i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 6 6 3 8 e6 6 4 5

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Investigation into the performance of a CoeMo based sour

shift catalyst using simulated coal-derived syngases

San Shwe Hla a,*, G.J. Duffy b, L.D. Morpeth a, A. Cousins a, D.G. Roberts a, J.H. Edwards b
a
CSIRO Energy Technology, PO Box 883, Pullenvale, QLD 4069, Australia
b
CSIRO Energy Technology, PO Box 330, Newcastle, NSW 2300, Australia

article info abstract

Article history: The performance of a commercially-available sour shift catalyst (SSC1) under selected
Received 28 October 2010 syngas compositions was investigated and kinetic parameters were obtained. The water-
Received in revised form gas shift experiments were carried out in a differential reactor using simulated syngases
8 February 2011 containing a constant level of H2S concentration of 1000 ppm on a wet basis at 450
C and
Accepted 12 February 2011 atmospheric pressure. The following kinetic relationship has subsequently been developed
Available online 21 March 2011 to describe the performance of catalyst SSC1 at a reaction temperature of 450
C (723 K) and
atmospheric pressure using a powerelaw model:
Keywords:    
60:3  1:3 0:750:12 0:310:08 0:070:02 0:090:02 1 PCO2 PH2
Wateregas shift reaction R ¼ 0:008  0:0004exp 0
PCO PH2 O PCO2 PH2 1 ,
RT K PCO PH2 O
Sour shift catalysts
Coal-derived syngas
Kinetics The effect of varying H2S concentration on the performance of the sour shift catalyst
Effect of sulfur was investigated using simulated dry-feed coal-derived syngas. It was found that its
reactivity is significantly improved by the presence of sulfur. The reaction order with
respect to H2S concentration in the feed gas was calculated to be 0.52  0.02 for a wide
range of H2S concentrations (330e2670 ppm). The activity of the sour shift catalyst is very
poor compared to those of commercial high-temperature wateregas shift catalysts when
the concentration of H2S in the syngas is lower than 500 ppm. It was found that the sour
shift catalyst has an advantage over the high-temperature catalysts tested in this study
only if the H2S concentration in the coal-derived syngas is consistently maintained at
levels greater than 1000 ppm on a wet basis.
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction and H2. This is an equilibrium reaction that favours the

formation of CO2 and H2 at low temperatures. In practice
The capture of CO2 in a coal-based gasification system for H2 catalysts are required to increase the rate of formation of CO2
production or power generation, or the use of coal-derived and H2 to ensure that the equilibrium conversion of CO is
syngas for the synthesis of fuels and chemicals, requires approached under the selected reaction conditions.
adjustment of the H2, CO and CO2 ratios in the syngas The WGS process is a mature technology that has been
produced from the gasifier. This is achieved via the wateregas applied for many decades [1,2] to the processing of syngases
shift (WGS) reaction where CO is reacted with H2O to form CO2 which are largely produced by the reforming or partial

* Corresponding author. Tel.: þ61 7 3327 4125; fax: þ61 7 3327 4455.
E-mail address: [Link]@[Link] (S.S. Hla).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/[Link].2011.02.075
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 6 6 3 8 e6 6 4 5 6639

oxidation of oil and natural gas. However, coal-derived syn- between performances of high temperature WGS catalysts and
gases contain a larger concentration of CO and lower H2 levels sour shift WGS catalysts at the same conditions (such as
than those produced from natural gas, putting greater demands temperature, pressure and gas composition) are available. Sour
on the performance of WGS catalysts. A comprehensive feasi- shift catalysts are claimed to be not only sulfur-tolerant but
bility study to investigate how commercially-available, high- their activity is also claimed to be improved by the presence of
temperature catalysts perform under conditions relevant to sulfur [2]. However the influence of sulfur contained in coal-
coal-derived syngases was conducted by the authors [3]. Our derived syngases on the performance of sour shift catalysts is
previous research [3] concluded that an iron-based commercial not known in detail.
catalyst can be used for the WGS reaction with coal-derived In this present study, we first tested the performance of
syngases from both dry-feed type gasifiers (which produce high a commercially-available sour shift catalyst under selected
concentrations of CO), and slurry-feed type of gasifiers (which syngas compositions and obtained relevant kinetic parame-
produce higher concentrations of H2), and that they would be ters. These results were then compared with the performance
suitable for processing gases at the backend of catalytic of two HT catalysts (HTC1 and HTC2) presented in our
membrane reactors where the level of CO2 will be very high due previous study [3]. Finally, the effect of H2S concentration on
to the membrane-driven extraction of the hydrogen product. the performance of the sour shift catalyst was investigated
Unlike syngases from natural gas, which are mostly free of using simulated dry-feed coal-derived syngas.
impurities such as sulfur and nitrogen compounds, as well as
particulates, coal-derived syngases contain a wide range of
major and trace impurities depending on the composition of 2. Experimental methods
the coal and the type of gasifier used [4]. Of these impurities,
H2S tends to be present at the highest concentration in raw 2.1. Experimental setup
coal-derived syngases, but can vary significantly
(1000e13,000 ppmv) depending on the sulfur level in the feed The experiments were carried out in a fixed-bed reactor,
coal [5]. This major impurity can have deleterious impacts on details of which have been presented previously [3]. The gases
the downstream processing of syngases and it is important to (CO, H2, CO2, N2 and H2S) were fed into the reactor through
understand its effect on the performance of WGS catalysts. The individually controlled mass flow controllers. A steady flow of
authors [6] have investigated the effect of H2S on the perfor- de-ionized water was metered by a HPLC pump and vaporised
mance of a commercial iron-based high temperature (HT) inside an electrically-heated preheating tube before entering
catalyst. It was found that the HT catalyst continued to operate the reactor. At the reactor outlet a water-cooled condenser
with a sulfur-containing syngas but at a reduced activity, with was used to remove water from the product gases. The
deactivation at higher levels (1201100 ppmv) approximately composition of the dry product gases was measured by gas
proportional to the square root of the H2S concentration. Our chromatography (Varian CP4900) at 3 min intervals.
previous study [6] also showed that H2S poisoning is reversible
and that the HT catalysts tested can tolerate small quantities of 2.2. Catalyst samples
sulfur (<50 ppm) without adverse effects upon their activity.
To overcome the deactivation by H2S, a highly active sulfur- A commercial sour shift catalyst (SSC1) was chosen as a model
tolerant (referred to as sour shift) catalyst may have some catalyst. Table 1 gives vendor-supplied details of SSC1. Both
advantage in this regard [1,2]. Some researchers have reported HTC1 and HTC2 are copper-promoted iron chromium oxide
that sulfided forms of Co/Mo and Ni/Mo supported on Al2O3 based HT catalysts and their specifications have been pre-
showed good catalytic activity in the presence of sulfur [7e10]. sented in our previous papers [3,6]. The catalyst pellets were
Sulfided catalysts are widely used in commercial processes, ground and sieved to a particle size of þ53150 mm to mini-
such as in hydro-desulfurisation, hydro-denitrogenation, mize the possibility of internal diffusion limitations on the
hydro-demetallisation, and FishereTropsch reactions [7,8]. kinetics study.
These catalysts can be used in reactions involving oxygenated
compounds such as the WGS reaction, methanation and 2.3. Sulfidation of SSC1
methanol synthesis [8]. A study [11] has concluded that sour
shift is the preferred process with respect to costs and effi- As the sour shift catalyst samples are supplied in oxide form,
ciency for treating syngas from a slurry-feed gasifier. Syngas they require sulfiding before they become active. Approxi-
from a slurry-feed gasifier usually contains considerable mately 1.2 g of SSC1 samples was packed in the center of the
amounts of valuable steam which would have to be condensed
prior to sulfur removal if conventional iron-based catalysts
were to be used. This steam would then have to be added to the Table 1 e Specifications of SSC1.
syngas stream again prior to the WGS reactor. While there are
Composition
numerous studies on high-temperature catalysts available in
the open literature, only limited information about the active CoO (wt%) 2
forms of sulfur-tolerant WGS catalysis is available [8,9,12e16]. MoO3 (wt%) 8
Whilst two well-known reviews in the field of WGS catalysis MgO (wt%)  24
Al2O3 (wt%)  50
[1,2] suggest that the application of sour shift catalysts for
Promoter (wt%) Balance
processing coal-based syngases containing significant sulfur Shape [Commercially available] Pellet
contents may have some advantages, no direct comparisons
6640 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 6 6 3 8 e6 6 4 5

reactor between layers of inert material (quartz wool). The only the LangmuireHinshelwood and the powerelaw models
samples were first heated under N2 at a rate of 2.5
C min1 up could accurately describe the reaction behaviour over the
to 110
C and maintained at this temperature for 1 h to dry the temperature and concentration ranges investigated. Accord-
sample. The N2 stream was then switched to the sulfiding gas ing to Podolski and Kim [26] a powerelaw model is a reason-
mixture consisting of H2S (4%) and H2 (96%) with a gas flow at able alternative to the more complex LangmuireHinshelwood
atmospheric pressure of 5 L h1g1 of catalyst. The reactor model (which is derived from detailed and specific reaction
temperature was then increased from 110
C to 450
C with mechanisms). Several studies [1,2,20,21,27e30] have demon-
a heating rate of 2.5
C min1. The catalyst was then sulfided strated the usefulness of a simple empirical powerelaw
at 450
C for 4 h. After sulfidation, the desired gas stream was expression as a tool for an integrated and optimized simula-
introduced to the reactor for the experimental investigation. tion of a fuel processing system and for reactor design studies.
A powerelaw form has therefore been used to express the
2.4. Selection of syngas compositions kinetics of the high temperature WGS reaction over SSC1.
The kinetics for the WGS reaction at 450
C (723 K) over
The syngas compositions investigated in this study have been SSC1 were measured with gas compositions characteristic of
chosen to be consistent with those that might be encountered a dry-feed coal-derived syngas and downstream of WGS
in both a dry-feed type gasifier and a slurry-feed type gasifier. reactor (Table 2). The reaction order of each component in
The rationale for selection of these inlet gas compositions was the WGS reaction was determined by varying only one
discussed previously [3]. Four different gas compositions component concentration while the concentrations of the
representative of what might be encountered within coal- others were kept constant. The total flow rate was kept
based gasification systems were selected for this study and constant for all experimental runs by adjusting the N2 flow
are listed in Table 2. The first two compositions are charac- rate. Fig. 1 presents plots of ln [CO conversion rate/(1-b)]
teristic of what might be the syngas compositions entering the versus the log of partial pressure of each component (CO,
WGS reactor, while the last two compositions are what might H2O, CO2 or H2). (b is the term reflecting the reverse reaction
be encountered at the backend of a membrane WGS reactor or or approach to equilibrium.) All the plots in Fig. 1 are found to
a conventional fixed-bed WGS reactor respectively. All the be linear, verifying that the kinetics of the WGS reaction over
experimental runs in this study were carried out with a steam SSC1 can be expressed by using the empirical powerelaw
to carbon molar ratio of 3:1. The performance and kinetics model. The gradient of each straight line in Fig. 1 can be used
studies of SSC1 were conducted at the four selected gas inlet to determine the reaction order with respect to the individual
compositions under a constant wet gas velocity at 450
C with species. From Fig. 1, the reaction orders for CO, H2O, CO2 and
a constant level of H2S (1000 ppm on a wet basis). H2 are found to be 0.75  0.12, 0.31  0.08, 0.07  0.02 and
0.09  0.02 respectively. Similar reaction orders for H2O and
CO2 were reported by Srivatsa and Weller [16] who investi-
3. Results and discussions gated WGS kinetics over a commercial sulfided Co/Mo cata-
lyst at 300
C (see Table 3). However, a larger CO reaction
3.1. Kinetics of wateregas shift reaction over SSC1 order (0.75  0.12) was found in this study compared to that
(0.52) from Srivatsa and Weller [16]. This may be due to the
For the design and optimization of WGS reactors, an essential different temperatures and gas compositions used in the two
piece of information is the kinetics of the WGS reaction. A different studies.
number of different kinetic rate expressions have been Apparent activation energy was determined by means of
proposed [17e25] and tested to evaluate the WGS reaction. An an experiment where the reactor temperature was slowly
excellent review on WGS reaction kinetics [26] concluded that ramped from 350 to 450
C with simulated dry-feed coal-

ln P (kPa)
3.6 3.8 4.0 4.2
Table 2 e Experimental inlet gas composition (dry basis)
ln [rate/(1-β)], (mol gcat 1s 1)
ln [rate/(1-β)], (mol gcat 1s 1)

tested with a constant level of H2S and constant wet gas -13.41
−
−

-11.0 CO2
velocity.
−
−

-11.2
Conditions CO H2 CO2 N2 H2 -13.44
(% d.b.) (% d.b.) (% d.b.) (% d.b.)
-11.4
dry-feed coal-derived syngas 65 30 2 3 -13.47
-11.6
slurry-feed coal-derived 44 37 16 3
H2O
syngas -13.50
-11.8 CO
backend of catalytic 7 12 78 3
membrane reactor -12.0 -13.53
(retentate side)
backend of WGS reactor 4 55 38 3 1.0 1.5 2.0 2.5 3.0
ln P (kPa)
Weight of SSC1 samples ¼ 1.2g.
Constant wet gas velocity ¼ 79.7 cm s1 at 450
C and 1 atm. Fig. 1 e Determination of powerelaw rate model reaction
H2O:C ratio (constant for all conditions) ¼ 3.
orders: Logelog plots for the effect of CO, CO2, H2O and H2
Inlet H2S concentration (w.b.) ¼ 1000 ppm.
partial pressure on reaction rates over SSC1.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 6 6 3 8 e6 6 4 5 6641

Table 3 e Calculated powerelaw model parameters for the WGS reaction over SSC1 compared with other commercial SS
and HT catalysts.
Catalyst Apparent reaction orders E (kJ mol1) Sources

a [CO] b [H2O] c [CO2] d [H2]

a
SSC1 0.75  0.12 0.31  0.08 0.07  0.02 0.09  0.02 60.3  1.3 This study
Commercial sulfided Co/Mo catalyst. 0.52 0.21 0.10 not considered not reported Srivatsa & Weller [16]
HTC1 1.00  0.03 0.0 0.36  0.04 0.09  0.007 111  2.6 Our previous study [3]
HTC2 0.90  0.04 0.31  0.06 0.16  0.08 0.05  0.006 88  2.2 Our previous study [3]
Fe-Cr oxide based catalyst 0.81 0.024 0.16 0.044 100 Podolski & Kim [26]
Rhodium promoted Fe-Cr oxide catalyst 1.45 0.44 0.12 0.22 63 Lei et al. [28]
Commercial Fe-Cr oxide based catalyst 0.9 (0.8e1.0) 0.25 (0.2e0.35) 0.6 (e0.5 toe0.65) 0.0 115 Bohlbro [31]

a  values in Table 3 represent the 95% confidence interval of the values of slope of the plots presented in Fig. 1.

derived syngas. The heating rate used in this experiment was These experiments were carried out using a reactor tube of
0.5
C min1 which was slow enough to investigate the effect 13 mm inside diameter with a constant wet gas velocity of
of temperature on CO conversion rate. An average tempera- 79.7 cm s1 at 450
C and atmospheric pressure. It can be seen
ture during GC sampling time was defined as the operating that WGS reaction rates over SSC1 are an order of magnitude
temperature for a particular gas sample. Fig. 2 shows the plot less than those measured over HTC1 and HTC2 in all cases. It
of the logarithmic values of CO conversion rates versus should be noted that the performances of the HT catalysts
inverse temperature. This Arrhenius plot is found to be linear presented in Fig. 3 are for a sulfur-free gas stream and the
indicating that experiments were conducted under differen- performances of the SSC1 catalyst presented in Fig. 3 are only
tial reactor conditions where mass transport limitations are those obtained for the inlet gases containing a constant level
not significant. To obtain the apparent activation energy, the of H2S (1000 ppm on a wet basis). The performance of SSC1
gradient (E/R) of the linear Arrhenius plot was determined under inlet gas compositions containing different H2S
using the linear least-squares method. It was found to be concentrations was also investigated and the results are pre-
7250, which gives an apparent activation energy of 60.3 kJ sented in the next section.
mol1. The pre-exponential factor was then calculated using When SSC1 catalytic activities are compared at different
the values of the reaction orders and activation energy. The inlet gas compositions, it is found that the highest CO
kinetics of the WGS reaction over SSC1 at 450
C and atmo- conversion is achieved with a dry-feed coal-derived syngas
spheric pressure under selected inlet conditions can therefore composition where inlet gas CO content is highest and CO2
be described by the following powerelaw rate expression: content is lowest. The lowest CO conversion is found with the

 
60:3  1:3 0:750:12 0:310:08 0:070:02 0:090:02
R ¼ 0:008  0:0004exp 0
PCO PH2 O PCO2 PH2 ð1  bÞ (1)
RT

for T ¼ 450
C (723 K). backend of WGS reactor gas composition where inlet gas CO
where R0 ¼ 8.3144  103 kJ mol1 K1 content is lowest and H2 content is highest (see Fig. 3). These
b is defined as results are similar to the patterns observed with HTC1 and
b ¼ 1=K,PCO2 PH2 =PCO PH2 O , where K is the equilibrium HTC2.
constant for the WGS reaction. The reaction orders with respect to CO, H2O, CO2 and H2
The values of b in our experiments were in the range of over SSC1 presented in Section 3.1 are listed in Table 3
0.0002e0.07, which indicates that the reaction was carried out together with the reaction orders reported in the literature
far from equilibrium. for the WGS reaction over Fe based catalysts. From Table 3 it
can be seen that, except for CO2, the reaction orders over SSC1
3.2. Comparison between sour shift catalyst (SSC1) & are similar to those for the high-temperature catalysts, espe-
high temperature catalysts cially HTC2 and a commercial FeeCr based HT catalyst
investigated by Bohlbro [31]. The lower CO reaction order of
The performance of SSC1 at the four selected inlet gas SSC1 (0.75) means that its reaction rate has a lower depen-
compositions is shown in Fig. 3 and is compared with the dence on CO concentration than the high temperature cata-
performance of two high temperature catalysts at the same lysts (HTC1 & HTC2) for which the CO reaction orders were 1.0
experimental conditions as reported previously [3]. It should and 0.9 respectively. The reaction rate is retarded by
be noted that the data presented in Fig. 3 represent the last 30 increasing CO2 and H2 concentrations (reaction orders are
data points (interval between each data point was approxi- negative) due to the reverse WGS reaction. From Table 3 it can
mately 3 min) of each experimental run when the reactor was be seen that CO2 reaction order is significantly less negative in
running under steady state conditions. Upper and lower the case of SSC1 compared with those for the high tempera-
confidence limits were calculated at a 95% confidence level. ture catalysts.
6642 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 6 6 3 8 e6 6 4 5

3.3. Effect of H2S concentration on the performance of

-11.6 SSC1
ln (rate, mol gcat 1 s 1)

To investigate the effect of H2S on the performance of the

−

-12.0 SSC1 catalyst at 450
C, a series of experiments were carried

−

out using the dry-feed coal-derived syngas containing H2S

concentrations ranging from 330 ppm to 2670 ppm on a wet
basis (10008000 ppm on a dry basis). It has to be noted that
-12.4
experiments presented in this section were conducted using
a slightly larger reactor tube of 15 mm inner diameter; the
calculated wet gas velocity was 55.1 cm s1 at 450
C and
-12.8
approximately atmospheric pressure.
The CO conversion rates over SSC1 using simulated dry-
feed coal-derived syngas containing various levels of H2S at
-13.2
450
C are presented in Fig. 4. The catalyst was stabilised
0.0014 0.0015 0.0016
during the first 15 h under a base case gas composition: in this
−
Reciprocal temperature, 1/T (K 1) experiment base case is defined as a dry-feed coal-derived
syngas composition with 1000 ppm (w.b.) of H2S which is the
Fig. 2 e Arrhenius plot for the WGS reaction over SSC1 same gas composition used in the kinetics study and perfor-
using dry-feed coal-derived syngas at 1atm, 350
CL450
C mance tests of SSC1. The inlet concentration of H2S was then
and steam:carbon ratio of 3. lowered to 670 and 330 ppm, before being increased back to
1000 ppm (w.b.). The test was then continued with higher
levels of H2S at concentrations of 1330 ppm, 1670 pmm,
2000 ppm and 2670 ppm. Finally the performance of SSC1 at
If we consider the effects of the reaction orders only, we
the base case was measured again. Each condition at
may conclude that SSC1 would be suited to a membrane
a particular concentration of H2S in the feed gas was run for
reactor application where the CO concentrations are low and
515 h before another H2S level was introduced.
the resultant high CO2 concentrations would have less impact
Fig. 4 shows that a stable and steady CO conversion level
on the CO conversion rate than for the conventional high
was quickly achieved at each H2S concentration. From Fig. 4, it
temperature catalysts. However, it has to be noted that the
is very clear that the performance of SSC1 was significantly
overall performance of SSC1 is significantly lower than those
enhanced with the increasing H2S concentration. It is
of the high temperature catalysts as shown in Fig. 3. As dis-
observed that the activity of SSC1 quickly dropped back to its
cussed in the previous study [3], H2O reaction order deter-
initial activity level when H2S level in feed gas was reduced to
mined using HTC2 was found to be significantly positive even
the base case value of 1000 ppm (activity of SSC1 for the base
at high H2O: carbon ratios, unlike the case for HTC1, where the
case is highlighted by a dashed line in Fig. 4). This behavior is
effect of changes in H2O concentration was insignificant (i.e.
totally contradictory to what was observed with the HT cata-
zero order). SSC1 was found to have the same order with
lysts, the activities of which were reduced by H2S-containing
respect to H2O concentration as HTC2.
feed gas [6]. From Fig. 4, it can be seen that the performance of
SSC1 depends significantly on the concentration of H2S in the
1.6e-4
CO conversion rate (mol gcat 1 s 1)

syngas. At higher concentrations of H2S in the feed gas (at

−

HTC1 w1330 ppm and at w2670 ppm), the catalyst activity increases
−

2e3 times respectively compared to its activity at the lowest

1.2e-4 HTC2

SSC1

8.0e-5 2670 ppm

25 2000 ppm
CO conversion (%)

1670 ppm
20 1330 ppm
1000 ppm 1000 ppm
4.0e-5 1000 ppm
15

10
0.0
dry-feed slurry-feed backend of backend of 670 ppm
syngas syngas membrane WGS reactor
5
reactor 330 ppm
Inlet gas compostion 0
0 20 40 60 80 100
Fig. 3 e Comparison between performance of SSC1 (under
Time (hr)
a constant level of H2S 1000 ppm w.b) and HT catalysts
(under sulfur-free gas stream) with four selected gas Fig. 4 e Performance of SSC1 at various concentrations of
compositions (temperature [ 450
C, pressure z1 atm, wet H2S (330e2670 ppm w.b.) in the simulated dry-feed coal-
gas velocity [ 79.7 cmsL1 and steam:carbon ratio of 3). derived syngas at 450
C and at approximately 1 atm.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 6 6 3 8 e6 6 4 5 6643

concentration of H2S tested (340 ppm). This highlights the

Reaction rate (mol gcat 1s 1)

2.0e-4

−
necessity of maintaining a minimum level of H2S in the syngas HTC2

−
to keep the sour shift catalyst at a sufficient level of activity. SSC1
1.5e-4
Frank [12] reported that a total sulfur content above 550 ppmv
is required to keep a sulfided catalyst active under the spec-
1.0e-4
ified process conditions and at a temperature of about 440
C.
Fig. 4 shows that the increase in CO conversion rate is
5.0e-5
proportional to the concentration of H2S added. A graph of ln
[CO conversion rate] versus ln [H2S concentration] is plotted in
Fig. 5. It can be seen that the slope of this plot is linear over the 0.0

1000 ppm

1670 ppm
0 ppm
50 ppm
120 ppm

330 ppm
450 ppm

1100 ppm
1330 ppm

2000 ppm
2670 ppm
250 ppm

670 ppm
700 ppm
whole range of H2S concentrations tested. This indicates that
an empirical powerelaw method can be used to interpret the
effect of H2S on the performance of SSC1 catalyst and it can be
H2S concentration (ppm on w.b.)
expressed using a correlation of the form:
Fig. 6 e Comparison between performance of SSC1 and
R ¼ A½H2 Sn (2)
HTC2 catalyst on dry-feed coal-derived syngas containing
where R is reaction rate, A is a constant related to the catalyst different levels of H2S (temperature [ 450
C,
and the experimental conditions used, and n is the H2S reac- pressure z 1 atm, wet gas velocity [ 55.1 cm sL1 and
tion order with respect to H2S concentration. The reaction steam:carbon ratio of 3).
order with respect to H2S concentration in the feed gas over
SSC1 was calculated to be 0.52  0.02 for the range of H2S
concentrations tested (330 ppme2670 ppm).
Fig. 6 shows the performance of SSC1 at various levels of
similar levels of H2S-containing syngas. Fig. 6 shows that
H2S concentration from this study compared with the
the activity of SSC1 under a gas stream containing 1330 ppm
performances of HTC2 at a range of H2S concentrations
of H2S at 450
C was 25% higher than the activity of HTC2
reported in our previous study [6]. These two sets of
under a gas stream containing 1100 ppm of H2S at the same
experiments were carried out under the same experimental
operating conditions. For dry-feed coal-derived syngas
conditions (i.e. temperature ¼ 450
C, pressure z 1 atm, wet
with lower concentrations of H2S (<500 ppm), the perfor-
gas velocity ¼ 55.1 cm s1 and steam:carbon ratio of 3). As
mance of HTC2 was found to be significantly higher than
we discussed in Section 3.2, the level of activity of HTC2 in
that of SSC1.
a sulfur-free reaction stream is much higher than the
From Fig. 6, it can be generally concluded that sour shift
performance of SSC1 in the base case gas stream containing
catalysts have advantage over HT catalysts when coal-derived
1000 ppm of H2S. However, when the two catalysts activities
syngas contains levels of H2S greater than 1000 ppm on a wet
are compared in sulfur-containing gas streams, it was
basis. However, maintaining such a level of sulfur in the gas
observed that SSC1 has a better performance in the dry-feed
stream in coal-based gasification systems is impractical,
coal-derived syngas with high concentrations of H2S
particularly when the plant is operating on low-sulfur coals. In
(>1000 ppm) compared to the performance of HTC2 under
addition, the wet basis H2S concentration in the syngas will be
reduced after additional steam is added to promote the
WGS reaction rate. Therefore, using sour shift catalysts for
ln [CO conversion rate, mol gcat 1 s 1]

enhancing the WGS reaction could be a better option only if

−

-9.4
the minimum sulfur content in the syngas were kept above
−

-9.6 1000 ppmv in the WGS reactor to ensure that a consistently

high CO conversion rate is achieved. It has to be noted that
-9.8 this conclusion has been drawn without considering the fact
that there are also some drawbacks in the process of handling
-10.0
high levels of sulfur-containing gas streams, such as corrosion
-10.2 n =0.52 ± 0.02 in equipment and instrumentation.

-10.4

-10.6 4. Conclusions

-10.8 The present work is a continuation of our previous study

5.5 6.0 6.5 7.0 7.5 8.0 focusing on assessing the performance of commercially-
ln [H2S in ppm (w.b.)] available WGS catalysts for their suitability to process coal-
derived syngases. The ultimate purpose of this research is to
Fig. 5 e Logelog plot for the effect of H2S concentration on generate power with low production of greenhouse gas
reaction rates over SSC1 using the simulated dry-feed coal- emissions. In this study, a detailed kinetics study of the WGS
derived syngas at 450
C, approximately 1 atm and H2O:C reaction over a sour shift catalyst was carried out under
ratio of 3. a constant wet gas velocity at 450
C with a constant level of
6644 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 6 6 3 8 e6 6 4 5

H2S (1000 ppm on a wet basis), using a powerelaw rate performance of an iron/chromium-based high-temperature
equation with six parameters to describe the observed wateregas shift catalyst using simulated coal-derived
kinetics. The reaction orders with respect to CO, H2O, CO2 syngas. Catal Commun 2009;10:967e70.
[7] Park J-N, Kim J-H, Lee H-I. A study on the sulfur-resistant
and H2 over SSC1 are found to be similar to those previously
catalysts for water gas shift reaction III. Modification of Mo/
measured with an HT catalyst (HTC2). The performance of g-Al2O3 catalyst with iron group metals. Bull Korean Chem
SSC1 was investigated using four selected gas inlet compo- Soc 2000;21:1233e8.
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with a dry-feed coal-derived syngas composition where inlet 25e38.
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forms for wateregas shift reactin on NiMoeSulfide catalysts.
The effect of H2S on the performance of SSC1 was inves-
Appl Catal A Gen 1999;179:223e8.
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enhanced by the presence of H2S. This behavior is contrary to water gas shift reaction II. Effect of alkali metal salt on the
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Acknowledgment low-temperature water-gas shift reaction on the catalyst
oxygen activity as investigated by wavefront analysis. J Catal
The authors wish to acknowledge the support provided 1983;80:328e39.
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