Energy Conversion and Management 65 (2013) 755763

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Energy Conversion and Management

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Thermodynamic equilibrium analysis of coal gasication using Gibbs energy

minimization method
Syed Shabbar, Isam Janajreh
Masdar Institute of Science and Technology (MIST), Mechanical Engineering Program, P.O. Box 54224, Abu Dhabi, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: A thermodynamics analysis of gasication process is performed using the Gibbs energy minimization
Available online 31 July 2012 approach through Lagrange multiplier method. Three different methods of gasication are analyzed to
convert bituminous (RTC) coal into syngas (CO and H2). These methods use air, air-steam and solar-
Keywords: steam, respectively, for gasication. Initially the properties of coal are experimentally determined using
Gasication efciency bomb calorimeter, simultaneous DSC/TGA Q600 thermal analyzer and Flash 2000 (CHNO-S) analyzer to
Coal measure higher heating value, proximate and ultimate composition, respectively. Using the experimental
Gibbs energy minimization
data an empirical formula of coal is derived to formulate a gasication model. The model accounts 44 spe-
Lagrange multiplier method
cies in the product that also includes for the solid carbon and sulfur. The result of gasication model is
presented in terms of equilibrium composition of product gases with the inclusion of minor. In the
end, the cold gasication efciency is calculated that shows the efciency of 70.94%, 71.64% and
90.67% for air, air-steam and solar-steam gasication, respectively. The cold gasication efciency clearly
shows an added efciency for solar-steam gasication process.
2012 Published by Elsevier Ltd.

1. Introduction from coal, biomass and industrial/municipal/agricultural waste.

The global increase in energy consumption and environmental
pollution elevate the demand of fuel that is cleaner and sustain-
able. The beginning of 20th century gives an imminent call for
the new challenges to tackle upcoming energy crises and global
warming. That brings the new era for the renewable energy and
cleaner fuel implementations. The use of conventional hydrocar-
bon in past two centuries rise the burden on environment in term
of green house gases that are one of the major causes of global
warming.
Thermo-chemical conversion (combustion, gasication, and
pyrolysis) is a core technology that can be utilized broadly to gen-
erate energy without polluting the environment. Because of its
many applications, it is currently enjoying a considerable renais-
sance [1]. Gasication is a thermo-chemical conversion process
which can be used to produce clean fuels. It is compatible with
new applications in the area of biomass conversion coal-to-liquid,
superior environmental performance especially with regard to CO2
capture and sulfur removal, and offers substantial efciency
improvement when incorporated in Integrated Gasication Com-
bined Cycle plants (IGCC).
Using the gasication process, a wide range of carbonaceous
material can be converted into high value fuel. The range covers
Corresponding author. Tel.: +971 2 698 8170; fax: +971 2 698 8121.
E-mail address: ijanajreh@mist.ac.ae (I. Janajreh).
The product of gasication is normally composed of syngas that
is a mixture of hydrogen and carbon monoxide. The production
of syngas using gasication is a complex process that is based on
several factors including the composition of feedstock, the gasier
temperature/pressure and the amount as well as type of oxidizer
and moderator [2]. The research previously accomplished in Waste
to Energy Lab at Masdar Institute shows a high potential of syngas
through gasication process [36].
The process of gasication utilizes the partial combustion of
feedstock by carefully controlling the amount of oxidizer. The
amount of oxidizer also controls the temperature of the gasica-
tion process that is the most important parameter of gasier, as re-
ported by Walawender [7].
There are three different methods of gasication that are cur-
rently implemented and under high focus of research. Gasication
using air as an oxidizer is the most widely used method [8] to pro-
duce syngas. Using different feedstock and operating condition a
diverse composition of product gases can be achieved [911].
The use of steam as a moderator during the gasication process
is also broadly implemented for gasication to enhance the yield
of fuel gas and reduce the tar content by cracking and reforming
[1214]. A relatively new technology of gasication using solar en-
ergy is also emerging for producing clean fuel enjoying an elevated
stress in research area [1517]. Gasication using the solar irradi-
ation skips the use of oxidizer that enhances the yield of product
syngas.

0196-8904/$ - see front matter 2012 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.enconman.2012.02.032
756 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763

Nomenclature

a number of atom of an element present in a specie T temperature

A total number of atom corresponds of specic elements TGA thermogravimetric analysis
C carbon X mole fraction
CGE cold gasication efciency k Lagrange multiplier
DSC differential scan calorimeter l chemical potential
f fugacity of specie
F function for total Gibbs energy of system Subscript
G total gibbs energy of the system c combustion
H hydrogen f formation
h enthalpy i total number of species present in the system free index
HHV higher heating value corresponding to elements
IGCC integrated gasication combined cycle w total number of elements present in the system.
m kmole of air wt% weight percentage
N nitrogen
n specie present in the system Superscript
O oxygen o standard
p kmole of H2O s kmole of sulfur present per kmole of carbon
P pressure t total
Q amount of solar energy x kmole of hydrogen present per kmole of carbon
R universal gas constant y kmole of oxygen present per kmole of carbon
S sulfur z kmole of nitrogen present per kmole of carbon

The gasication can be model using the Gibbs energy minimiza- ticles are segregated using a series of sieves shaker, schematics is
tion method that utilizes a zero dimensional approach. Gibbs en- shown in Fig. 1. The sieves are stacked in nine different sizes ranges
ergy minimization can be used by direct approach as reported by from 2 mm to 20 lm aperture sizes. The particle size used is 100
the literature [1820] or either through the Lagrange multiplier 200 lm sizes that came from the eight stacks of the sieves, as the
method as mentioned in the literature [2123]. In the forth going stack above it sizes 200 lm.
study the use of Gibbs minimization though Lagrange multiplier
method is used due to its fast convergence. Jarungthammachote
and Dutta [21] has used the Gibbs free energy minimization ap-
proach to determine the gasication product for spouted bed and
spout-uid gasier. Using the Lagrange multiplier approach, six
major components, CO, CO2, CH4, H2O, H2 and N2 are determined
in the mixture of producer gas. Li [24] used the free energy mini-
mization method to predict the performance of air blown circulat-
ing uidized bed coal gasier. The model is developed by
considering ve elements and 44 species in both solid and gas 2 MM
phase. Tang [19] developed a thermodynamic model to estimate
equilibrium composition for super critical water gasication of bio-
1.25 MM
mass using Gibbs free energy minimization approach. A variety of
literature [23,2528] is available that utilize the potential of the
free energy minimization for the gasication purpose. 850 MIC
In the present study, an attempt is made to explore the poten-
tial of Gibbs free energy minimization approach through Lagrange 710 MIC
multiplier for gasication process. For this purpose, RTC-coal is
gasied under different operating condition for gasication using 600 MIC
air, air-steam and solar heat. Starting with the material character-
ization for RTC-coal using proximate analysis, ultimate analysis 425 MIC
and calorimetric value, a gasication model is developed. The mod-
el predicts 44 species in the product stream that also accounts for 200 MIC
solid un-burn carbon and sulfur. The inclusion of energy balance
between product and reactants also provides the process adiabatic 100 MIC
temperature. After validation, the model is used to investigate the
composition of product of gasication. The gasication is per- 20 MIC
formed using air, air-steam and solar-steam scenario. Finally, the
cold gasication efciency is calculated and compared.

2. Feedstock characterization
Collection pan
The baseline characterization of RTC is followed by series of
steps. The rst step begins with the crushing of coal pieces with
hammer to make them at appropriate size. Then these crushed par- Fig. 1. Stack of sieves with aperture size ranges from 2 mm to 20 lm.
 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763 757

In the second step, the RTC-coal sample is tested in Parr 6100

bomb calorimeter to calculate the higher heating value (HHV) of
the sample. Initially the calorimeter is calibrated with the standard
benzoic acid. After calibrating the instrument, four sample of RTC
coal comprises of different weight are tested. The results presented
in Table 1 show the average heating value is 30.42 MJ/kg.
In the third step proximate analysis of the RTC-coal is per-
formed. The analysis is performed using simultaneous DSC/TGA
Q600 thermal analyzer. The main purpose of using this analysis
is to calculate the percentage of moisture, volatiles, xed carbon
and ash present in the sample. Initially, the instrument is cali-
brated using calcium oxalate (CaC2O4) sample for weight and heat
ow standardization.
After calibration three samples of RTC-coal are tested. The
weights of the samples are 7.98 mg, 10.13 mg and 8.33 mg, respec-
tively. All three samples are tested with a same operating condition
Fig. 2. DSC/TGA curve of RTC-coal with respect to time.
adopted from the literature [29]. Initially the sample is place in the
equipment and equilibrates at 25 C for 4 min. Then sample is
heated till 110 C with constant heating rate of 20 C/min. A con- Table 2
stant purging of nitrogen gas with ow rate of 100 ml/min is used. Summary of the proximate analysis of RTC-coal sample.
Sample is held at 110 C for 6 min to ensure the complete moisture Composition Weight (%)
release. In next stage, sample is heated from 110 C to 900 C with
Moisture 0.30
20 C heating rate. This heating evolves the volatiles present in the Volatiles 37.81
sample. As temperature reaches at 900 C the nitrogen purging is Fixed carbon 54.65
switched with air for combusting the char present in the sample. Ash 7.22
This combustion is performed isothermally for 15 min with Total 100

100 ml/min of constant air purging. The duration of 15 min is care-

fully and specically selected for RTC-coal sample that allows the
only the percentage of oxygen present in the sample is analyzed
complete combustion of the char present in the sample. The result
whereas second part is used to analyze the percentage carbon,
of DSC/TGA is presented in Fig. 2.
hydrogen, nitrogen present in the sample. Each part is comprised
The isothermal heating of sample at 110 C results in the loss of
of series of measurements that starts from the calibration of the
0.30% of weight that corresponds to the moisture release from the
instrument to the nal result. For oxygen analysis, initially two
sample. It took 14.2 min to complete the moisture release that also
blank sample holders are tested for any possible contamination
includes the time to equilibrate i.e. 4 min.
present in the sample holder itself. Then another two sample hold-
The heating of sample from 110 C to around 900 C results in
ers are tested with 23 mg of standard BBOT sample. The BBOT
the volatiles evolution. Total 37.81% of volatiles are calculated in
sample has a known weight percentage of carbon, hydrogen, nitro-
the sample from the quantitative data of the TGA curve and it took
gen, oxygen and sulfur. These samples are run in bypass mode that
37.8 min after moisture release. Before reaching 900 C the purge
runs the sample with an unknown composition mode. After that
gas is switched to air that allows the combustion of char. The
three more sample of BBOT are analyzed in standardization mode
weight of the sample quickly drops and the resident time of
to ensure the right calibration of the instrument. When the instru-
15 min allow a complete combustion of char present in the sample.
ment is fully calibrated then ve sample of RTC-coal weighting 2
The end of combustion resulted in an iso-weight line, as shown in
3 mg are tested in Flash 2000 to ensure the good quality results of
Fig. 2, following 900 C. The iso-weight line corresponds to the un-
oxygen concentration. Similar steps are taken to measure the
burnt ash present in the sample. The quantitative results corre-
amount of Carbon, hydrogen, nitrogen and sulfur present in the
sponding to iso weight line provides a 7.22% of total ash after the
sample. Only a slight change is adopted during the sample prepa-
combustion. Therefore, using the weight percentage of moisture,
ration by adding about 10 mg of vanadium penta-oxide (V2O5). The
volatiles and ash the amount of char present in the RTC-coal is cal-
vanadium penta-oxide is used to magnify the concentration of sul-
culated to be 54.65%. The heat ow in Fig. 2 shows an exothermic
fur in the sample. The result of ultimate analysis for RTC-coal is
process between 53 and 64 min on time scale that corresponds to
presented in Table 3 showing the high weight percentage of carbon
the combustion. The result of proximate analysis is presented in
present in the sample. The ultimate analysis can only be compare
Table 2.
to proximate analysis by compare the amount of ash present in
Finally, in the last step the sample is tested in the Flash 2000
the sample. Both analyses show a difference of 4.49% of ash on
(CHNO-S) analyzer to nd out the ultimate composition of the
average.
sample. The ultimate analysis provides the overall percentage of
The higher heating value of the coal is compared with a corre-
carbon, hydrogen, nitrogen, oxygen and sulfur present in the sam-
lation presented in the literature [30]. This correlation is based
ple. This analysis is divided mainly into two parts. In the rst part
on fty proximate analysis and heating value of different samples
of coal. This relation is also useful to estimate the reliability of the
Table 1 proximate analysis conducted in this study.
HHV of coal sample.  
MJ
HHV 0:03Ash  0:11Moisture 0:33Volatiles
Sample ID Weight (g) HHV (MJ/kg) kg
1 3.40 30.22 0:35Fixed carbon 1
2 1.78 30.82
3 1.71 30.41 The values of ash, moisture, volatiles and xed carbon present
4 1.60 30.22
in above equation are based on weight percentage. Using the
Average HHV (MJ/kg) 30.42
weight percentage present in the value of HHV for coal is found
758 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763

Table 3
Results of ultimate analysis for RTC-coal.

Sample ID Nitrogen (wt%) Carbon (wt%) Hydrogen (wt%) Sulfur (wt%) Oxygen (wt%) Ash balance (wt%)
1 2.29 76.51 5.32 0.80 8.11 6.94
2 2.19 73.22 5.01 1.08 7.79 10.69
3 2.23 73.86 5.08 1.01 7.63 10.16
4 2.13 66.78 4.64 1.00 7.84 17.59
5 2.13 71.11 4.70 1.07 7.73 13.22
Average 2.19 72.30 4.95 0.99 7.82 11.72

to be 31.35 MJ/kg. The calculated value of HHV is in close proxim-
ity with the measured value presented in Table 1. Also the above
correction emphasizes the direct proportionality of HHV of coal
to the amount of volatiles and xed carbon present in the sample.
While, increase in the moisture content and ash present in the
sample decrease the potential of HHV. Although, the effect of ash
on HHV is much less than moisture present in the sample.
In similar fashion, another correlation is used from literature
[31] to calculate the HHV of the RTC-coal. This correlation is based
on the ultimate analysis and it also provides a sight on the reliabil-
ity of ultimate analysis.
 
MJ
HHV 0:04913 Cwt 1:1783 Hwt 0:1005 Swt
kg
 0:10340 Owt  0:0151 Nwt  0:0211 Ashwt
where Cwt, Hwt, Swt, Owt, Nwt and Ashwt represent the weight per-
centage of carbon, hydrogen, sulfur, oxygen, nitrogen and ash pres-
ent in the sample. Using the averaged data from Table 3 the value of
HHV is calculated to be 30.09 MJ/kg. This value is almost the same
for HHV that is experimentally measured in Table 1. In this way the
experimental data of all three analyses (higher heating value, prox-
imate and ultimate analysis) are veried using the correlated
expressions.
3. Experiment to modeling
To perfume the simulation using the experimental data it is
necessary to convert the proximate and ultimate analysis into an
empirical formula. The empirical formula of RTC-coal is useful to
evaluate the overall gasication stoichiometric equation. This for-
mula is based on the unit kilo mole carbon to the corresponding
kilo mole of hydrogen, oxygen, nitrogen and sulfur. Although, the
ultimate analysis is sufcient to calculate the empirical formula
but the use of proximate analysis enable to subtract the effect of
moisture present in the ultimate analysis. Initially, the results of
both proximate and ultimate analysis are converted into ash free
condition. This enables one to reduce the discrepancy caused by
the difference in the ash contents of both analyses. The results of
ash free proximate and ultimate analysis are presented in Table 4.
The result of proximate analysis shows 0.32% of moisture pres-
ent in the sample, on ash free bases. The moisture composes of
both hydrogen and oxygen atoms. Thus, by consider the weight
contributes 11.11% of weight of moisture while oxygen balances
the rest i.e. 88.88%. Therefore in 0.32% of moisture hydrogen takes
its share of 0.03% while oxygen accounts of remaining 0.28%. By
subtraction these value from the ultimate analysis provided the re-
sult on dry bases. The weight percentage of nitrogen, carbon and
sulfur remain same but the value of hydrogen and oxygen reduced
to 5.58% and 8.57% respectively. Although, the change in the
weight percent of hydrogen and oxygen is quite small, but it pro-
vides an accurate formulation of empirical formula. Now the data
of ultimate analysis is again revised to sum up 100% as shown in
Table 5. In the next step, each element present in the ultimate anal-
ysis is divided by their respective atomic weigh to get their molar
number. Finally the molar number of each element is divided by
the molar number of carbon to get the moles of each atom per
2 atom of carbon present in the sample, as shown in Table 5.
Therefore the empirical formula of RTC-coal becomes CH0.8173
O0.0785N0.0260S0.0052, on dry ash free (DAF) bases. The empirical for-
mula of RTC-also provides its unit molecular weight i.e. 14.60 kg/
kmole. Using the unit molecular weight of coal the HHV is con-
verted into kmole bases and found to be 444259.15 kJ/kmole.
4. Gasication model
The gasication model is based on Gibbs free energy minimiza-
tion approach using Lagrange multiplier method. The formulation
of the model is taken from the literature [21,32]. This method does
not require any detail of chemical reactions taking place in the sys-
tem. The selections of appropriate intermediate gasication reac-
tions using equilibrium constant approach are not required [33
35]. This method minimize the total Gibbs energy of the system
using constrain mass balance equation, allowing to consider many
species during the gasication process with ease. The total Gibbs
energy of the system is given by,
GtT;P gn1 ; n2 ; n3 ; . . . ; ni 3
where GtT;P
is the total Gibbs energy of the system and ni is referred
to each species. The problem is to nd the set of ni for which the to-
tal Gibbs energy of system is minimized. This can be achieved by
series of steps. The rst step is to dene the material balance for
each element present in the system,
P
ni aik Ak k 1; 2; . . . ; w 4
i

contribution of hydrogen and oxygen atom present in the moisture where aik is the number of atoms of the kth element present in each
the actual weight fraction of both atoms is calculated. Hydrogen molecule of the chemical species i, Ak is the total number of atomic
masses of the kth element in the system and w is the total number
Table 4
of atoms present in the system. In the next step, Lagrange multipli-
Ash free result of proximate and ultimate analysis. ers (kk) is introduced in Eq. (4) by summing over the range of k.
 
Proximate analysis wt% Ultimate analysis wt% P P
kk ni aik  Ak 0 5
Moisture 0.32 Nitrogen 2.49 k i
Volatiles 40.76 Carbon 81.90
Fixed carbon 58.92 Hydrogen 5.61 Now a new function is formed by adding Eqs. (3) and (5),
Sulfur 1.13  
Oxygen 8.86 P P
F GtT;P kk ni aik  Ak 6
Total 100.00 Total 100.00
k i
 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763 759

Table 5
Calculations based on the ultimate analysis.

Ultimate analysis Previous wt (%) New wt (%) Molar number Carbon normalization
Nitrogen 2.49 2.50 0.17 0.0260
Carbon 81.90 82.17 6.84 1.0000
Hydrogen 5.58 5.60 5.59 0.8173
Sulfur 1.13 1.13 0.03 0.0052
Oxygen 8.57 8.60 0.53 0.0785
Total 99.68 100

The above equation is similar to Eq. (3) as the second term on can be used that utilize both partial combustion heat and solar en-
the right hand side is equal to zero. The minimum value of F is oc- ergy for the syngas production.
curred when the partial derivative with respective of each specie The model is structured using the 44 species in the product
approaches to zero at specied temperature and pressure, mixture. The list of product species are taken from literature [24]
and presented in Table 6. Therefore the global reaction for both
@F @Gs P air and solar gasication can be written as,
kk aik 0; i 1; 2; . . . ; n 7
@ni @ni k
CHx Oy Nz Ss mO2 3:76N2 pH2 O Q ! Table 6 12
The rst term on the right hand side of the above equation is
where the values of x, y, z and s can be taken from last column of
known as the chemical potential (li), so the Eq. (7) can be written
Table 5, m is the kmole of air input per kmole of feedstock (RTC-
as,
coal) and it is only available of air gasication, p is the amount of
P
li kk aik 0 8 moisture present in the sample or the additional steam in system
k and Q is the solar heat provide to the system. The right hand side
The chemical potential is dene as, of the Eq. (12) consists of all the species present in Table 6.
 
fi 6. Mass balance
li Goi RT ln 9
fio
All the species are combination of ve basic elements i.e. car-
where Goi DGofi is the standard state Gibbs energy of formation, R is bon, hydrogen, oxygen, nitrogen and sulfur. Therefore, initially ve
the universal gas constant, T is the temperature and f is the fugacity constrain mass balance are written that represent each element
of the species. If all the gases considered as ideal gases at standard conservation in the system as given by Eq. (4).
pressure then fugacity ratio can be replaced by mole faction of the Carbon balance:
species,
  nc nCH nCH2 nCH3 2nC2 H2 2nC2 H4 nCo nCO2
ni nHCO nNCO nCN nHCN nHCNO nCOS nCS
li DGofi RT ln 10
ntotal
nCS2 nC;S  1 0 13
Putting the above equation in Eq. (7) gives,
Hydrogen balance:
 
ni P nCH 2nCH2 3nCH3 4nCH4 2nC2 H2 4nC2 H4 nH 2nH2
DG0fi RT ln kk aik 0; i 1; 2; . . . ; n 11
ntotal k nOH 2nH2 O 2nH2 O2 nHCO nHO2 nNH 2nNH2 3nNH3
The above equation represents n equilibrium equation refers to nHCN nHCNO nHS 2nH2 S  x  2p 0 14
each species present in the system. Consequently, for each species
present in the system an equation is taken from the Eq. (11) the Oxygen balance:
remaining equations for Langrange multiplier comes from the nO 2nO2 nCO 2nCO2 nOH nH2 O 2nH2 O2 nHCO 2nHO2
mass constraint equations. nNCO nN2 O nNO 2nNO2 nHCNO nSO 2nSO2
3nSO3 nCOS  y  2m  p 0 15
5. Model formulation
Nitrogen balance:
The model is formulated from both solar assisted and air gasi- nN 2nN2 nNCO nNH nNH2 nNH3 2nN2 O nNO nNO2
cation. In air gasication the feedstock (RTC-coal) is partially oxi- nCN nHCN nHCNO  z  7:52 m 0 16
dized to convert the remaining feedstock into the syngas (H2 and
CO). In solar assisted gasication, instead of providing heat of reac- Sulfur balance:
tion via partial combustion of feedstock, the heat from the solar en-
nS 2nS2 nSO nSO2 nSO3 nCOS nCS 2nCS2
ergy is used to raise the temperature. In solar assisted gasication
the need of air as oxidizer is omitted. Also, a hybrid formulation nHS nH2 S nS;s  s 0 17

Table 6
List of species considered in the model.

Species
C (g) CH CH2 CH3 CH4 C2H2 C2H4 C2H6 C3H8 H H2
O O2 CO CO2 OH H2O H2O2 HCO HO2 N N2
NCO NH NH2 NH3 N2O NO NO2 CN HCN HCNO S (g)
S2 (g) SO SO2 SO3 COS CS CS2 HS H2S C (s) S (s)
760 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763

Now using Eq. (11) a set of equation are written for each species Adding Eqs. (25)(27) yields,
present in the product. A formulation for few species are shown x
below, C H2 0:5y O2 ! CHx Oy
2
For methane: x
Dhf HHV  285; 830  393; 546 kJ=kmol 28
g CH4   k1 4k2 2
ln xCH4 0 18
RT RT The above formula is used to calculate the enthalpy of forma-
tion of feedstock.
For hydrogen:
g H2   2k2 8. Model summary
ln xH2 0 19
RT RT
The model is comprised of 50 unknown that include 44 product
species moles, 5 Lagrange multipliers and an adiabatic gasication
For carbon monoxide: temperature. So, in order to calculate the unknowns, 50 equations
g CO k1 k3 are required. Five equations come from the mass balance of ele-
ln xCO 0 20 ment from Eqs. (13)(17), 44 equation are included using Eq.
RT RT
(11) and demonstration of these equations are presented in Eqs.
(18)(21) and the last equation is contributed in term of energy
For solid carbon:
balance, as given by Eq. (23). The equations are simulated using
g C;s k1 Engineering Equation Solver (EES) software using initial values
lnxC;s 0 21 and lower/upper limits for the solution. The process efciency of
RT RT
the system is calculated using the cold gasication efciency
For solid sulfur: (CGE) of the product using the following formula,
g S;s k5
lnxS;s 0 22 HHV of product gases
RT RT CGE 29
HHV of coal Q
where xi is the mole fraction of each species present in the product.
The CGE is calculation at each discrete point during the para-
The solid carbon and sulfur is assumed to be converted into gaseous
metric study for oxidizer, moderator and solar-energy. Therefore,
carbon and gaseous sulfur.
CGE also allow point out the maximum process efciency by plot-
ting it at each discrete point.
7. Energy balance
9. Model validation
The energy balance between reactants and product species is
established in order to calculate the adiabatic gasication temper- The model results are compared to those obtained by work of Li
ature of the system. Using Eq. (12) an energy balance equation is et al., [24] that are present in Fig. 3. The high vale coal is used for
formulate as: validation purpose having the empirical formula of CH0.6923
o P O0.2124N0.0105S0.0013 and 21.1 MJ/kg of higher heating value. The
hfCHONS mDhO2 pDhH2 O Q ni Dhi 23
iproduct 0.3 mol of air is used per mole of coal and both air and coal to-
o
gether heated to 6001600 K temperature range. The result of
where hfCHONS is the enthalpy of formation of RTC-coal and Dh repre- the model for high vale coal is presented in Fig. 4 showing the equi-
sents the absolute enthalpy of each species present in the system. librium concentration with respect to temperature range. The
The value of absolute enthalpy is taken from NIST-JANAF thermo overall trend of the species concentration predicted by the model
chemical tables [36]. The enthalpy of formation of feedstock is cal- is similar to that presented in Fig. 3. Although the model results
culated using the method dened in literature [34]. The general for- are over predicted the CH4 and under predicted the CO; The results
mulation to calculate enthalpy of formation of feedstock is follows in the literature is presented using 115 kPa and the model present
as, in this paper use standard pressure, i.e. 1 atm, that may be one
x y reason in the variation of the results.
C H2 O2 ! CHx Oy 24
2 2

The above reaction shows a hypothetical reaction showing the

formation of feedstock. The near to realistic mechanism that con-
tribute the formation feedstock follows as,
C O2 ! CO2 Dhc 393; 546 kJ=kmol 25
x x x x
H2 O2 ! H2 ODhc 285; 830 kJ=kmol 26
2 4 2 2
The value of heat of combustion in Eq. (26) is based on the heat-
ing value of the feedstock. If the lower heating value (LHV) is used
then it is necessary to use the heat of formation of water vapor. In
the present calculations the HHV of the feedstock is used, therefore
the heat of formation of liquid water is used. The resultant reaction
attributed to HHV of feedstock is written as,
x
CO2 H2 O ! CHx Oy 1 0:25x  0:5yO2 Dhc HHV 27 Fig. 3. Variation of equilibrium gas composition with temperature for high-vale
2 coal [24].
 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763 761

100 N2 10000
HS
COS
Equlibrium molar content (%)
CO 1000
10 H2
CO 2 H 2S SO2
NH3
1 H 2O 100 NO

PPM (mole)
0.1 10
CS2
CH 4 HCN
1
0.01
0.1
0.001
0.01
0.0001
600 800 1000 1200 1400 1600 0.001
Temperature (K) 0.1 0.3 0.5 0.7 0.9 1.1
Air ratio (Kmole/Kmole of RTC-coal)
Fig. 4. Result for high value gasication for model validation at a = 0.3.
Fig. 6. Equilibrium composition of minor species for air gasication.

1 70.94%. This efciency is achieved at 1247 K with air ratio input of

0.9 Temperature (K) 0.57. At this state the yield of CO, H2 and CH4 are found to be 0.79,
2000
0.8 C(s) 0.31 and 0.00 kmoles, respectively.
CO Fig. 6 shows the results of minor species present in the mixture
CO2
0.7
Temperature (K)

1500 of product over the region of interest. It shows that CS2 and HCN
0.6 are only relatively present over small range. The maximum yield
Kmoles

0.5
0.4
H2
0.3
0.2
0.1
0
CH4
0.1 0.6 1.1
Air ratio (Kmole/Kmole of RTC-coal)
Fig. 5. Equilibrium composition of major species for air-gasication.
10. Results and discussion
Initially a parametric study is performed by varying the amount
of air. The results presented in Fig. 5 used RTC-coal and air, at stan-
dard temperature and pressure i.e. 298.15 K and 1 atm. The results
show that a maximum temperature of 2161 K is achieved with cor-
responding air input of 1.14 kmole. At this state, around 91% of car-
bon is converted into carbon dioxide and 97% of hydrogen present
in the system is converted into steam (H2O). The maximum yield of
hydrogen (H2), i.e. 0.33 kmole, is achieved at 1107 K. Similarly for
carbon monoxide (CO) maximum 0.80 kmole is produced at
1287 K.
Fig. 5 shows that as the amount of air starts to increase the solid
carbon present in the feedstock tend to convert into CO, CO2 and
methane (CH4). At 0.65 kmole of air input the temperature reaches
to 1429 K and almost all the solid carbon converted into gaseous
species. The trend of graph shows that beyond 840 K all methane
is depleted. The cold gas efciency of the system that measures
of COS and NH3 only hold for low air ratio and after that its starts
H 2O 1000 fall down with increasing air ratio. The PPM of H2S also shows a
decreasing trend with increasing air ratio. On the other hand, the
PPM of NO and SO2 are showing a growing trend with increasing
500
air ratio that because of rise in the temperature.
The next simulation is preceded for the air-steam gasication of
0 RTC-coal. In this simulation 0.95 kmoles of H2O is used per kmole
1.6 of feedstock and a parametric study is performed using varying air
input. The result of the simulation is presented in Fig. 7. Maximum
process temperature of 1936 K is achieved with air input ratio of
1.16. The value of maximum temperature is lower than that ob-
tained in the air-gasication case. At this state around 97.34% of
solid carbon and 97.39% of hydrogen present in feedstock con-
verted in the CO2 and H2O. The maximum yield of hydrogen pro-
duced is 0.69 kmole at temperature of 1002 K with air input ratio
of 0.49. The yield of hydrogen is much higher as compare to air-
gasication case and also at lower temperature. The maximum
yield of hydrogen is achieved when 49.16% of solid carbon and
30.21% of input steam is converted into CO2 and H2, respectively,
with addition to the hydrogen present in the feedstock. Similarly,
the maximum yield of CO is found to be 0.49 kmole at 1209 K with
0.63 kmole of air ratio. The value of maximum CO yield is almost
40% less compared to air gasication yield. The maximum yield
of CO is achieved when 49.90% of solid carbon present in the feed-
1.4 2500
1.2
H 2O Temperature (K) 2000
1
Temperature (K)

the maximum potential of H2 and CO lies in the temperature range

1500
Kmoles

11071287 K (0.330.80 air ratio). It is evident from the graph that 0.8
CO2
at the maximum yield of CO (i.e. 0.80 kmole) a considerable
0.6 C(s)
amount of solid carbon (Cs) and H2 present in feed stream is con- 1000
verted into CO2 and H2O. The percentage of Cs and H2 converted 0.4
into CO2 and H2O at this stage are calculated to be 17.21% and CO 500
CH4 H2
26.74% by mole percentage, respectively. Similarly, at maximum 0.2
yield of H2 (i.e. 0.33 kmole) the molar percentage of Cs and H2 con-
0 0
verted into CO2 and H2O are calculated to be 14.28% and 9.45%,
0.1 0.6 1.1 1.6
respectively. It means that a considerable amount of feedstock is
Air ratio (Kmole/Kmole of RTC-coal)
consumed by the process itself to provide the energy to the system.
The maximum cold gas efciency of the process is calculated to be Fig. 7. Equilibrium composition of major species for air-steam gasication.
762 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763

10000 10000 HS
HS H 2S COS
COS
1000 1000
H2S SO2
100 100 NH3
NH3
PPM (mole)

PPM (mole)
NO
10 10
CS2 CS2
HCN HCN
1 1

0.1 0.1

0.01 0.01 SO 2
NO

0.001 0.001
0.1 0.3 0.5 0.7 0.9 1.1 500 700 900 1100 1300 1500 1700 1900
Air ratio (Kmole/Kmole of RTC-coal)
Temperature (K)
Fig. 8. Equilibrium composition of minor species for air-steam gasication.
Fig. 10. Equilibrium composition of minor species present in the solar assisted
gasication.
stock is converted in the CO2. The maximum cold efciency of air-
steam gasication is found to be 71.64% at 1087 K with air input
ratio of 0.56. At this state the yield of CO, H2 and CH4 are found Table 7
to be 0.46, 0.66 and 0.00 kmoles respectively. Fig. 8 shows the Summary of Gibbs minimization model.

equilibrium composition of minor species for the air-steam gasi- Air Air-steam Solar
cation of RTC-coal. Although the trend of the graph is similar to the gasication gasication gasication
air-gasication process but due to inclusion of H2O the overall Maximum CGE 70.94% 71.64% 90.67%
graph is slightly shifted toward the air mole consumption (right) Temperature (K) 1247 1087 1516
due decrease in temperature. CO (kmole) 0.79 0.45 0.94
H2 (kmole) 0.31 0.66 1.3
In the proceeding simulation, an attempt is made to model the
CO2 (kmole) 0.16 0.49 0.01
steam gasication process via solar energy. To replicate the solar Feedstock consumption 16.60% 46.52% 1.32%
assisted gasication process, a set of conditions are employed. (wt%)
Firstly, solar energy is modeled by a heat source in the energy Air input (kmole) 0.57 0.56 0
H2O input (kmole) 0 0.95 0.95
equation. Secondly, no air input is incorporated as used in previous
Additional Heat input 0 0 264,070
cases, i.e. air-gasication and air-steam gasication process. The (kJ/kmole)
input to simulation is only consisting of a unit kmole of RTC-coal
and 0.95 kmole of H2O with addition to heat input in energy equa-
tion to replicate the solar energy. Fig. 10 shows the composition of minor species present in the
The results are presented in Fig. 9 and intuitively shows that as product stream. The graph shows a growing trend of HS, HCN
the heat input increase the temperature rise. Temperature increase and NO over the increase in temperature. While, COS, H2S and
allows Cs and H2O reaction to produce forming CO, CO2, CH4 and NH3 tend to decrease with temperature rise. On other hand, the
H2. The CH4 starts to convert into CO and H2 and around 1000 K CS2 starts to form around 550 K and achieved highest yield at
all of it is depleted. Similarly, after the maximum yield of CO2 900 K and then starts of decompose that nishes around 1775 K.
around 1000 K it starts to reduce into CO and H2. Around 1600 K
all the CO2 decompose into CO by following bouduard reaction. Fi-
11. Conclusion
nally all the solid carbon and steam reacted together and converted
into CO and H2. The maximum cold gasication efciency of
Three different routs of gasication are compared for the zero
90.67% is achieved during the process. This maximum efciency
dimensional analysis using minimization of Gibbs energy through
is achieved with solar heat input of 264,070 kJ/kmole of coal the
Lagrange multiplier method. RTC-coal is used as a baseline feed-
produce temperature of 1516 K. At this state the yield of CO and
stock to perform the analysis. The feedstock properties are experi-
H2 are 0.95 kmole and 1.31 kmole, respectively.
mentally determined using Bomb calorimeter, simultaneous DSC/
1.4 3.5E+05 TGA Q600 thermal analyzer and Flash 2000 (CHNO-S) analyzer for
higher heating value, proximate analysis and ultimate analysis
H2
1.2 3.0E+05 respectively. The experimental results are veried using the empir-
Heat input
ical relations for the higher heating value. In the next step, an empir-
Heat input (KJ/Kmole)

1 2.5E+05 ical formula for RTC-coal is developed using the result of proximate
H 2O CO
and ultimate analysis that is used in the simulation. A gasication
0.8 2.0E+05 model is formulated using the 44 species in the product stream.
Kmole

C(s) Combined with elemental conservation and energy balance the 44

0.6 1.5E+05 species model is then validated by the result of published data. After
validation of model, three different scenario of gasication are sim-
0.4 CH 4 1.0E+05 ulated that are based on air gasication, air-steam gasication and
CO 2 solar-steam gasication. In the end the cold gasication efciency
0.2 5.0E+04 of all gasication process are calculated that shown the maximum
process efciency of 70.94%, 71.64% and 90.67% for air, air-steam
0 0.0E+00
500 1000 1500 2000 and solar-steam gasication, respectively. The cold gasication ef-
ciency clearly shows the high potential of solar-steam gasication
Temperature (K)
over other two processes. The result of the Gibbs energy minimiza-
Fig. 9. Equilibrium composition of major species for solar assisted gasication. tion model is summarized in Table 7.
 S. Shabbar, I. Janajreh / Energy Conversion and Management 65 (2013) 755763
Acknowledgments
The nancial support of Masdar Institute allowing conducting
this work is highly acknowledged. Our thanks also extended to
the rest of the members of the Waste to Energy Lab at Masdar
Institute.
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