrinking core, active surface
area, adsorption equations, VM/FC ratios, etc. Gasication models can be used for the
reactor design. The authors studies have shown that organo-rening and steam pyrolysis
may boost the steam gasication reactivity of coal by increasing the active surface area,
exposing the mineral matter constituents and by making available the residual volatile
matter in coal to render the coal/char reactive. Stepwise conversion of coal may help in
solving some of the problems in the steam gasication of coal and may also enhance the
reactivity.
References
Ahmaruzzaman, M., and Sharma, D. K. 2005a. Non-isothermal kinetic studies on coprocessing of
vacuum residue, plastics, coal and petrocrops. J. Anal. & Appl. Pyrolysis 73:263275.
Ahmaruzzaman, M., and Sharma, D. K. 2005b. Adsorption of phenol from wastewater. J. Colloid.
& Interface Sci. 287:1424.
Ahmaruzzaman, M., and Sharma, D. K. 2007a. Co-processing of petroleum vacuum residue with
plastics, coal and biomass and its synergistic effect. Energy & Fuels 21:891897.
Ahmaruzzaman, M., and Sharma, D. K. 2007b. Kinetic studies on co-cracking of petroleum vacuum
residue with biomass (petrocrop). Pet. Sci. & Tech. 25:925936.
Ahmaruzzaman, M., and Sharma, D. K. 2007c. Chemical reaction engineering studies on co-
cracking of petroleum vacuum residue with coal, plastics and biomass (bagasse and petrocrop).
Pet. Sci. & Tech. 25:937947.
Elliot, M. A. 1981. Chemistry of Coal Utilization, Second supplementary volume. New York: Wiley
Interscience.
Everson, R. C., Hain, W. J. P., Neomagus, R. K., Falcon, R., and du Cann, V. M. 2008. Properties
of high ash coal char particles derived from inertinite rich coal: Gasication kinetics with
carbon dioxide. Fuel 87:34033408.
Everson, R. C., Neomagus, H. W. J. P., Kasini, H., and Njapha, D. 2006. Reaction kinetics of
pulverized coal-chars derived from inertiniterich coal discards. Gasication with carbon
dioxide and steam. Fuel 85:10761082.
Giri, C. C. 1995. Studies on development of a process for solvent deashing of coal to obtain
environmentally clean fuels and characterization of products. Ph.D. Thesis, Indian Institute
of Technology, Delhi, New Delhi, India.
Giri, C. C., and Sharma, D. K. 2000. Kinetic studies and shrinking core model on solvolytic
extraction of coal. Fuel Proc. Technol. 22:97109.
Goler, F., de Steene, L. V., Salvador, S., Mermoud, F., Oltean, C., and Bues, M. A. 2009. Impact
of peripheral fragmentation on the steam gasication of an isolated wood charcoal particle in
a diffusion controlled regime. Fuel 88:14981503.
Johnson, J. F. 1981. Fundamentals of gasication. In: Chemistry of Coal Uilization, Second Suppl.
Vol., Elliot, T. S. (Ed.). New York: Wiley Interscience.
Kasaoka, S., Sakata, Y., and Shimada, M. 1987. Effects of coal carbonization conditions on rate
of steam gasication of char. Fuel 66:697701.
Kim, Y. J., Lee, J. M., and Kim, S. D. 2000. Modeling of coal gasication in an internally circulating
uidized bed reactor with draught tube. Fuel 79:6977.
Kuo, J. C. W. 1984. Gasication and indirect liquefaction. In: The Science & Technology of Coal
and Coal Utilization, Cooper, B. R., and Ellingson, W. A. (Eds.). New York: Plenum Press.
Levenspiel, O. 1992. Chemical Reaction Engineering, Second Ed. New Delhi, India: Wiley Eastern
Ltd.
D
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w
n
l
o
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d
e
d

b
y

[
I
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i
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e

o
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T
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c
h
n
o
l
o
g
y

-

M
u
m
b
a
i
]

a
t

2
2
:
2
8

0
2

J
u
l
y

2
0
1
4

70 D. K. Sharma
Lee, T. V., and Beck, S. R. 1984. A new integral formula for kinetic analysis of nonisothermal
TGA data. AICHE J. 30:517519.
Liu, G. S., Tate, A. G., Bryant, G. W., and Wall, T. F. 2000. Mathematical modelling of coal char
reactivity with CO
2
at high pressure and temperature. Fuel 79:11451154.
Miura, K., Hashimoto, K., and Silverston, P. L. 1989. Factors affecting the reactivity of coal chars
during gasication and indices representing reactivity. Fuel 68:14611475.
Molina, A., and Mondragon, F. 1998. Reactivity of coal gasication with steam and CO
2
. Fuel
77:18311839.
Ni, Q., and Williams, A. 1995. A simulation study on the performance of an entrained-ow coal
gasier. Fuel 74:102110.
Pande, S., and Sharma, D. K. 2001. Studies of kinetics of diffusion of N-methyl-2-pyrrolidone
(NMP), ethylenediamine (EDA) and NMPCEDA (1:1, vol/vol) mixed solvent system in
Chinakuri coal by solvent swelling techniques. Energy & Fuels 15:10631068.
Pande, S., and Sharma, D. K. 2002. Ethylenediamineassisted solvent extraction of coal in N-
methyl-2-pyrrolidone. Synergistic effect of ethylenediamine on extraction of coal in N-methyl-
2-pyrrolidone. Energy & Fuels 16:194204.
Rossa, D. P., Yana, H., Zhong, Z., and Zhanga, D. 2005. A non-isothermal model of a bubbling
uidised-bed coal gasier. Fuel 84:14691481.
Sharma, D. K. 1992. Pyrolysis of coal in steamA review. J. Sci. & Ind. Res. 51:964972.
Sharma, D. K. 2008. Cleaner coal technologiesConcept of coal reneries for added value and
efcient use of coal. Ind. Chem. Engr. 50:155168.
Sharma, D. K. 2010. Enhancing the steam gasication reactivity of coal by boosting the factors
affecting the gasication reactions in the stepwise coal conversion. Energy Sources 32:1727
1736.
Sharma, D. K., and Giri, C. C. 1994. Solvent deashing of coal to get an environmentally clean
and high caloric value fuel by batch extractive rening technique under ambient conditions.
Fuel Sc. & Tech. Intl. 12:191210.
Sharma, D. K., and Mirza, Z. B. 1983. Role of mineral matter in chemical reactivity of coal. Fuel
62:916917.
Sharma, D. K., and Singh, S. K. 1993. Effect of solvolytic extraction and pyrolysis pretreatments
on the low temperature gasication reactivity of coal and reduction of tar formation in product
gases for the integrated combined cycle power generation. Fuel Sc. & Tech. Intl. 11:1655
1677.
Sharma, D. K., and Singh, S. K. 1995. Studies on stepwise coal conversion. Fuel Sc. & Tech. Intl.
13:11851198.
Sharma, D. K., Sandle, N. K., Singh, S. K., and Venugopal, M. 1991. Solvolytic extractive
disintegration and gasication of coal. J. Mines, Metals & Fuels 34:6064.
Sharma, D. K., Sarkar, M. K., and Ganapathi, M. 1994. Kinetics studies of the devolatilization
of Indian coals in isothermal and nonisothermal conditions in thermobalance and in a batch
reactor. Fuel Sc. & Tech. Intl. 12:795811.
Sharma, D. K., Singh, S. K., and Mathew, S. K. Steam gasication of coal under milder low
temperature conditionsNonisothermal kinetics studies for reactor design. Energy Sources
(in press).
Sharma, D. K., Sulimma, A., and van Heek, K. H. 1986a. Comparative studies on pyrolysis of coal
in hydrogen, steam and argon atmospheres. Erdoel & Kohle-Erdgas-Petrochemie 39:173176.
Sharma, D. K., Sulimma, A., and van Heek, K. H. 1986b. Hydropyrolysis of coal in steam
atmosphere. Fuel 65:15711574.
Sharma, D. K., Sulimma, A., van Heek, K. H., and Juentgen, H. 1986c. Characterization of tar
obtained from the pyrolysis of coal in argon, steam and hydrogen atmospheres. Erdoel and
Kohle-Erdgas-Petrochemie 39:357360.
Smoot, L. D., and Smith, P. J. 1985. Coal Combustion and Gasication. New York: Plenum Press.
van Heek, K. H., and Muehlen, H.-J. 1985. Aspects of coal properties and constitution important
for gasication. Fuel 64:14051414.
D
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b
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2
0
1
4

Modeling the Steam Gasication Reactions for Reactor Design 71
van Heek, K. H., Muehlen, H.-J., and Juentgen, H. 1987. Progress in kinetics of coal and char
gasication. Chem. Eng. & Tech. 10:411419.
Vamvuka, D., Woodburn, E. T., and Senior, P. R. 1995. Modelling of an entrained ow coal gasier.
1. Development of the model and general predictions. Fuel 74:14521460.
Yan, H. M., and Zhang, D. K. 2000. Modelling of uidised-bed coal gasiers: Elimination of the
combustion product distribution coefcient by considering homogeneous combustion. Chem.
Eng. Proc. 39:229237.
Yan, H. M., Heidenreich, C., and Zhang, D. K. 1999. Modelling of bubbling uidised bed coal
gasiers. Fuel 78:10271047.
Zhang, Y., Hara, S., Kajitani, S., and Ashizawa, M. 2010. Modelling catalytic gasication kinetics
of coal char and carbon. Fuel 89:152157.
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