Accepted Manuscript

Thermodynamic Equilibrium Analysis of Water-gas Shift Reaction Using Syngases

-Effect of CO2 and H2S Contents

Rei-Yu Chein, Ching-Tsung Yu

PII: S0360-5442(17)31654-7

DOI: 10.1016/j.energy.2017.09.133

Reference: EGY 11627

To appear in: Energy

Received Date: 23 December 2016

Revised Date: 03 June 2017

Accepted Date: 26 September 2017

Please cite this article as: Rei-Yu Chein, Ching-Tsung Yu, Thermodynamic Equilibrium Analysis of
Water-gas Shift Reaction Using Syngases -Effect of CO2 and H2S Contents, Energy (2017), doi:
10.1016/j.energy.2017.09.133

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Highlights

►Water-gas shift reaction (WGSR) was analyzed based on thermodynamic equilibrium.

►Coal-derived syngases with various CO2 and H2S contents were used as the feedstock.

► CH4 and carbon formations were enhanced when the syngas CO2 content increases.

► CH4 and carbon formations can be suppressed by increasing the S/C ratio.

► WGSR performance was enhanced due to CO2 and H2S removals by CaO.
 ACCEPTED MANUSCRIPT

Thermodynamic Equilibrium Analysis of Water-gas Shift Reaction Using

Syngases -Effect of CO2 and H2S Contents
Rei-Yu Chein1, Ching-Tsung Yu2
1Dept. of Mechanical Engineering, National Chung Hsing University, Taichung, Taiwan 40227
2Division of Chemistry, Institute of Nuclear Energy Research, Taoyuan, Taiwan, 32546

ABSTRACT

Thermodynamic equilibrium of water-gas shift reaction (WGSR) under various temperatures,

pressures and steam-to-CO (S/C) ratios was analyzed by Gibbs free energy minimization method.

Coal-derived syngases with various CO2 and H2S contents were used as the feedstock. Based on the

obtained results, it was found that CH4 and carbon formations were enhanced when syngas CO2

content increases. Carbon-free WGSR can be resulted using high S/C ratio. However, CH4-free

WGSR cannot be resulted even with low S/C ratios. From the H2O conversion and H2 yield

variations, the temperature at which reverse WGSR occurs can be identified and found to decrease

with the increase in S/C ratio. Solid CaO sorbent was employed for both CO2 and H2S removals in

WGSR when sour syngas was used as the feedstock. It was found that WGSR performance was

enhanced due to the CO2 and H2S removals by CaO. The H2S concentration can be decreased with

decreased S/C ratio while increasing the reaction pressure was not favourable for H2 production and

H2S removal in WGSR with CaO. Because WGSR performance enhancement due to CO2 and H2S

removals occurred at high temperature, catalysts can be eliminated in sorption-enhanced WGSR.

Keywords: water-gas shift reaction (WGSR), coal-derived syngas, thermodynamic equilibrium,

CH4 and carbon formations, and CO2/H2S removals.

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1. INTRODUCTION

Coal-derived syngas produced from Integrated Gasification Combined Cycle (IGCC) plants

represents an attractive pathway for H2 production combined with electricity generation and the

synthesis of valuable chemicals [1, 2]. For such coal-to-H2 process, H2 is produced mainly through

the water-gas shift reaction (WGSR). In addition to IGCC applications, WGSR also serves as a key

reaction for enhancing H2 selectivity in many H2 production processes such as hydrocarbon

conversion using total and partial oxidation, steam reforming and dry reforming [3-6]. Because of

its important role in these processes, WGSR has attracted new interest in recent years.

The WGSR is an exothermic reaction limited by thermodynamic equilibrium,

CO  H 2 O  CO2  H 2 , H 298 K  41.2 kJ / mol (1)

The exothermic nature of WGSR causes it to be thermodynamically unfavorable at higher

temperatures [7]. However, the reaction is kinetically limited at lower temperatures. Because of

catalyst limitations WGSR is carried out practically in two stages　as shown in Figure 1: a high-

temperature (350~450°C) shift reactor with Fe-Cr as the catalyst to increase the chemical reaction

rate and low-temperature (200~250°C) shift reactor with Cu-Zn as the catalyst to increase the

conversion efficiency. For IGCC applications this implies that the syngas produced from the

gasifier needs to be cooled to around 450°C to carry out the high-temperature shift reaction and

further reduced to 250°C for the low-temperature shift reaction.

The WGSR presented in Eq. (1) can be regarded as the idealized version which assumes that there

are no other species in the gas stream except the resulting products (H2 and CO2), and unreacted

reactants (CO and H2O). In reality, syngas produced from various sources (natural gas, coal, and

biomass) using gasification may be used as the feedstock for WGSR. Syngas produced from

gasification processes primarily consists of CO, CO2, CH4, H2, and with certain contaminants like

sulphur compounds. As syngas is used as the feedstock for WGSR, H2 and CO2 are also present in

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addition to CO and H2O in the reactant. Moreover, many side reactions are possible that produce

products other than CO2 and H2. For example, the production of CH4 is possible due to CO/CO2

methanation reaction [8, 9]. The CH4 formation is undesirable because it reduces the H2 yield.

Another undesirable product during WGSR is the carbon formation. Carbon deposited onto the

catalyst surface is detrimental because it results in irreversible catalyst deactivation [10]. Carbon

formation will also cause loss of effective surface area and lower the heat transfer rate from the

catalyst to gas [11].

For gasification processes, sulphur in the feedstock is converted mainly into hydrogen sulphide

(H2S), with some amounts of carbonyl sulphide (COS) and carbon disulphide (CS2). These

compounds need to be removed prior to utilization to avoid detrimental effects on the system

equipment. For the application in IGCC plants, the allowable H2S concentration is considered to be

100 ppm [12, 13]. In spite of the excellent efficiency in using amine-based absorption process for

desulfurization, it is thermally inefficient because it requires the gas to be cooled below the dew

point and then reheated downstream. Thus, operating desulphurization at higher temperature,

known as hot gas desulphurization (HGD), would be desirable to avoid gas cooling and the related

heat exchangers. A review on the HGD is provided in the study of Meng et al. [14] in which both in

situ and external sulphur captures are discussed. In general, solid sorbents are employed in HGD to

remove sulphur via the sorption reaction. Similar to CO2 sorbents, many types of metal oxides can

be used for syngas desulfurization [15-18]. Among these oxides, CaO is widely used because of its

low cost and ability in simultaneously absorbing CO2 and H2S [19]. In many gasifiers, CaO is

usually added directly to the gasification chamber for an in situ desulphurization. The WGSR with

CO2 sorbent, known as the sorption-enhanced WGSR (SEWGSR), has also received great attention

because of the enhanced H2 production according to Le Chatelier’s principle [20-23].

In our previous study [24], capability of various CO2 sorbents on WGSR performance

enhancement was analyzed based on thermodynamic equilibrium theory. The syngas without sulfur

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compounds was used as the feedstock. Extending from this study, a more detail study on the effect

of steam-to-carbon ratio on WGSR using both sweet and sour syngases as feedstock under a wide

range of reaction temperature is carried out in this study. Special focus is on the effect of CO2

content in syngas on carbon and CH4 formations which are unwanted products in WGSR. In the

sour syngas, both CO2 and H2S have acidic character, they may strongly interact with the sorbent

material. The behavior of the CO2 sorption material in the presence of H2S has not been thoroughly

studied yet [16]. Therefore, another focus of this study is on the effect of simultaneous CO2 and H2S

adsorptions on WGSR performance from thermodynamic point of view.

2. METHODOLOGY

The syngas is introduced into the shift reactor to perform the WGSR and produce CO2 and H2 as

described in Eq. (1). Because of the presence of CO, CO2, H2O, CH4, and H2, several side reactions

may also be possible as described below:

CO disproportionation: 2CO  C  CO2 , H 298 K  172.4 kJ / mole (2)

CO hydrogenation: H 2  CO  C  H 2O , H 298 K  175.3 kJ / mole (3)

CO2 hydrogenation: 2 H 2  CO2  C  2 H 2O , H 298 K  134.4 kJ / mole (4)

CH4 decomposition: CH 4  C  2H 2 , H 298 K  74.9 kJ / mole (5)

CO methanation: CO  3H 2  CH 4  H 2O , H 298 K  206.1kJ / mole (6)

CO2 methanation: CO2  4 H 2  CH 4  2 H 2O , H 298 K  165.0kJ / mole (7)

CH4 dry reforming: CH 4  CO2  2CO  2 H 2 , H 298 K  165.0kJ / mole (8)

From these reactions, the carbon formation might be produced from Eqs. (2) ~ (5) while the CH4

might result from the CO/CO2 methanation reactions described by Eqs. (6) and (7). Since the

reaction mixture contains CO2 and CH4, dry reforming of CH4 for producing CO and H2 is also

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possibly to occur [4]. Note that many other side reactions are possible in addition to those shown in

Eqs. (2) ~ (8), depending on the operating conditions and syngas composition. In a practical WGSR,

the catalyst might be deactivated due to carbon deposition onto catalyst while CH4 formation results

in reduced H2 yield. Therefore, carbon and CH4 formations are two major concerns in WGSR. For

these reasons and to reduce the analysis complexity, only the reactions involving CH4 and carbon

formations are considered in this study. For the syngas containing H2S, the following side reactions

may also be present [25, 26]:

CO2  H 2 S  COS  H 2 O , H 298 K  33.27 kJ / mole (9)

CO  H 2 S  COS  H 2 , H 298 K  7.87 kJ / mole (10)

COS  H 2 S  CS 2  H 2 O , H 298 K  34.47 kJ / mole (11)

Eleven species in WGSR are considered in this study, including CO, H2O, H2, CO2, CH4, H2S, COS,

CS2, N2, Ar, and elemental solid carbon C(s). N2 and Ar serve as inert gases in the system. The

initial CO molar flow rate is used as the reference to evaluate WGSR performance. The conversions

of reactants CO and H2O are defined as follows,

Fi ,in  Fi ,eq
Xi  ( )  100% , i=CO, H2O (12)
Fi ,in

The yields of the product species are defined as,

Fi ,eq  Fi ,in
Yi  ( )  100% , i=H2, CO2, CH4, and C(s) (13)
FCO ,in

In Eqs. (12) and (13), Fi ,in and Fi ,eq are the initial and equilibrium molar flow rates of species i,

respectively.

The RGibbs reactor provided in the Aspen Plus (v8.6) is used to predict the product equilibrium

composition based on the Gibbs free energy minimization method [27]. For a system of chemical

reaction, the Gibbs free energy can be expressed as,

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NG NG NG
G   ni Gi0  RT  ni ln y i  RT  ni ln p (14)
i 1 i 1 i 1

where Gi0 , ni , y i , and pi are the Gibb’s free energy under standard conditions, number of mole,

mole fraction, and partial pressure of species i, respectively, R is the universal gas constant (8.3144

J/mol K), T is the absolute temperature, and N G is the number of species in the reacting system. In

RGibbs reactor the calculation varies the number of moles of each species in each phase subject to

the stoichiometric constraints, reaction pressure and temperature, and finds a solution that

minimizes the total Gibbs energy G of the system. Detail mathematical formulation of total Gibbs

energy minimization of a reacting system can be found in many studies [28-30]. The reaction

temperature T varied in the 100~1000°C range is chosen as the primary parameter in this study. The

molar flow rate of CO is fixed as 1 kmole/sec and used as the reference molar flow rate. The molar

ratio of H2O to CO, denoted as S/C, is varied in the range of 0.5 to 5 to examine its effect on WGSR.

The reaction pressure p is varied from 1 to 20 atm to examine its effect on WGSR performance.

An appropriate property method is required to provide rigorous thermodynamic correlations to

carry out thermodynamic equilibrium analysis. Because the Peng-Robinson equation of state is

capable of dealing with systems containing hydrocarbons, water and air [31, 32], it is used to

perform this calculation.

3. RESULTS AND DISCUSSION

3.1 Syngases

Four syngases listed in Table 1 are used as the feedstock for WGSR. Syngas #1, which is referred

to as the pure syngas, containing CO only. Synagses #2 and #3 were taken from the study of Hla et

al. [33]. According to Hla et al. [33], the gas compositions were obtained from a dry-feed Shell-type

gasifier (syngas #2), and a slurry-feed Texaco-type gasifier (syngas #3). Syngases #1~#3 can be

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regarded as sweet syngases because there are no sulfur compounds contained in these syngases.

Syngas #4 was taken from the study of Lu et al. [34] which was obtained from high-sulfur Illinois

No. 6 coal gasification. Syngas #4 is referred to as the sour syngas because of the presence of H2S.

3.2 Model verification

To ensure the developed model is correct, CO conversion predicted from the RGibbs reactor at

various S/C ratios and reaction temperatures is compared with the theoretical model given as [35],

xCO2 ,in xH 2 ,in

(  X CO )( X CO )
xCO ,in xCO ,in
K eq  (15)
( S / C  X CO )(1  X CO )

where xi ,in is the initial mole fraction of species i and K eq is the equilibrium constant for WGSR

expressed as [36],

K eq  exp{z[ z (0.63508  0.29353 z )  4.1778]  0.31688} , z  (1000 / T )  1 (16)

Note that the side reactions are not considered in Eqs. (15) and (16). The equilibrium composition

evaluation using Eqs. (15) and (16) can be regarded as the conventional approach, as described in

classical thermodynamic textbooks [37]. As shown in Figures 2(a) and 2(b), the results from

RGibbs reactor and conventional approach are identical for both syngases #1 and #3, respectively.

This comparison ensured the correctness and accuracy of using the RGibbs reactor in Aspen Plus.

Based on this comparison, the RGibbs reactor is extended for further studies on WGSR with

various operating conditions and syngas compositions.

Also from Figure 2, it is seen that all reactant conversions and product yields are identical if no

side reactions are included according to Eq. (1). Both conversions and yields decrease with the

increasing temperature because WGSR is an exothermic reaction. For syngas #3 in which 16% CO2

is present, it is seen that the conversions and yields as shown in Figure 2(b) are lower than the case

without CO2 as shown in Figure 2 (a). That is, the presence of CO2 as one of the reactant has the

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tendency of decreasing the reactant conversions and product yields in WGSR. As also shown in

Figure 2(b) is that very low conversions and yields are resulted at high temperature regime when

S/C ratio is low.

In Figure 3, the CO conversions predicted from present numerical simulation and experimental

measurement reported by Hla et al. [38] are compared using the syngas #2 as feedstock. The

reaction temperature and pressure are 600°C and 17 bar, respectively. The CeO2-La2O3-based Cu

catalyst was used in the WGSR measurement. Because the results from chemical equilibrium can be

regarded as the theoretical limit of reaction, measured CO conversion is lower than the numerically

prediction as shown in Figure 3. However, the variation trend of measured data agrees well with the

numerical prediction. As indicated in Eqs. (2) ~ (8), CO conversion can be enhanced when carbon

and CH4 are formed during the reaction. This leads to CO conversion obtained with side reactions is

higher than that excluding side reactions as shown in Figure 3. Because WGSR is generic and large

amount of experimental results can be found in the literature. Detail comparison between

equilibrium prediction and experimental results using various types of syngas and catalyst can be

found in the recent review papers provided by Gradisher et al. [2] and LeValley et al. [3]. Based on

these two studies, experimentally obtained water-gas shift reaction performance characterized by

CO conversion and H2 yield is always lower than the equilibrium result. It is also to be noted that

most of these comparisons were made for using simple CO as feedstock.

3.3 Effect of S/C ratio on CH4 and carbon formations in WGSR

The results shown in Figure 2 are referred to as the ideal WGSR performance because the side

reactions are excluded. When including all possible side reactions described in Eqs. (2)~(8), Figure

3 shows the WGSR performance as functions of reaction temperature T and S/C ratio using syngas

#1 as feedstock. As shown in Figure 4(a), 100% CO conversion can be obtained even when the S/C

ratio is lower than the stoichiometric amount. Because of the exothermic reaction, CO conversion

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decreases as T is higher than 400°C. With lower S/C ratio, such as S/C=0.5 and 1 cases, large drops

in CO conversion to low value are found. With higher S/C ratios, high CO conversion can still be

obtained when T is high. From the H2O conversion variation, it is seen that H2O conversion

increases with T, reaches a maximum value, and then decreases with the increase in T. The decrease

in H2O conversion implies that the reverse water-gas shift reaction (RWGSR) occurs. The

temperature at which RWGSR occurs depends on the S/C ratio. From Figure 4(a), the temperatures

at which RWGSR occur are 720°C, 660°C, 580°C, and 560°C for S/C=0.5, 1, 3, and 5, respectively.

It should be also noted that as T is higher than that for RWGSR to occur, both CO and H2O

conversions become identical.

Figure 4(b) shows the H2 and CO2 yields as functions of T and S/C ratio. Similar to the H2O

conversion shown in Figure 4(a), both the H2 and CO2 yields increase with T, reach maximum

values, and then decrease with increasing T. Because of the side reactions, the temperatures at

which maximum H2 and CO2 yield occur are different, as shown in Figure 4(b). Note that nearly

zero H2 is produced at low temperatures because H2 is consumed by the methanation reactions as

discussed below. In a practical catalytic WGSR operated with T in the 200~450°C range, the H2

production is enhanced while the methanation reaction is inhibited by the catalyst [39, 40].

Figure 4(c) shows the carbon yield from the carbon formation reactions. Significant carbon yield

results for S/C=0.5 and 1 cases. For S/C=3, the carbon is formed for T at less than 120°C. As T is

higher than 120°C, carbon-free WGSR is resulted. When S/C=5, carbon-free WGSR results for the

entire temperature range studied. The temperature at which no carbon is formed depends on the S/C

ratio. Higher temperature for carbon-free WGSR is required as S/C ratio is low. The result in Figure

4(c) indicates that carbon formation can be inhibited by increasing the S/C ratio. That is, carbon

formation can be inhibited with sufficient hydrogen and oxygen supplies from H2O. However, the

increase in S/C ratio implies a decrease in power output in the IGCC plant because steam is

extracted from the steam turbine [41]. The other way to inhibit the carbon formation is to carry out

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WGSR at high temperature because the carbon formation reactions as shown in Eqs. (2) ~ (4) are

exothermic reactions.

Figure 4(d) shows the CH4 yield in WGSR as functions of T and S/C ratio. From Eqs. (2) ~ (7),

the reactions result in either solid carbon (C(s)) or gaseous carbon (CH4) form. Based on Figures

4(c) and (d), carbon formation reactions dominate at low T regime when the S/C ratio is low

(S/C=0.5 and 1) because the carbon formation reactions (Eqs. (2) ~ (4)) are exothermic reactions

with lower heat of reaction as compared with the methanation reactions as shown in Eqs. (6) and (7).

Under such condition, higher carbon yield and lower CH4 yield are obtained in the low T regime.

As the temperature increases, methanation reactions become the dominant reactions. Solid carbon

formation decreases while gaseous carbon (CH4) formation increases. From Figure 4(d), it is seen

that CH4 yields increases to a maximum value, reaches a maximum value and then decreases as T

increases for S/C=0.5 and 1 cases. For S/C=3, smaller CH4 yield is obtained for T less than 120°C

because of the solid carbon formation in this temperature range. CH4 yield has the maximum value

at T=120°C and decreases to zero as the temperature increases. Without the solid carbon formed for

S/C=5, the CH4 yield has a maximum value of 25% at T=100°C and then decreases to zero as the

temperature increases. Also note that CH4 yield increases with the increase in S/C ratio for S/C in

the range of 0.5 to 3 because of H2 supply from H2O. When S/C ratio increases from 3 to 5, CH4

yield decreases. According to Eqs. (6) and (7), H2O is the product from methanation reaction.

Therefore, increase in H2O is unfavorable for CH4 formation. This results in decrease in CH4 yield

as S/C ratio increases from 3 to 5. This implies that an increase in S/C ratio can also inhibit CH4

formation in WGSR. As mentioned above, an increase in S/C ratio for WGSR reduces the overall

power output in the IGCC plant.

Figure 5 presents WGSR performance using syngas #2. As shown in Figures 5(a) and 5(b),

variations in reactant conversions and product yields have similar variation trends as those shown in

Figures 4(a) and 4(b) except for the value ranges. One hundred percent CO conversion for WGSR

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can be obtained when the temperature is low. In Figures 5(a) and 5(b), negative H2O conversion

and H2 yield are obtained. Based on the definitions given in Eqs. (12) and (13), negative H2O

conversion means that the initial H2O amount is less than the equilibrium H2O amount while

negative H2 yield means that the equilibrium H2 amount is less than the initial H2 amount. Similar

to syngas #1, reactant conversions and product yields become identical for temperature in the

RWGSR regime. As compared results shown in Figures 4(c) and 5(c), the maximum carbon yield

increases from 48% of syngas #1 to 62% of syngas #2. The comparison between Figures 4(d) and

5(d) shows that the maximum CH4 yield increases from 25% of syngas #1 to 36% of syngas #2.

That is, the increase in CO2 content in the syngas enhances the carbon and CH4 formations in

WGSR.

Figure 6 presents WGSR performance using syngas #3 a feedstock. In this case, higher initial CO2

concentration is involved compared with syngas #2. Under such initial composition, Figure 6(a)

shows that 100% can be obtained for all S/C ratios studied when the temperature is lower than

400°C. However, as the temperature increases further, CO conversion drops to a larger extent

compared with syngas #2, as shown in Figure 6(a). A similar conclusion can be made for the H2O

conversion. Using the maximum H2O conversion as an example, H2O conversion for syngas # 3 is

lower than that for syngas# 2, as shown in Figure 6(a). Note that the CO and H2O conversions

become identical as the temperature is in the RWGSR regime. Figure 6(b) shows that H2 and CO2

yields are also lower than those obtained from syngas#2 because of higher initial CO2 amount. With

more CO2 involved in the reaction, more C(s) and CH4 can be formed based on the comparisons

between Figures 5(c), 5(d), 6(c), and 6(d).

Figure 7 shows WGSR performance using syngas #4 as feedstock. As shown in Figure 7, all

reactant conversion and product yield variations are similar to other syngases shown in Figures 4, 5,

and 6. However, with the appearance of CH4 and H2O in the initial syngas composition, CO and

H2O conversions do not have the same value as the temperature is in the RWGSR regime, as shown

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in Figure 7(a). In the RWGSR temperature regime, the H2O conversion is higher than the CO

conversion. In Figure 7(b) the H2 yield is higher than the CO2 yield for temperatures in the RWGSR

regime. The higher H2 yield indicates that less H2 is consumed for CH4 formation. In addition, H2S

conversion due to endothermic reactions shown in Eqs. (9) and (11) may also contribute to the

increased H2 yield and H2O conversion when T is high. Since the initial content of CO2 is slightly

lower than that in syngas #3, Figures 7(c) and 7(d) show that the resulting C(s) and CH4 yields are

about the same as those shown in Figures 6(c) and 6(d).

Table 2 summarizes the maximum H2, CH4 and carbon yields and temperatures at which these

maximum values occur based on the results shown in Figures 4 ~ 7. From Table 2, the temperature

at which RWGSR occurs depends on the S/C ratio, regadless of the syngas composition. For

S/C=0.5, 1, 3, and 5, the temperatures at which RWGSR occurs are found to be 720°C, 660°C,

580°C, and 560°C, respectively. The CH4 and carbon yields increase with the increased CO2

amount in the initial syngas composition. The temperature at which maximum carbon yield occurs

is 100°C for all syngas compositions and S/C ratios studied. Carbon-free WGSR can be obtained

using high S/C ratios. As discussed ealier, the carbon formation is mainly due to the exothermic

reactions shown in Eqs. (2) ~ (4). The CH4 formation is due to the methanation reactions of CO and

CO2. As shown in Eqs. (6) and (7), the methanation reactions are unfavorable at high temperature

since they are exothermic reactions. Unlike carbon formation, CH4-free WGSR cannot be resulted

for all the S/C ratios studied.

3.4 WGSR with H2S removal

Syngas #4 is used to examine the WGSR characteristics when sour syngas is used as the feedstock.

Figure 8(a) shows the equilibrium H2S concentration as a function of T and S/C ratio. From Figure

8(a), the equilibrium H2S concentrations depend on the reaction temperature and S/C ratio. With

more steam used, lower H2S concentration is obtained because of the dilution effect. Figure 8(a)

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shows H2S concentration increases with T, reaches a maximum value, and then decreases to a

constant value slightly lower than the initial concentration. With the presences of CO, CO2, H2O,

and H2 in the syngas, it can be seen that the H2S concentration obtained in Figure 8(a) is due to the

reactions shown in Eqs. (9) ~ (11). For low T, H2S concentration increases due to the reverse

reactions of Eqs. (9) and (11) and forward reaction of Eq. (10). As T increases, forward reactions of

Eqs. (9) ~ (11) occur and H2S is converted to COS, H2, and H2O. As noted earlier in discussion of

Figure 7, higher H2 yield and H2O conversion are contributed by H2S conversion for sour syngas.

As shown in Figure 8(b), H2S conversion depends on both T and S/C ratio. It is seen that H2S

conversion increases with increase in T and decrease in S/C ratio. Based on Eqs. (9) and (11), H2O

is product of the H2S conversion. Increase in H2O amount is therefore unfavorable for H2S

conversion [19].

As shown in Figure 8(b), H2S conversion is quite low in WGSR. For practical syngas utilization,

H2S concentration must be reduced to avoid equipment corrosion. For HGD, various sorbents have

been extensively studied for H2S removal from syngas [15-18]. CaO is adopted in this study as the

H2S sorbent to reduce the H2S amount in the syngas [19]. Note also that CaO serves as CO2 sorbent

to reduce the amount of CO2 in the reaction mixture. The WGSR with CO2 absorption, also known

as sorption-enhanced WGSR (SEWGSR) [20-23]. In SEWGSR, both CO2 and H2S can be

simultaneously absorbed, resulting in enhanced H2 production and desulfurization. The

stoichiometric reactions involved in SEWGSR with CaO as the sorbent for syngas containing H2S

are [14, 19],

Carbonation:

CaO  CO2  CaCO3 , H 298 K  178 kJ / mol (17)

H2S capture:

CaO  H 2 S  CaS  H 2 O , H 298 K  68.7 kJ / mol (18)

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COS capture:

CaO  COS  CaS  CO2 , H 298 K  102 kJ / mol (19)

Based on Eqs. (17) ~ (19) for using CaO as the sorbent in SEWGSR, CaO, CaCO3, and CaS are

added into the analysis in addition to the eleven species described above. In this study, the CaO

molar flow rate is fixed as 1 kmole/sec which is the same as the CO in the syngas. Figure 9

compares WGSR performances both with and without CaO using syngas #4 as feedstock for S/C=3.

Figure 9(a) shows that both CO and H2O conversions can be enhanced as the CaO is introduced in

WGSR because of the CO2 absorption. Note that CO and H2O conversions do not have the same

value for T in RWGSR regime because of the presences of CH4 and H2O in the syngas and H2S

conversion to H2 and H2O. When T is greater than 740°C, CO and H2O conversions for with and

without CaO cases become identical indicating that CaO loses its ability in CO2 absorption. This

can also be identified from the CO2 yield variation shown in Figure 9(b). Figure 9(b) shows that

CO2 yield increases sharply in the case with CaO as T is greater than 740°C. In SEWGSR, the

thermodynamic constraint of WGSR is overcome by the removal of CO2 from the reaction mixture,

which enhances H2 production as shown in Figure 9(b). Figure 9(b) shows that H2 yield with value

close to 100% can be obtained for T in the range of 500 ~ 740°C. This is achieved by the concurrent

WGSR and carbonation reaction of CaO to form CaCO3, thereby removing CO2 from the reaction

mixture. Because the combined reaction for enhanced WGSR performance occurs at high

temperature, the need for a WGSR catalyst can be eliminated [42]. Figure 9(c) shows carbon-free

WGSR can be obtained by the introduction of CaO for S/C=3. Although lower CH4 yield can be

obtained in SEWGSR, CH4 formation cannot be completely suppressed.

Figure 10 shows the species mole fractions corresponding to the results in Figure 9. The

temperature at which RWGSR occurs can be identified from the H2O and H2 mole fraction

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variations shown in Figure 10(a). The temperature for RWGSR to occur in SEWGSR is higher than

that in WGSR. With S/C=3, carbon formation is completely inhibited for the SEWGSR case.

In addition to CO2 removal, CaO sorbent is also capable of reducing sulfur concentration in

SEWGSR. Figure 10(b) compares the H2S concentrations in both with and without CaO cases. The

H2S concentration is found to depend significantly on the temperature. For the case without CaO,

H2S concentration increases with T, reaches a maximum value at about T=200°C, and then

decreases to a value close to initial value as T increases. This has been described above in Figure

8(a). For the case with CaO, H2S concentration can be reduced to below 100 ppm when T is low.

This is because both H2S and COS capture reactions are exothermic and favorable at low

temperatures. As temperature increases, reverse reactions of Eqs. (9) and (11) may be dominated

and resulted in increased H2S concentration with value close to the case of without CaO. H2S

concentration increases with T and reaches a maximum value at T=300°C. With T higher than

300°C, the H2S concentration decreases gradually, followed by a sharp drop, reaching a minimum

value at about T=700°C, and then increases as the temperature increases further. For S/C=3, the

minimum H2S concentration has the value of 250 ppm which is still higher than the allowable H2S

concentration in practical IGCC applications. The result shown in Figure 10(b) is similar to those

obtained by Elseviers and Verelst [13], and Meng et al. [14]. For IGCC applications only the

temperature range above 300°C is of interest for HGD because absorption kinetics becomes too

slow for the sorbents when the temperature is lower than 300°C.

Figure 11 shows the S/C ratio effects on the H2S concentration using syngas #4 for the SEWGSR.

From Figure 11(a), H2S concentrations lower than 100 ppm can only be reached for the low S/C

ratio cases. According Eq. (18), H2O is the product for H2S capture reaction. Therefore, high H2O

concentration is unfavorable for H2S capture. However, with lower S/C ratios, WGSR performance

might be degraded. That is, CO conversion and H2 yield might be decreased and CH4 and carbon

formations might be enhanced, as shown in Figures 11(b) and 11(c), respectively. Also shown in

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Figure 11(c) is that CH4 formation cannot be inhibited in the SEWGSR system by increasing the

S/C ratios. However, complete inhibition of carbon formation can be obtained by the increased S/C

ratio in the SEWGSR.

Figure 12 shows the reaction pressure effect on SEWGSR performance. Figure 12(a) indicates

that the H2S concentration cannot be reduced by increasing the reaction pressure. The minimum

H2S concentration increases with the increase in pressure. At high temperatures the H2S

concentration is independent of the pressure. With increased pressure the CO conversion can be

enhanced while the H2 yield is decreased, as shown in Figure 12(b). The decrease in H2 yield is due

to more CH4 formed, as shown in Figure 12(c), as the pressure is increased. Although the CO

conversion can be enhanced by increasing the reaction pressure, H2 production and desulfurization

are degraded.

4. CONCLUSIONS

Thermodynamic equilibrium analysis of WGSR using sweet and sour syngases as the feedstock

was performed based on the Gibbs free energy minimization method. For the sweet syngas,

particular focus is on the effect of steam-to-carbon (S/C) ratio on the carbon and CH4 formation.

For the sour syngas, CaO sorbent is introduced in WGSR for removing CO2 and H2S

simultaneously. The following conclusions are made based on the obtained results:

(1) Regardless of the syngas composition, reactant conversion and product yield have similar

variation trends for the reaction temperature and S/C ratio ranges studied.

(2) Carbon and CH4 yields were found to increase with the initial CO2 amount in the syngas. Both

carbon and CH4 yields decrease as the temperature increases and can be suppressed by increasing

the S/C ratio.

(3) Carbon-free WGSR can be resulted using higher S/C ratio. However, CH4-free WGSR cannot

be resulted using high S/C ratio because of more hydrogen supply from H2O.

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(3) With the introduction of solid sorbent CaO, simultaneous CO2 and H2S absorptions occur and

lead to enhanced WGSR performance and reduced H2S concentration. CH4 and carbon formations

were also suppressed by the introduction of CaO. Because the enhanced WGSR performance occurs

at temperature in the range of 500 to 740°C, the catalyst for WGSR can be eliminated.

(4) H2S concentration below 100 ppm can be reached using lower S/C ratio in the sorption-

enhanced WGSR. Both H2 production and HGD were unfavorable as the SEWGSR reaction

pressure increases.

ACKNOWLEDGEMENT

This research was partially supported by the Ministry of Science and Technology in Taiwan

through Grant MOST104-3113-E-042A-001.

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List of Tables

Table 1 Syngas composition used in this study.

Table 2 Comparison of WGSR performance for syngas containing various CO2 amounts.

List of Figures

Figure 1 Conventional WGSR process.

Figure 2 ASPEN PLUS RGibbs reactor model verification using the conventional approach [35, 36]

with various S/C ratios. (a) syngas #1 and (b) syngas #3. p=1 atm, i=CO, H2O, CO2, and H2.

Side reactions are not included.

Figure 3 ASPEN PLUS RGibbs reactor model verification using experimental data reported by Hla

et al. [38]. Syngas #2 is used as the feedstock. Operation pressure and temperature are 17

bar and 600°C, respectively. CeO2-La2O3-based Cu catalyst was used in WGSR.

Figure 4 WGSR performance using syngas #1 as feedstock. (a) CO and H2O conversions, (b) H2

and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

Figure 5 WGSR performance using syngas #2 as feedstock. (a) CO and H2O conversions, (b) H2

and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

Figure 6 WGSR performance using syngas #3 as feedstock. (a) CO and H2O conversions, (b) H2

and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

Figure 7 WGSR performance using syngas #4 as feedstock. (a) CO and H2O conversions, (b) H2

and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

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Figure 8 (a) Equilibrium H2S concentration and (b) H2S conversion as functions of temperature and

S/C ratio.

Figure 9 Effect of sorbent CaO on WGSR performance. S/C=3, p=1 atm. (a) CO and H2O

conversions, (b) H2 and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

Figure 10 Comparisons of (a) species mole fractions and (b) equilibrium H2S concentrations for

WGSR with and without CaO. S/C=3, p=1 atm.

Figure 11 S/C ratio effect on WGSR performance with CaO. p=1 atm. (a) H2S concentration, (b)

CO conversion and H2 yield, and (c) C(s) and CH4 yields.

Figure 12 Pressure effect on WGSR performance with CaO. (a) H2S concentration, (b) CO

conversion and H2 yield, and (c) C(s) and CH4 yields.

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Table 1 Syngas composition used in this study

Syngas CO H2 CO2 N2 H2S H2O CH4 Ar Ref.
(vol%) (vol%) (vol%) (vol%) (vol%) (vol%) (vol%) (vol%)
#1 100 0 0 0 - - - -

#2 65 30 2 3 - - - - [33]

#3 44 37 16 3 - - - - [33]

#4 37.3 31.2 11 - 0.6 17.1 1.3 1 [34]

Table 2 Comparison of WGSR performance for syngas containing various CO2 amounts.

Syngas Max. H2 yield (%) Max. CH4 yield (%) Max. C(s) yield (%)
/ temperature (°C) / temperature (°C) / temperature (°C)
S/C=0.5
#1 ( 0% CO2) 37 / 720 4 / 340 48 / 100
#2 ( 2% CO2) 28 / 720 13 / 340 62 / 100
#3 (16% CO2) 10 / 720 18 / 340 78 / 100
#4 (11% CO2) 20 / 720 20 / 340 81 / 100
S/C=1
#1 ( 0% CO2) 58 / 660 12 / 380 42 / 100
#2 ( 2% CO2) 48 / 660 22 / 380 53 / 100
#3 (16% CO2) 30 / 660 26 / 380 71 / 100
#4 (11% CO2) 40 / 660 30 / 380 72 / 100
S/C=3
#1 ( 0% CO2) 86 / 580 25 / 120 6 / 100
#2 ( 2% CO2) 88 / 580 36 / 120 10 / 100
#3 (16% CO2) 70 / 580 46 / 180 27 / 100
#4 (11% CO2) 80 / 580 49 / 140 28 / 100
S/C=5
#1 ( 0% CO2) 94 / 560 25 / 120 Carbon free
#2 ( 2% CO2) 90 / 560 36 / 120 Carbon free
#3 (16% CO2) 85 / 560 46 / 180 Carbon free
#4 (11% CO2) 93 / 560 46 / 140 Carbon free

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Syngas Two-stage
Gasifier WGS reactors
cooling and
(~1000°C) (200°C~450°C)
purification

H2/CO2 CO2
separation sequestration

Combined
cycle or Fuel
cells

Figure 1 Conventional WGSR process.

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100

90

80
5
3
70

60 1
Xi, Yi (%)

50
S/C=0.5
40

30

20

10
(a)
0
100 200 300 400 500 600 700 800 900 1000
T (oC)

100

90

80

70 S/C=5

60
Xi, Yi (%)

3
50

40

30 1
20
0.5
10
(b)
0
100 200 300 400 500 600 700 800 900 1000
T (oC)
Figure 2 ASPEN PLUS RGibbs reactor model verification using the conventional approach [35, 36]
with various S/C ratios. (a) syngas #1 and (b) syngas #3. p=1 atm, i=CO, H2O, CO2, and H2. Side
reactions are not included.

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100

90

80

70

60
XCO (%)

50

40

30
with side reactions
20
without side reactions
experiment, Hla et al. [38]
10

0
0 1 2 3 4 5 6 7
S/C

Figure 3 ASPEN PLUS RGibbs reactor model verification using experimental data reported by Hla
et al. [38]. Syngas #2 is used as the feedstock. Operation pressure and temperature are 17 bar and
600°C, respectively. CeO2–La2O3-based Cu catalyst was used in WGSR.

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50
100 (c)
(a)
90
S/C=5 S/C=0.5
40
80
3
70
30
60 1

YC(s) (%)
Xi (%)

50 1
20
40
0.5
30
10
20
CO
10 H 2O 3 5
0
0
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

100 25
(b)
90 (d)
S/C=5
80 20 S/C=5
3
70
3
60 15
YCH4 (%)
Yi (%)

50 1

40 10
1
0.5
30

20 5
H2 0.5
10 CO2

0 0
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

Figure 4 WGSR performance using syngas #1 as feedstock. (a) CO and H2O conversions, (b) H2
and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

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70
100 (c)
(a)
90
S/C=5 60
80
70 3
50
60
50
S/C=0.5
40
1

YC(s) (%)
40
Xi (%)

30
0.5 30
20 1
10
20
0
-10
10
-20 CO
H 2O 3
-30 5
0
-40
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

100 40
(b) (d)
90
80 S/C=5 35
70
3
60 30 S/C=5
50
25 3
40 1
YCH4 (%)
Yi (%)

30
0.5 20 1
20
10
15
0
0.5
-10 10
-20
-30 H2 5
-40 CO2

-50 0
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

Figure 5 WGSR performance using syngas #2 as feedstock. (a) CO and H2O conversions, (b) H2
and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

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80
100 (c)
(a)
70
75 S/C=5
60
3
50
50 S/C=0.5

YC(s) (%)
25 1
Xi (%)

40
0.5 1
0 30

-25 20
3
CO 10
-50
H 2O
5
0
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

100 50
(b) (d)
45
75 S/C=5
40 S/C=5
50 3
35 3
25 1 30
YCH4 (%)

0.5
Yi (%)

0 25 1

20
-25
0.5
15
-50
10
H2
-75
CO2 5

-100 0
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

Figure 6 WGSR performance using syngas #3 as feedstock. (a) CO and H2O conversions, (b) H2
and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

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100 100
(a) S/C=5 (c)

75 3

75
50

25 S/C=0.5

YC(s) (%)
Xi (%)

50

0
0.5 1
1
-25 25

-50 CO 3
H 2O
5
0
-75
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

100
(b) 3 5 (d)
50
75
45

50
S/C=5
40

35
3
25
1
YCH4 (%)

30
Yi (%)

0
25
1 0.5
-25 S/C=0.5 20

15
-50
10
H2
-75
CO2 5

-100 0
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

Figure 7 WGSR performance using syngas #4 as feedstock. (a) CO and H2O conversions, (b) H2
and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

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7000
(a)

6000
S/C=0.5

1
5000
yH2S (ppm)

initial yH2S
4000 equilibrium yH2S

3
3000

5
2000
100 200 300 400 500 600 700 800 900 1000
o
T ( C)

5
(b)

S/C=0.5

3
1
XH2S (%)

2
3
5
1

0
100 200 300 400 500 600 700 800 900 1000
o
T ( C)

Figure 8 (a) Equilibrium H2S concentration and (b) H2S conversion as functions of temperature and
S/C ratio.

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30
100 (c)
(a)
90
CO
25
80

70
20
60

50

YC(s) (%)
Xi (%)

15
40 H 2O
30 C(s)
10
20 S/C=3
10 S/C=3 without CaO
5 with CaO
0 without CaO
with CaO
-10
0
-20
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

100 (b) (d)

50

CO2 45

40
50
35

30
YCH4 (%)
Yi (%)

H2 CH4
0 CO2 25

20

15 S/C=3
-50 without CaO
H2 S/C=3 10 with CaO
without CaO 5
with CaO
0
-100
100 200 300 400 500 600 700 800 900 1000 100 200 300 400 500 600 700 800 900 1000
T (oC) T (oC)

Figure 9 Effect of sorbent CaO on WGSR performance. S/C=3, p=1 atm. (a) CO and H2O
conversions, (b) H2 and CO2 yields, (c) C(s) yield, and (d) CH4 yield.

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(a)
0.7 S/C=3
without CaO
0.6 with CaO

0.5
H 2O
mole fraction yi

0.4

H2
0.3

0.2 CO2
CH4
0.1
C(s) CO
0
100 200 300 400 500 600 700 800 900 1000
T (oC)

4000
(b)
equilibrium yH2S
3500

3000

2500
yH2S (ppm)

initial yH2S
2000

1500

1000
S/C=3
500 without CaO
with CaO

0
100 200 300 400 500 600 700 800 900 1000
T (oC)

Figure 10 Comparisons of (a) species mole fractions and (b) equilibrium H2S concentrations for
WGSR with and without CaO. S/C=3, p=1 atm.

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4500
(a)
p=1 atm
4000

3500

3000

yH2S (ppm) 2500

S/C=5
2000
3
1
1500
0.5
1000

500

0
100 200 300 400 500 600 700 800 900 1000
T (oC)

(b)
100

75
5
S/C=5
3
XCO, YH2 (%)

3
50

25
1

1
0.5
0 0.5
XCO
YH2
-25
100 200 300 400 500 600 700 800 900 1000
T (oC)

(c)
35

30 S/C=0.5
1
25 3

20 CH4
Yi (%)

C(s)

15 5

10
0.5
5
1, 3, 5
0
100 200 300 400 500 600 700 800 900 1000
T (oC)

Figure 11 S/C ratio effect on WGSR performance with CaO. p=1 atm. (a) H2S concentration, (b)
CO conversion and H2 yield, and (c) C(s) and CH4 yields.

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4000
(a) S/C=3
3500

3000
p=1atm
2500
yH2S (ppm) 10 atm
20 atm
2000

1500

1000

500

0
100 200 300 400 500 600 700 800 900 1000
T (oC)

(b)
100

75

p=1 atm
XCO, YH2 (%)

50
10 atm
20 atm
25 20 atm 10 atm
1 atm

0 S/C=3
XCO
YH2
-25
100 200 300 400 500 600 700 800 900 1000
T (oC)

(c)
35
S/C=3
CH4
30 C(s)

25 p=1 atm

20
10 atm
Yi (%)

20 atm
15

10

5
1 atm, 10 atm, 20 atm
0
100 200 300 400 500 600 700 800 900 1000
T (oC)

Figure 12 Pressure effect on WGSR performance with CaO. (a) H2S concentration, (b) CO
conversion and H2 yield, and (c) C(s) and CH4 yields.

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