Fuel 236 (2019) 501–515

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Full Length Article

Detailed parametric investigation of dry gasification oxy-combustion power T

cycle using ASPEN Plus simulations
⁎
Ashitosh Darekar Dattatray, Vidyasagar Shilapuram
Chemical Engineering Department, National Institute of Technology, Warangal, Telangana State 506 004, India

A R T I C LE I N FO A B S T R A C T

Keywords: Dry gasification oxy-combustion (DGOC) power cycle is a novel, zero-emission power production scheme. This
DGOC work presents the detailed parametric study of various process performance variables namely gasifier tem-
CO2 sequestration perature, gasifier pressure, fraction of recycle gas from combustor, molar gasification agents ratio, different type
Power cycle of sorbents on the process performance measured in term of product gas quality and quantity, total heat gen-
Sulfur removal
erated for power production and sulfur removal efficiency using the ASPEN Plus simulator. Various sorbents
ASPEN Plus
namely CaCO3, Fe2O3, MnO, CuO are considered for this study. Results shows that different sorbents posses
Coal
different behavior. Temperature has significant affect on the DGOC performance. Fe2O3 is not a suggested
sorbent in DGOC. CuO appears to be good sorbent in terms of temperature in the gasifier required or energy
input required to the gasifier, and sulfur removal efficiency. MnO appears to be good sorbent in terms of syngas
quality and total heat generated which was used to produce power by DGOC cycle.

1. Introduction power generation by turbine. Conventionally hydrogen sulfide is re-

Conventional thermal power plants emits huge amount of carbon
dioxide (CO2) into the atmosphere. CO2 emissions have significant af-
fect on global warming and climate change. Carbon capture and storage
(CCS) is one of the most efficient and practical way of minimizing the
carbon credits into the environment [1]. Various attempts to capture
CO2 in power generation plants were obstructed by thermal efficiency
penalty due to huge energy consumption with conventional processes
such as amine based carbon capture.
Renganathan et al. [2] suggested use of CO2 to gasify coal to syngas
can play a major role in CO2 recycle. This result in not only recycle of
CO2 but also it is used as a gasification agent for power production as
well as reduction of emission of CO2 into atmosphere. Pettinau et al. [3]
carried out techno-economical comparison between different technol-
ogies for CO2 free power generation. Results suggested that oxy-com-
bustion is the promising technology and it is regarded as a possible CCS
option for power generation.
Power production by integrated gasification combined cycle (IGCC)
consists of gasifier to produce syngas followed by a gas turbine engine
for power production. In gasifier of IGCC, if the sulfur is present in the
fuel it is predominantly converted to hydrogen sulfide. This would
cause severe corrosion of downstream equipments hence the sulfur
compounds have to be removed prior to utilization of syngas used for
moved by wet absorption or zinc sorption method but the disadvantage
with these methods is that hot gas has to be cooled down to ambient
temperature for sulfur removal [4].
Rodriguez et al. [5] noticed that syngas produced from gasification
normally contains various contaminating gases viz. SO2, HCl, etc. with
the most predominant contaminant being H2S. This syngas stream is
suggested for purification before it goes to gas turbine (in case of
combined cycle plants). Use of wet processes for purification demands a
reduction in the temperature for treatment of syngas. This give rise to
series of thermodynamic losses. So for better thermal efficiency hot gas
desulfurization (HDP) techniques has obtained increased attention
[4,6]. Meng et al. [6] concluded that hot gas desulfurization (HDP) can
improve the thermal efficiency and lower the capital costs of the IGCC
system due to the elimination of flue gas cooling and associated heat
exchanger equipment. In this method various sorbents are extensively
used to capture sulfur containing compounds in situ or downstream of
gasifier. Metal oxide like CuO, MnO and Fe2O3 are chosen as sorbents.
Results showed that at the temperature over 900 °C calcium based
sorbent exhibit a better potential than other metal oxide. However,
desulfurization capacity is strongly dependent on appropriate tem-
perature range and gas composition especially the H2O and CO2 con-
tent.
Allen et al. [7] also suggested use of calcium oxide to remove H2S.

⁎
Corresponding author.
E-mail address: vidyasagars@nitw.ac.in (V. Shilapuram).

https://doi.org/10.1016/j.fuel.2018.09.023
Received 8 December 2017; Received in revised form 2 September 2018; Accepted 5 September 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
A.D. Dattatray, V. Shilapuram
Nomenclature
HHV higher heating value of coal in kW
PG gasifier pressure, MPa
Q1 sensible heat by cooling fluegas up to 94 °C (heat ex-
changer H3 of Fig. 1), kW
Q2 heat from CaS combustion (oxidiser of Fig. 1), kW
Q3 heat from gasifier, kW
Q4 sensible heat from Sequestration stream (heat exchanger
H6 of Fig. 1), kW
Q5 sensible heat from flue gas cooling (heat exchanger H4 of
Abbasian et al. [8] carried out to investigate the oxidation of byproduct
CaS (unstable solid waste) to stable calcium sulfate from coal gasifier
that utilizes limestone as the sorbent for sulfur capture. Calcium sulfide
is unstable and has the tendency to decompose when it comes in contact
with moisture in the air by releasing the hydrogen sulfide into the at-
mosphere. Results confirmed that the feasibility of CaS oxidation to
stable CaSO4 is suitable for disposal. Performance of Mn and Cu mixed
oxides as a regenerable sorbent for hot coal gas desulfurization is stu-
died by Gracia et al. [9]. Sasaokaet al. [10] examined six kinds of he-
matite at different compositions as H2S sorbent at high temperature.
The hematite ores were confirmed to be effective sorbent of H2S in H2O
poor/H2 rich gas.
Recent study showed that DGOC is most promising with improved
net plant efficiency with simultaneous carbon capture and in situ sulfur
removal by sorbents [11]. Walker et al. [11] proved through their si-
mulation studies that DGOC is beneficial over integrated gasification
combined cycle (IGCC), and atmospheric oxy-combustion carbon cap-
ture and sequestration (CCS). However, this work did not cover wide
range of temperature, pressure, and other process parameters. Results
were only belongs to a temperature of 1093 °C, pressure of 6 MPa, Ca/S
ratio of 2 and for a flue gas composition of 61% CO2 and 32% H2O, and
CaCO3 as a sorbent for sulfur removal. Results also concluded that H2/
CO ratio in the syngas produced can be adjusted by selecting the con-
centration of CO2 fed to a gasifier, resulting in operational and eco-
nomic advantages.
To the best of authors knowledge only one study available on DGOC
[11]. Various sorbent such as CaCO3, CuO, Fe2O3, and MnO have been
extensively studied to remove H2S in a gasifier but not its effect on a
power cycle [5–6,10,12]. Hence, in the present study, wide range of
gasifier temperature, gasifier pressure, fraction of recycle of product of
combustor, mole ratio of H2O/CO2 in the recycle, different sorbents
(viz., CaCO3, MnO, Fe2O3, and CuO) and different sorbent/S ratio on
the DGOC performance in terms of sulfur removal efficiency, product
gas composition from gasifier and combustor, number of moles of
syngas formed as well as heat produced in individual stream and total
heat generated in the DGOC cycle is studied. The reason for recycle of
CO2 alone or in combination with steam is described as follows. Since
DGOC is a two step process i.e., partial oxidation followed by complete
combustion, hence, recycle of CO2 alone or in combination with steam
into gasifier favours syngas formation via water gas shift reaction (a
wide range of H2/CO ratio in syngas can be achieved to suit different
application). Also recycle of CO2 into the combustor act as a tempera-
ture moderator. Use of CO2 recycle results in active chars producing
more volatiles resulting efficient gasification. Use of CO2 instead of
nitrogen along with O2 for gasification results in flue gas with high
percentage of CO2 suitable for direct recovery and recycle of CO2 [2].
2. Simulation methodology
DGOC comprised of sulfur capture from feed stock by a sorbent as
well as partial oxidation in the gasifier followed by oxy-combustion in
the combustor, power production for heat released and CO2
502
Fuel 236 (2019) 501–515
Fig. 1), kW
Q6 sensible heat by cooling fluegas up to 312 °C (heat ex-
changer H1 of Fig. 1), kW
TG gasifier temperature, °C
Total Q total heat used for power generation, kW
SF split fraction, (–)
Xs Sulfur removal efficiency in %
Symbols
ΔHr standard heat of reaction KJ/kmol
sequestration. In this process, portion of product gas out from the
combustor is recycled to moderate the flame temperature in the com-
bustor and also acts as a gasifying agent in the gasifier. Sulfur present in
the feed stock is reacted with sorbent and separated as a solid product
from the gasifier. This solid product is undergoing for oxidation with
the energy released from the exothermic oxidation step is reintegrated
to heat the boiler feed water for power production.
In other words, DGOC comprised of various units to carry out the
following processes: partial oxidation of feed stock, pre-combustion
sulfur capture, oxy combustion of partially oxidised feed stock, recycle
of combusted products acts as gasifying agent, net power production
from oxidation of pre-combusted sulfur captured by sorbent as well as
the energy production from the combustor and CO2 sequestration [11].
2.1. Simulation input parameters, description and calculation methods
Simulations are carried out using Aspen Plus (Version 8.4) process
simulators. Flow sheet for simulations involved assigning the MIXCINC
stream class to the simulation. This allowed fluid and aqueous streams
(MIXED), conventional solid streams (CISOLID), and non-conventional
solid streams (NC). The PENG ROBINSON equation of state is used.
2.2. Component definition and inputs
Solid coal was modelled using user defined, non-conventional solid
based on proximate, ultimate and sulfur analysis. Furthermore, the
enthalpy and density of coal were approximated using coal properties.
The methods used by ASPEN Plus for these calculations are HCOALGEN
and DCOALIGT respectively.
Fluid stream were modelled using conventional component for
which thermophysical data is already available in ASPEN Plus.
Therefore no data input were required for these components. The
components added for simulation study include argon (Ar), hydrogen
(H2), oxygen (O2), nitrogen (N2), sulfur (S), sulfur dioxide (SO2)
chlorine (Cl2), hydrogen chloride (HCl), carbon monoxide (CO), carbon
dioxide (CO2), water (H2O), and hydrogen sulfide (H2S). Additionally,
solid components were modelled using conventional solids which also
have necessary thermophysical data in ASPEN Plus databank. The
components added include calcium carbonate (CaCO3), calcium oxide
(CaO), calcium sulfide (CaS), calcium sulfate (CaSO4), copper monoxide
(CuO), dicopper sulfide (Cu2S), copper (Cu), manganese oxide (MnO),
manganese monosulfide (MnS), manganese (Mn), hematite (Fe2O3)
iron-monosulfide (FeS), magnetite (Fe3O4), ferrous-oxide (FeO) and
carbon (C). Carbon content in the coal is assumed as graphite. MnSO4
formation is neglected because it is not produced within the operating
range of gasifier.
2.3. Flowsheet description
The DGOC flowsheet is shown in Fig. 1. Stream 1 contains solid coal
feed. This nonconventional component has to be split into its con-
stituent elements before giving it as input to a reactor. Hence two
A.D. Dattatray, V. Shilapuram
Fig. 1. Aspen Plus flowsheet used for DGOC simulations.
reactors, viz, the RYIELD [DECOMP] and RGIBBS [GASIFIER] reactors
are used to simulate the gasification process. RYIELD[DECOMP] reactor
is used to split the coal into its constituent elements. The constituent
elements stream O1 along with sorbent stream 2 and gasifying agents
stream O12 were fed to gasifier. Gasifying agents consist of mixture of
H2O, CO2 and O2. RGIBBS reactor was used to perform multiphase-
reaction equilibrium calculations based on the Gibbs free energy
minimization approach. RGIBBS model do not consider kinetics and
hydrodynamics of a gasification into account.
The output from gasifier consists of syngas and solids. The solids
stream coming out of gasifier contains unconverted carbon, un-
converted sorbent, CaS and ash. Solids and syngas are separated by
using cyclone separator [CY1]. SSplit model from model palette has
been used to represent the cyclone separator. This divides feed into
solid stream [8] and syngas stream [O3] based on splits specified for
each sub stream. Further one more RGIBBS[OXIDISER] reactor is used
to carry out oxidation reaction between solids stream 8 (CaS) coming
out from gasifier with air stream 10A.
The syngas [O3] coming out from cyclone separator [CY1] is then
mixed with high pressure oxygen stream 4 and recycle flue gas stream
6B from oxy-combustor is than send to the combustor [COMB].
Combustor is considered as a stoichiometric reactor where complete
combustion is carried out. Input specifications for combustor is the
reaction stoichiometry and extent of reaction. In this simulations
complete combustion is assumed.
The flue gases stream 5 at high temperature coming out from
combustor [COMB] is cooled in a cooler [H1] in order to extract heat
from flue gases. Temperature or heat duty is an input specification for a
cooler. The temperature 312 °C was set as an input to cooler [H1] which
means that flue gases were cooled to a temperature of 312 °C. The heat
extracted from flue gas is used for steam generation. Stream O5 con-
tains all the flue gas stream from the combustor. Part of this product
stream from combustor is fed to gasifier, recycled back to combustor
and remaining for CO2 sequestration with different ratios. This can be
performed by adopting the splitter from model pallette. In splitter, all
the inlet and outlets have the same conditions and properties. S1 and S2
are the material splitters while HS1 is the heat stream splitter. From
splitter S1 two material streams were recycled namely 6A and 6B which
were fed to gasifier and combustor respectively. The non-recycled flue
gas stream [O10] from splitter S1 which mainly consists of H2O and
CO2 is sent to sequestration.
In flowsheet, mixer blocks (M1, M2, and H2OMIX) were used to
combine material streams into one outlet stream whereas mixer bock
i.e., HEATMIX is used to combine all heat streams coming from GASI-
FIER (i.e.Q3 stream), OXIDESER (i.e. Q2 stream), heat stream splitter
503
Fuel 236 (2019) 501–515
[HS1], and from various coolers [H1, H4, and H6] to extract heat into
one heat outlet stream. M1, M2, H2OMIX are mixture used for material
stream while HEATMIX is used for mixing heat streams. FSplit option
available in model pallette is used to divide material streams (or heat
streams) into one or more stream based on split fraction specified.
Recycled flue gas is used as a moderator to maintain the combustor
temperature between 1950 °C and 2000 °C. Different recycle fractions
with different molar ratio of gasifying agents (CO2 to H2O) within re-
cycled fraction has been considered for simulations. The un-recycled
flue gas [O10] is send for sequestration. Before sending to sequestration
step flue gas is send to oxygen preheater [HS1] where sensible heat
from flue gas was used to raise the temperature of high pressure oxygen
feed [O2IN] of the gasifier and remaining heat [Q1] is used to boiler
feed water through HEATMIX. Design specs option available in Aspen
Plus was used to perform this work. The oxygen is produced from
ambient air using air separation unit and it is fed as stream 3 to the
gasifier system at 94.4% purity.
2.3.1. CO2 sequestration step
In CO2 sequestration step, to get CO2 rich stream H2O must be re-
moved. This is achieved by lowering the temperature of non-recycled
flue gas so that water will get condensed. Cooler is used to cool the flue
gas based on temperature specified. To model this cooling process, heat
exchanger and flash combinations from model pallette was used. Two
stage cooling process has been adopted. First stage cooling consists of
H3 and FLASH1 to bring the product gas to 94 °C while second stage
cooling consists of H4 and FLASH2 to further bringdown the product
gas to 40OC. The first cooler operates at 94 °C and 5.62 MPa this allows
for the condensation/recovery of 95.65% of water in flue gas. The heat
recovered in condensation step is significant and used to heat boiler
feed water. A second cooler is operated at 40 °C. Small amount of water
is recovered after passing flue gas through this second condenser. This
water is mixed with water from first condenser condensate for total
process water recovery of 99.53%. The remaining water must be re-
moved using desiccant. Finally the dry CO2 stream is compressed to
15.3 MPa and can be transported for sequestration.
Reason for choosing the combination of Heat exchanger with FLASH
is to remove the condensed water from the FLASH. In ASPEN Plus
condenser having only one outlet so the condenser block is used to
lower the temperature of flue gases but does not perform to separate the
water, hence, FLASH unit is added to separate water and gases. This is
equivalent to condenser separating the water from flue gas in real time.
FLASH1and2 performs rigorous vapor-liquid phase equilibrium calcu-
lations. To achieve this, two out of the four given specifications viz.,
flash temperature, flash pressure, heat duty, and the fraction of the feed
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

vaporized needs to be provided. FLASH2 produces one vapor outlet Table 2

stream, and one liquid outlet stream. Two liquid streams 11A and 11B Total H2O Effluent Stream.
coming out from FLASH1 and FLASH2 respectively are mixed in a mixer Total H2O effluent stream
H2OMIX. The liquid stream 11C is rich with water (99.86 mol %) while
the vapor stream 9 coming from flash is rich with CO2(89.9%) is Flash temperature (°C) 94/40
Total H2O removal (% recovery) 99.53
compressed, ready for sequestration.
Total effluent mass (%) 16.33
Composition (mole %)
H2O 99.86
2.3.2. Steam Rankine cycle for power production
CO2 0.1268
Steam Rankine Cycle is used to calculate power output. The simu- SO2 0.000000098
lations are set up assuming isentropic steps for the rotating equipment. N2 0.000129
The blocks from Model Palette used are 2 heaters, a turbine as pressure O2 0.001579
changer (ComprICON3 from model palette)), and pump (hydraulic HCl 0.001766

turbine ICON1 from model palette). The temperature, flow rate and
vapor fraction are input specification for COND-IN stream. Saturated
Table 3
liquid with zero vapor fraction at temperature of 20 °C are specified.
Wet CO2 Sequestration Stream.
The flow rate of water is manipulated by Design Specs option available
in ASPEN Plus by targeting heat out from heater (H2) as zero. Water Wet CO2 sequestration stream
from the condenser [C1] at low pressure is pumped into the boiler
Sequestration temperature (°C) 21.1
(heater, H2) at high pressure using pump [CND-PUMP]. Pump and Sequestration pressure (MPa) 15.3
driver efficiencies are specified as 1 to define an ideal pump. Water is Total effluent mass (%) 83.67
converted into steam at constant pressure by the addition of heat in the Composition (mole %)
heater [H2]. The temperature and pressure drop specified for heater H2 O 0.2165
CO2 89.9
[H2] were 599 °C and zero respectively. The steam produced was then SO2 2.17669E−06
expanded in turbine [STM-TUR] to get work output. Discharge pressure N2 2.28
was specified at 0.01 MPa. W1 stream shows work output from steam O2 2.69
turbine. Property method STEAM‐TA is used instead of PENG-ROB for Ar 4.64
turbine for better accuracy. The low pressure steam coming out from
turbine is converted into water in the condenser [COND1] by rejecting
this heat released[Q2] can be used to heat boiler feed water to calculate
heat at constant pressure. In condenser block vapor fraction is specified
net power produced.
as zero (i.e. outlet is saturated liquid). CALCULATOR block option is to
Table 1 shows the range of different parameters studied for DGOC.
feed forward the condenser’s pressure to the turbine’s discharge pres-
Ultimate analysis of the coal used in the present study is same as that of
sure.
Walkaer et al. [11]. Table 2 shows the water effluent stream composi-
tion from the flash column which is actually representing the condenser
2.3.3. Assumptions, range of parameters studied, and calculation in DGOC. Table 3 shows the wet CO2 sequestrated stream composition
methodology employed from the compressor. Stream compositions obtained in our study pre-
The simulations were carried out using a coal flow rate of sented in Table 2 and 3 are almost same as that of Walker et al., [11].
249235 kg/h. The sorbent to sulfur input molar feed rate was set to 2. H2S is the sulfur related compound formed during gasification. One
These conditions chosen were similar to as that of Walker et al. [11]. mole of sulfur forms 1 mol of H2S. Sulfur removal efficiency is defined
The gasifier is operated under isothermal conditions for various tem- as follows
peratures viz., 1093 °C, 982 °C and 871 °C. Simulations are conducted
[Sulfur into the gasifier from coal−Hydrogen sulfide out from gasifier]
for various fractions of product gas from the combustor with different Xs = × 100
Sulfur into the gasifier from coal
CO2 to H2O mole ratio in the product gas as the recycled gasifying agent
to the gasifier. (1)
Sulfur present in the coal is reacted in the gasifier and appears as the The higher heating value (HHV) of non-conventional fuel was cal-
H2S in the predominant form. This hydrogen sulfide readily reacts with culated by using the correlation proposed by Channiwala and Parikh
sorbent (example: calcium oxide) under gasification conditions to give [13] as given below
CaS and H2O. CaS is a solid coming out of gasifier along with un-
converted carbons, sorbent and ash. Solids and syngas are separated by kj
HHV = 349.1C + 1178.3H + 100.5S−103.4O−15. N −21.1A ⎜⎛ ⎞⎟
using cyclone separator. CaS is in unstable form which can be separated
⎝ kg ⎠ (2)
from other solids and can be oxidised to form stable product i.e., CaSO4.
The oxidation reaction of calcium sulfide is an exothermic reaction and where C, H, S, O, N and A are the mass percent of carbon, hydrogen,

Table 1
Range of different paremeters studied for DGOC using Aspen Plus.
S.No Sorbent Gasifier Gasifier Split fraction Sorbent/S CO2/H2O mole
Temperature Pressure ratio
(TG, °C) (PG, MPa)

1 CaCO3 871, 898, 925, 982, 3,4,5,6 0.1,0.11,0.12,0.13,0.14,0.2,0.21,0.22,0.23,0.24,0.25, 0.5,0.6,0.7, 0.66,1,1.33, 1.67,
1035, 1093 0.26,0.27,0.28,0.29,0.3 0.8,0.9,1,1.5,2,2.5,3 2
2 CuO 871, 982, 1093 6 0.1,0.11,0.12,0.13,0.14,0.2,0.21,0.22,0.23,0.24,0.25, 0.2, 0.8, 1, 0.66,1,1.33, 1.67,
0.26,0.27,0.28,0.29,0.3 1.2,1.4,1.6,1.8,2,2.5,3 2
3 Fe2O3 871, 982, 1093 6 0.1,0.11,0.12,0.13,0.14,0.2,0.21,0.22,0.23,0.24,0.25, 0.2,0.3,0.4,0.5,0.6,0.7 0.66,1,1.33, 1.67,
0.26,0.27,0.28,0.29,0.3 2
4 MnO 871, 982, 1093 6 0.1,0.11,0.12,0.13,0.14,0.2,0.21,0.22,0.23,0.24,0.25, 0.2,0.4,0.6 0.66,1,1.33, 1.67,
0.26,0.27,0.28,0.29,0.3 2

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A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

sulfur, oxygen, nitrogen, and ash respectively. Above correlation is
valid for the range 0 < H/C < 1.81 and 0 < O/C < 0.83. Above
correlation can be valid since the coal used in our study are having H/C
and O/C values of 0.108, and 0.07 respectively.
Thermal efficiency of power production is defined as amount of net
work produced divided by thermal input rate [higher heating value
(HHV)]. The net work produced is calculated by subtracting the total
auxiliaries from net turbine work.
Net power produced (kW)
nt =
Thermal input rate [HHV] (kW)
CO2 and H2O are the gasifying agents which are major components
in the product gas from the combustion unit of the DGOC. As mentioned
above, portion of the combusted product is used for power production
and simultaneous CO2 capture, and the remaining product gas is re-
cycled back to the gasifier as a gasification agent. Hence, split fraction
or fraction of recycle flue gas to the gasifier is defined as the mole ratio
of recycled product gas to the total moles of product gas from the
combustion unit.
3. Results and discussion
Objective is complete removal of sulfur to meet 100% sulfur re-
moval efficiency. From the definition shown in Eq. (1) expecting no or
least amount of H2S from the gasifier outlet or complete conversion of
H2S. All the simulation results showed that no SO3, very less quantity of
SO2, and significant quantity of H2S formation is noticed. Hence, in the
gasifier, it is assumed that sulfur present in the coal is converted to H2S.
Fig. 2 shows the effect of temperature on the decomposition of
CaCO3 to give CaO, and CO2 as per the reaction mentioned below.
kj
CaCO3 ↔ CaO + CO2 ΔHr = 1, 78, 000
kmol
Reaction is highly endothermic in nature. Temperature has sig-
nificant affect on decomposition. Figure shows that decomposition re-
action starts around 830 °C and complete decomposition is noticed at
about 1060 °C, which is the calcination temperature of CaCO3. Sorbent
entering is in CaCO3 form but CaO is the actual sorbent for sulfur re-
moval according to Eq. (5). This means CaCO3 has to be decomposed
first to CaO and CO2 according to Eq. (4) before reaction with sulfur.
H2S removal with CaO sorbent involves the following exothermic re-
action.
kj
H2 S + CaO ↔ H2 O + CaS ΔHr = −1, 02, 900
kmol (5)
Accounting Eqs. (4) and (5) net overall reaction, as shown below, is
endothermic in nature.
(3)
kj
H2 S + CaCO3 ↔ H2 O + CaS + CO2 ΔHr = 75, 100
kmol (6)
Results showed that sulfur removal efficiency is maximum of 85.3%
at 1050 °C and it is decreasing beyond this. The reason being, above this
temperature, complete conversion of CaCO3 is possible leading to sharp
rise in partial pressure of CO2 and steam w.r.to reaction shown in Eq.
(6) would favour the backward reaction causing increase in H2S in the
gasifier outlet.
Fig. 3 shows the sulfur removal efficiency as function of Ca-
CO3(sorbent) to sulfur input molar feed ratio at various temperatures
and pressures. Results show that, at a particular gasification tempera-
ture, sulfur removal is increasing with increase in sorbent to S ratio i.e.,
with molar feed rate of CaCO3. This happens up to a particular CaCO3 to
sulfur molar ratio due to thermodynamic limitation. With further in-
crease in this ratio sulfur removal efficiency becomes plateau. Reason
can be explained as presented below. X-axis represents the molar ratio
of sorbent (CaCO3) to sulfur in the coal. Entire simulations were con-
ducted with of 249235 kg/h of coal for the chosen coal composition
same as that of Walker et al.[11]. This implies that the sulfur quantity
in the coal is fixed. Therefore, effect of CaCO3/S ratio is studied by
varying the CaCO3 fed to the gasifier. At a given gasifier conditions i.e.,
(4)
temperature and pressure there is definite quantity of H2S is formed. By
varying CaCO3/S ratio means CaCO3 input flow rate the concentration
of CaCO3 is increasing resulting in more amount of CaO is formed
through reaction (4). Hence, good quantity of sorbent CaO is available
for H2S removal by reaction (5). This is the reason for increase in sulfur

45000 90

40000 80

35000 70
CaCO3 in ,CaCO3 out from Gasifier, kg/hr

30000 60
Sulfur removal efficiency %

25000 50

20000 40

15000 30

CaCO3 in
10000 20
CaCO3 out

5000 10
Xs

0 0
750 800 850 900 950 1000 1050 1100 1150 1200
Gasifier temperature °C

Fig. 2. Effect of gasifier temperature on CaCO3 decomposition and sulfur removal efficiency (PG = 6 MPa, CaCO3/S = 2, SF = 0.1937).

505
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

100

90

80

70
Sulfur removal efficiency %

60 Pressure (Mpa) Temperature

3 1093°C
50 4 1093°C
5 1093°C
6 1093°C
40
3 982°C
4 982°C
30
5 982°C
6 982°C
20 3 871°C
4 871°C
10 5 871°C
6 871°C
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
[CaCO3 /S] Input molar feed ratio

Fig. 3. Effect of CaCO3/S molar flow rate on sulfur removal at various temperatures and pressures (SF = 0.1937).

removal efficiency with increase in CaCO3/S ratio. In addition, the re- similar to Walker et al. [11]. The following reactions from Eqs. (7)–(13)
action is thermodynamically limited in the temperature and pressure would be happening in the gasifier in addition to the reactions men-
range of gasifier conditions chosen in the present study since modeling tioned from Eqs. (4)–(6).
has been adopted RGIBBS which only performs chemical equilibrium. Combustion Reactions
As a result observed behavior (i.e. plateau of removal beyond a certain
kj
ratio). It is important to note that this behavior is the result of the way Cs + 0.5O2 ↔ CO ΔHr = −110, 500
kmol (7)
the gibbs model is treating the activity of solid CaO or CaCO3 in the
reactor (i.e., activity = 1). Therefore, the plateau point (and therefore kj
Cs + O2 ↔ CO2 ΔHr = −393, 500
the equilibrium constant, Kp of the reaction) is related only to the gas kmol (8)
phase components. Addition of more solid sorbent has no effect on the
Boudouard reaction (BD)
equilibrium position. Since overall reaction is endothermic, reaction
stoichiometry reveals that higher temperature and lower pressure re- kj
Cs + CO2 ↔ 2CO ΔHr = 172, 459
sults in higher sulfur removal efficiency. kmol (9)
Upon comparison of sulfur removal efficiency at various gasifier
Water Gas Shift (WGS)
conditions it is observed that temperature above calcination tempera-
ture pressure has no effect on sulfur removal efficiency as long as sor- kj
CO + H2 O ↔ CO2 + H2 ΔHr = −41, 166
bent to sulfur are in and above stoichiometric proportion. This can be kmol (10)
explained by Eq. (5). From this reaction, it can be noticed that number Primary Water Gas (PWG)
of gas phase moles on the reactant and product side are same and the
solids activity is 1. Hence, according to Le Chatelier principle, pressure kj
Cs + H2 O ↔ CO + H2 ΔHr = 131, 293
has no affect. Whereas below calcination temperature, the gasifier kmol (11)
conditions (temperature and pressure) affects the equilibrium condi- Methane Formation (MF)
tions to favour either forward or backward reaction which decides the
kj
extent of H2S converted or disappeared. Previous study shows that Cs + 2H2 ↔ CH4 ΔHr = −74, 520
kmol (12)
DGOC is usually operated at about 6 MPa, hence, all the rest of the
simulations are carried with this pressure in the present study for Methane reforming (MR)
parametric study [11].
kj
Sulfur removal efficiency as a function of molar ratio of gasifying CH4 + H2 O ↔ CO + 3H2 ΔHr = 205, 813
kmol (13)
agent to carbon in the fuel at various operating temperatures in a ga-
sifier for steam alone as the gasifying agent and steam with CO2 as the Most of the reactions are equilibrium controlled with some of the
gasifying agent has been studied. The split fractions are calculated reaction are endothermic and others exothermic with different extent of
using sensitivity analysis option in Aspen Plus. For both the gasifying endo- or exo-thermicity. Hence, affect of inlet concentration of feed and
agents, steam alone or steam with CO2, sulfur removal efficiency de- gasifying agent, and temperature results in different extent according to
creases with increase in gasification agent to C molar feed ratio. This the nature of each reaction and its sensitivity towards concentration
effect is significant at low temperatures while variation is negligible at and temperature. From the results noticed, higher temperatures and
higher gasification temperatures. These profiles and observations are lower gasification agent to C molar feed ratio is suggested for more

506
A.D. Dattatray, V. Shilapuram
sulfur removal efficiency. Nature of profiles noticed are similar with
gasification agent as steam alone or steam and CO2 together. Maximum
sulfur removal efficiency in either cases observed is about 85%.
In DGOC, gasifier is followed by combustor, the product gas of the
combustor may contain small amount of SO2, H2S, N2, etc. in addition
to CO2 and H2O. Steam and CO2 could be used as a gasifying agent to
the gasifier unit either as individual gasifying agent or CO2 with steam
together. Therefore, portion of gas fraction from the product gas of
combustor is recycled to the gasifier as a gasification agent. This split
fraction and also molar ratio of CO2 and steam in the recycle stream
would have effect on the sulfur removal efficiency as well as on the net
heat released.
Split fraction or fraction of recycle flue gas from the outlet of the
combustor to the gasifier is defined as the mole ratio of recycled pro-
duct gas to the total moles of product gas out from the combustion unit.
Hence, first parametric study considers the fraction of recycle gas to the
gasifier (or split fraction) and second as the H2O/CO2 mole ratio within
this recycle gas. Throughout the manuscript, split fraction and fraction
of recycled gas to the gasifier mean one and the same. They were used
interchangeably.
Fig. 4 shows that as the fraction of recycle gas increases the sulfur
removal efficiency decreases continuously. From all the above results,
from Figs. 2 and 3, it can be noticed that in most of the cases 100%
sulfur removal efficiency is not obtained. As explained for Fig. 2 there
might be a maximum sulfur removal efficiency at a definite gasifier
temperature. For the CaCO3/S ratio of 0.5, maximum sulfur removal
efficiency of 37.32% was noticed and it was decreased with increase in
fraction of recycle gas from 0.1 to 0.25 at various sorbent to sulfur ratio.
Reason is as the fraction of recycle gas is increased number of moles of
either steam or CO2 or both would be increasing resulting in backward
reaction showed in Eq. (6) is favoured over the forward reaction.
Hence, H2S moles out is increasing causing decrease in sulfur removal
efficiency. On the other hand, sulfur removal efficiency increases with
increase in CaCO3/S ratio due to increase in concentration of CaCO3
since availability of sorbent (CaO) is increasing. The 90% maximum
removal efficiency was noticed at CaCO3/S of 1 beyond which there is
110
CaCO3/S
100
90
80
Sulfur removal efficiency %
70
60
50
40
30
20
0.1
Fig. 4. Sulfur removal efficiency versus the fraction of recycle gas to gasifier for various CaCO3/S molar input feed ratio (TG = 1093 °C, PG = 6 Mpa).
Fuel 236 (2019) 501–515
no change with increase in CaCO3/S ratio up to 2.5. As per the reaction
stoichiometry, Eq. (6), above CaCO3/S of 1 amount of sorbent present is
excess in quantity over stoichiometric requirement for H2S removal,
hence no change beyond 1. Fig. A4b and A4c of Appendix shows that
maximum removal efficiency is decreased with temperature and the
CaCO3/S ratio above which no significant removal noticed was also
decreased.
Fig. 5 shows the individual heat streams (Q1 to Q6) and total heat
(Total Q) at various temperatures. In this Fig. 5 and Total Q is shown on
secondary y-axis while Q1 to Q5 are shown on primary y-axis. Results
show that maximum heat is produced utilising the heat released in the
combustor in cooling down its temperature to 312 °C, after this max-
imum heat is obtained from heat recovered from un-recycled flue gas
from combustor. The observation of this profiles can be answered by
simultaneously referring Figs. 7 and 8. Reason could be because the
number of moles of flue gas formed is changing and hence the quantity
of heat released with gasifier conditions viz., temperature, gasifying
agent moles, split fraction, and CaCO3/S ratio and also by the com-
bustion reactions involved for the syngas from the gasifier. It is also
noted that Q3 is a function of split fraction which is negative beyond
particular split fraction (for example beyond 0.2, 0.25 and 0.3 in case of
Fig. 5a,b and c respectively) because gasifier is operated under iso-
thermal condition at a specified temperature which would be influ-
enced by the quantity of recycle stream is coming at 312 °C through the
net endo- or exo-thermicity resulting from reactions (7)–(13). Q1, Q4,
Q5 are not influence by the split fraction. From Fig. A6a to r of
Appendix it can be noticed that at a given temperature Q2 is influenced
by the split fraction because this would cause change in amount of
gasifying agent which would affect on H2 formation and thereby H2S
formation. This lead to change in quantity of CaS formation from ga-
sifier which results in quantity of heat released (Q2) is changing with
the reaction presented in Eq. (14) occurring.
kj
CaS + 2O2 ↔ CaSO4 ΔHr = −960890
kmol (14)
Fig. 6 shows the syngas composition versus the fraction of recycle
gas to gasifier at various CaCO3/S molar input feed ratio at 982°C. For
0.5 0.6 0.7 0.8 0.9 1 1.5 2 2.5
0.15 0.2 0.25 0.3
Fraction of recycle flue gas to gasifier
507
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

(a) TG=1093 OC (b) TG=982 OC

100000 2000000 160000 2000000

90000 Q1 1800000
140000
Q2 1950000

Heat stream Q1, Q2, Q3, Q4,Q5 in kW

Heat stream Q1, Q2, Q3, Q4,Q5 in kW

Q3 Q1
80000 1600000
Q2

Heat stream Q6, Total Q in kW

Q4 120000

Heat stream Q6, Total Q in kW

Q3
70000
Q5 1900000 1400000
Q6 Q4

Total Q 100000 Q5
60000 1200000
Q6
1850000
Total Q
50000 80000 1000000

1800000
40000 800000
60000

30000 600000
1750000
40000
20000 400000
1700000 20000
10000 200000

0 1650000 0 0
0.1 0.15 0.2 0.25 0.3 0.1 0.15 0.2 0.25 0.3
Fraction of recycle flue gas to gasifier Fraction of recycle flue gas to gasifier

(c) T G=871 OC
450000 2000000

400000 1800000
Heat stream Q1, Q2, Q3, Q4,Q5 in kW

1600000
350000

Heat stream Q6, Total Q in kW

1400000
300000 Q1
Q2
Q3
1200000
250000
Q4
Q5 1000000
200000 Q6
Total Q 800000
150000
600000

100000
400000

50000 200000

0 0
0.1 0.15 0.2 0.25 0.3
Fraction of recycle flue gas to gasifier

Fig. 5. Heat generated by individual heat streams at various temperatures for various split fractions for CaCO3/S = 0.5 (a) TG = 1093 °C (b) TG = 982 °C (C)
TG = 871 °C.

other temperatures refer Figs. A7–A10 of Appendix. Results shows that affect hence split fraction affect has seen on sulfur conversion after this
sorbent/S ratio has insignificant affect compared to split fraction be- ratio. For CaCO3/S ratio of 1 and above there is increase in H2S con-
cause CaCO3 decomposition would alter only CO2 produced and H2S centration with increase in recycle gas fraction but the effect of CaCO3/
reacted with CaO. However, temperature shows significant affect. From S ratio negligible.
the Fig. 6a, it is clear that as the fraction of recycle gas to gasifier in- Fig. 7 depict the effect of split fraction of recycle gas on moles of
creases the mole fraction of H2 decreases. This is because of recycle gas individual components of a syngas as well as total moles of syngas
increases the total number of moles of syngas from gasifier as evidenced produced. It shows that recycle gas fraction increases the moles of CO2
from Fig. 7. Fig. 6b shows that mole fraction of carbon monoxide de- and H2O in the product syngas. It is expected because recycle gas
creases with increase in recycle gas fraction. Reason is same as ex- mostly consist of CO2 and H2O. Moles of H2 are continuously decreasing
plained above. Fig. 6c shows that mole fraction of carbon dioxide in- with increase in fraction of recycle gas, however, its decrease is not
creases with increase in recycle gas fraction. This is because CO2 is significant. Moles of syngas produced also increasing with fraction of
formed in the gasifier in addition to CO2 entering as a gasifying agent recycle which is obviously expected. Moles of CO formation is sig-
result in net increase in total number of CO2 moles. Fig. 6d shows that nificantly affected by the CaCO3/S ratio and temperature. Upon ob-
mole fraction of hydrogen sulfide remains nearly constant with increase servation of Fig. A11 of Appendix it is noticed that number of CO moles
in recycle gas fraction for CaCO3/S ratios from 0.5 to 0.7. For CaCO3/S goes to a maximum and then decrease or become plateau with increase
ratio of 0.8 onwards increases with increase in recycle gas fraction after in recycle gas fraction. The fraction of recycle at which this maximum
a particular recycle gas fraction. In other words, split fraction has no moles of CO produced is changing with change is CaCO3/S ratio as
effect of sulfur conversion at low sorbent to sulfur ratio but at higher shown from figures presented in Appendix.
sorbent to sulfur ratio split fraction has a significant affect up to par- Although the composition of the recycle gas is a dependent variable
ticular sorbent to sulfur ratio. Upon comparison of Fig. 3, it is noticed for the analysis purpose effect of H2O/CO2 molar ratio on sulfur re-
that CaCO3/S up to 0.9 sulfur conversion is increases beyond which no moval efficiency has been studied. Fig. 8 shows the effect of H2O/CO2

508
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

(a) H 2 mole fraction (b) CO mole fraction

0.3 0.5
CaCO3/S CaCO3/S
0.5 0.5
0.45
0.25 1 1

2 2

3 3

Mole fraction of CO
0.4
Mole fraction of H2

0.2

0.35

0.15
0.3

0.1
0.25

0.05 0.2
0.1 0.15 0.2 0.25 0.3 0.1 0.15 0.2 0.25 0.3
Fraction of recycle flue gas to gasifier Fraction of recycle flue gas to gasifier
(c) CO 2 mole fraction (d) H 2S mole fraction
0.4 0.005

0.35
0.004

0.3
Mole fraction of H2S
Mole fraction of CO2

0.003

0.25

CaCO3/S
0.002
0.5
0.2 CaCO3/S 0.6
0.7
0.5
0.8
1 0.001 0.9
0.15
2 1
2
3
3
0.1 0
0.1 0.15 0.2 0.25 0.3 0.1 0.15 0.2 0.25 0.3
Fraction of recycle flue gas to gasifier Fraction of recycle flue gas to gasifier

Fig. 6. Effect of split fraction of recycle gas on moles of individual components (a) H2 (b) CO (c) CO2 (d) H2S.

molar ratio in recycle gas on sulfur removal efficiency for various split sorbent it has to obtain from decomposition of CaCO3 so the reaction
fractions. In Fig. 8(a), H2O/CO2 molar ratio is determined by varying chemistry of CaCO3 additionally come into picture in influencing the
CO2 moles in recycle while H2O moles are fixed. Whereas in Fig. 8(b) to sulfur removal efficiency while in the case of other sorbents, it directly
get the desired H2O/CO2 ratio, CO2 moles are fixed at while H2O moles react with the H2S to remove sulfur compound.
are varied. Fig. 8(a) illustrates that increase in H2O/CO2 ratio increases Reactions involved with various sorbents with H2S are shown from
the sulfur removal efficiency since this ratio is increased by decreasing Eqs. (15)–(23). However, in addition to reactions (7)–(13) following
the molar flow of CO2. So the increased concentration of CO2 has ne- side reactions of sorbent with some of the syngas compounds may also
gative effect on sulfur removal. This can be confirmed by referring to be occurring with the sorbents chosen during gasification. In other
reaction involved in Eq. (6). This is assumed to be equilibrium reaction, words, sulfur removal is carried out through the following reactions
CO2 being the product the decrease in number of moles of CO2 increases depending on the sorbent chosen.
the consumption of H2S thereby increase in sulfur removal efficiency. In
Fig. 8(b), H2O/CO2 ratio is increased from 0.1 to 0.52 by increasing the (a) With Copper based sorbent (CuO)
moles of H2O, so the increased concentration of H2O also has negative kj
on sulfur removal. In both the results, at a given mole ratio of gasifying 2CuO + H2 S + H2 ↔ Cu2 S + 2H2 O ΔHr = −315900
kmol (15)
agent, lower the split fraction higher the sulfur removal is noticed.
All the above results from Figs. 2–8 shows the DGOC performance kj
CuO + H2 ↔ Cu + H2 O ΔHr = −128500
for various operating conditions with CaO as the sorbent. Similar stu- kmol (16)
dies has been studied with various metal oxides as the sorbents viz.,
kj
CuO, MnO, Fe2O3 on sulfur removal efficiency, product gas composition CuO + CO ↔ Cu + CO2 ΔHr = −125700
kmol (17)
from gasifier and combustor, number of moles of syngas formed as well
as on total heat produced. To avoid the repetition of similar figures like
(b) With Iron based sorbent (Fe2O3)
above w.r.to each sorbent results are not presented here. However,
results are presented in Appendix from Figs. A20–A52. In case of CaO as

509
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

60000 14100

H2

CO2
50000
H2O 14000

H2, CO2, H2O, syngas moleflow (kmol/hr) Syngas

CO
40000

CO moleflow (kmol/hr)
13900

30000

13800

20000

13700
10000

0 13600
0.1 0.15 0.2 0.25 0.3
Fraction of recycle flue gas to gasifier

Fig. 7. Effect of split fraction on moles of syngas (TG = 1093 °C, PG = 6 MPa, CaCO3/S = 2).

kj (c) With manganese based sorbent (MnO)

Fe2 O3 + 2H2 S + H2 ↔ 2FeS + 3H2 O ΔHr = −192000
kmol (18)
kj
MnO + H2 S ↔ MnS + H2 O ΔHr = −94130
kmol (21)
kj
3Fe2 O3 + H2 ↔ 2Fe3 O4 + H2 O ΔHr = −50030
kmol (19) kj
MnO + H2 ↔ Mn + H2 O ΔHr = 99070
kmol (22)
kj
3Fe2 O3 + CO ↔ 2Fe3 O4 + CO2 ΔHr = −43170
kmol (20)

100

95

90
Sulfur removal efficiency %

85

80

75

SF 0.1
70

SF 0.2

65
SF 0.3

60
0.5 1.5 2.5 3.5 4.5 5.5

H2O/CO2 molar ratio

Fig. 8a. Effect of H2O/CO2 molar ratio in recycle gas on sulfur removal efficiency (TG = 1093 °C, PG = 6 MPa CaCO3/S = 2).

510
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

100

95

Sulfur removal efficiency % 90

85

80

75

SF 0.1
70
SF 0.2

65
SF 0.3

60
0.1 0.2 0.3 0.4 0.5

H2O/CO2 molar ratio

Fig. 8b. Effect of H2O/CO2 molar ratio in recycle gas on sulfur removal efficiency(TG = 1093 °C, PG = 6 MPa CaCO3/S = 2) at various split fractions of recycle flue
gas (CO2 moles are fixed while H2O moles are varied).

kj value and then after a particular value it remains constant. The ratio at
MnO + CO ↔ Mn + CO2 ΔHr = 101930
kmol (23) which removal efficiency is constant is different for different metal
oxides. At equilibrium, 92.5% sulfur removal efficiency is possible for
Fig. 9 shows removal efficiency verses oxide (or sorbent) to sulfur CuO at CuO/S molar ratio of 2. This molar ratio is matching with the
molar feed ratio for various sorbents. Results show that sulfur removal reaction stoichiometry as shown in Eq. (15). With CaCO3 as a sorbent
efficiency increase with increase in oxide to sulfur ratio up to particular removal efficiency is 81.82% for CaCO3 to sulfur ratio of 0.9 and above.

100

80
Sulfur removal efficiency %

60

40
CaCO3/S

CuO/S

20
Fe2O3/S

MnO/S

0
0 0.5 1 1.5 2 2.5 3
Oxide to sulfur molar input ratio

Fig. 9. Effect of sorbent to sulfur molar input ratio on sulfur removal efficiency (TG = 1093 °C, PG = 6 MPa).

511
A.D. Dattatray, V. Shilapuram
This value is almost near to molar ratio as per the reaction stoichio-
metry (actual value is 1). Sulfur removal efficiency of 69% at MnO/S
molar feed ratio of 0.83–3 was noticed. Sulfur removal efficiency is very
insignificant i.e., near to zero for Fe2O3 (invisible in the figure). Reason
being reaction of Fe2O3 with CO and H2O is more favoured compared
with H2S (Reactions (18)–(20)). Heat of reaction shows that the reac-
tion is exothermic hence low temperature favours the reaction. This can
also be noticed by the effect of temperature on sulfur removal efficiency
in the case of Fe2O3 from Fig. 10. However, at low temperatures un-
converted coal is more in the gasifier thus reducing the net power ef-
ficiency and no sulfur removal. Of all the sorbents tested, maximum
sulfur removal is possible with CuO.
Fig. 10 shows the effect of gasifier temperature on sulfur removal
efficiency for various sorbents. Sulfur removal efficiency is maximum
for CuO at gasifier temperature range from 800 to 1200 °C among the
all sorbent and it is decreasing with increase in temperature. However,
effect of temperature is insignificant compared with other sorbents.
Similar trend was observed for MnO but increment in decrease of re-
moval was greater after temperature 900 °C. For Fe2O3sulfur removal is
very low, maximum noticed is 12% at temperature of 800 °C, and for
further increase in gasifier temperature it is decreased to zero. This is
because of Fe2O3 is reduced by H2/CO rather than reaction with H2S as
mentioned above. For CaCO3, the removal efficiency increases with
increase in gasifier temperature and goes to maximum i.e. 84.49% at
1060 °C, and with further increase in temperature decreases to 70%.
This is because of sorbent i.e., CaO formation depends on CaCO3 de-
composition which was greatly influenced by the temperature and also
on H2S reaction with CaO as well as H2S decomposition.
Figs. 11–14 shows syngas composition on dry basis for various
sorbent to sulfur molar feed ratio at split fraction of 0.19. The effect of
flow rate of various sorbent to sulfur on the mole fraction of H2S is
shown in Fig. 11. It is observed that H2S mole fraction decreases up to
particular value and then remains constant with further increase for all
the sorbents except Fe2O3. For CuO, the H2S mole fraction decreases
linearly and then becomes minimum at CuO/S ratio of 2 matching the
stoichiometric molar ratio. So it is possible to remove significant
amount of sulfur in the form H2S using CuO as sorbent. Fig. 12 shows
100
80
Sulfur removal efficiency %
60
40
20
0
800 850
Fig. 10. Effect of gasifier temperature on sulfur removal efficiency for various sorbents (PG = 6 MPa, Sorbent/S = 2).
Fuel 236 (2019) 501–515
that mole fraction of H2 increases and then remains constant for MnO.
In case of CaCO3, mole fraction of H2 slightly increase and then linearly
decreases as CaCO3/S molar input feed ratio increases. Reason being as
CaCO3/S ratio increases, the decomposition of CaCO3 produces more
CO2. For Fe2O3, mole fraction of H2 is continuously decreasing. Fig. 13
shows that two different type of CO profiles are noticed with different
type of sorbents. CaCO3, CuO and Fe2O3 show that CO concentration is
continuously decreases but the trend for CuO is different. Fig. 14 shows
that mole fraction of CO2 increases and then remains constant for MnO.
Reason being all the unconverted CO2 of gasifying agent is reflecting as
it is. In case of CaCO3 mole fraction of CO2 is continuously increasing.
Reason is same as mentioned above that CaCO3 decomposition is
temperature sensitive so decomposed CO2 as well as CO2 through ga-
sifying agent is reflecting in the product gas composition. CO2 con-
centration is increasing in case of Fe2O3 and CuO. The reason is re-
duction of these sorbent with CO present in syngas as shown by the
reactions (17) and (20).
Based on Figs. 11–14 upon comparison of various sorbents it is
noticed that CuO sorbent is suggested in terms of sulfur removal effi-
ciency and H2S in the product gas. MnO is suggested in terms of quality
of syngas (more amount of CO and H2 and less amount of CO2 forma-
tion) quality as well as net power produced.
This work gives an idea about the effect of process parameters on
the process performance. It will also give an idea about selection of
input or manipulated variables to implement control strategy to meet
desired output/performance variables. The present results help to find
maximum sulfur removal, syn gas quality and quantity, total heat
generated possible according to selection of process conditions. In ad-
dition, this work gives an idea about selection of sorbent and optimum
conditions according to requirement of process performance variables
set.
4. Conclusions
In the present study, Dry Gas Oxy Combustion simulations have
been conducted using Aspen Plus commercial process simulator.
Initially, literature results for CaCO3 sorbent has been validated. This
CaCO3
CuO
Fe2O3
MnO
900 950 1000 1050 1100 1150 1200
Gasifier temperature °C
512
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

0.012

0.01 CaCO3

CuO

0.008 Fe2O3
Mole fraction of H2S

MnO

0.006

0.004

0.002

0
0 0.5 1 1.5 2 2.5 3
Oxide to sulfur molar feed ratio

Fig. 11. H2S mole fraction versus sorbent to sulfur molar feed ratio (TG = 1093 °C, PG = 6 MPa, Sorbent/S = 2).

simulations has been extended to cover various sorbents namely CaCO3,
Fe2O3, MnO, CuO. Effect of various process conditions namely tem-
perature, pressure in the gasifier, recycle ratio of product gas from
combustor, molar ratio of gasification agents (H2O/CO2) in the recycled
gas to the combustor has been studied on the sulfur removal efficiency,
heat produced in each stream, total heat generated, and syn gas
quantity as well as composition. Following results are drawn from the
present study.
• Different sorbents shows different behavior on removal efficiency,
total heat generated and amount of product gas composition
• Temperature has significant affect compared to split fraction, H O/
2

0.192

0.19

0.188

0.186
Mole fraction of H2

0.184

0.182

CaCO3
0.18

CuO
0.178
Fe2O3

0.176
MnO

0.174
0 0.5 1 1.5 2 2.5 3
Oxide to sulfur molar feed ratio

Fig. 12. H2 mole fraction versus sorbent to sulfur molar feed ratio (TG = 1093 °C, PG = 6 MPa, Sorbent/S = 2).

513
A.D. Dattatray, V. Shilapuram Fuel 236 (2019) 501–515

0.49

0.488

0.486

0.484

0.482
Mole fraction of CO

0.48

0.478
CaCO3

0.476
CuO

0.474 Fe2O3

0.472 MnO

0.47
0 0.5 1 1.5 2 2.5 3
Oxide to sulfur molar feed ratio

Fig. 13. CO mole fraction versus sorbent to sulfur molar feed ratio (TG = 1093 °C, PG = 6 MPa, Sorbent/S = 2).

0.305

CaCO3

0.3
CuO

Fe2O3
0.295
MnO
Mole fraction of CO2

0.29

0.285

0.28

0.275
0 0.5 1 1.5 2 2.5 3
Oxide to sulfur molar feed ratio

Fig. 14. CO2 mole fraction versus sorbent to sulfur molar feed ratio (TG = 1093 °C,PG = 6 MPa, Sorbent/S = 2).

CO2 ratio in recycled gas, sorbent/S ratio of syngas quality and total heat generated used for power produc-
• Fe O appears to be not suggested sorbent due to less removal ef-
2 3 tion.
ficiency and incomplete conversion of coal to syngas
• all the sorbents studied, CuO appears to be good sorbent in terms
Of Acknowledgement
of temperature in the gasifier required or energy input to the gasi-
fier, sulfur removal efficiency. Authors would like to claim that this work has no financial conflict
• Of all the sorbents studied, MnO appears to be good sorbent in terms of interest.

514
A.D. Dattatray, V. Shilapuram
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.fuel.2018.09.023.
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