+ +

Ind. Eng. Chem. Res. 1996, 35, 2531-2538 2531

Microkinetics of Water-Gas Shift over Sulfided Mo/Al2O3 Catalysts

Carl R. F. Lund
Chemical Engineering Department, SUNYsBuffalo, Buffalo, New York 14260

A microkinetic model was developed to explain the catalysis of the water-gas shift reaction by
sulfided, alumina-supported molybdenum. In this model, the reaction takes place through a
regenerative (reduction-oxidation) scheme wherein the catalyst surface is alternately oxidized
by water and then reduced by carbon monoxide. The surface of the catalyst is equilibrated
with gas-phase H2S under all reaction conditions studied. Coverages predicted by the model
are consistent with the adsorption behavior of molybdenum sulfide catalysts. Simulations
indicate that the effects of steam and H2S levels are closely related. A maximum in CO
conversion with increasing steam level may only occur at certain H2S levels, and the ordering
of CO conversion with increasing H2S levels may invert as the steam level is changed.

There are two main classes of water-gas shift cata-
lysts that are used commercially: high-temperature
catalysts (typically oxides of iron and chromium) and
low-temperature catalysts (typically copper and zinc
based). It is also well established that supported,
promoted molybdenum sulfides are active shift catalysts
(Newsome, 1980). This paper describes a microkinetic
model for the catalytic activity of sulfided Mo/Al2O3
catalysts for water-gas shift. Sulfur-tolerant water-
gas shift (wgs) catalysts are very similar to catalysts
used for hydrodesulfurization, so that mechanistic
knowledge about water-gas shift over these catalysts
may provide some insight into hydrodesulfurization
catalysis. The present results will also provide a basis
for future comparison to sulfided CoMo/Al2O3 catalysts
for wgs.
There are few published studies of wgs using sulfided
Mo/Al2O3 as a catalyst. Hou et al. (1983) found that
the catalyst was inactive in the oxide form. ESCA
analysis of sulfided catalysts revealed that the Mo(V)
to Mo(IV) ratio changed as the ratio of H2S to H2 was
varied. As the mole fraction of H2S present in the feed
was increased, the catalytic activity also increased (over
the range up to 5000 ppm H2S). This led the authors
to suggest that one sulfur ligand could rapidly exchange
for an oxygen ligand as in eq 1. The oxygen ligands
so-generated were then proposed to participate in a
redox cycle wherein CO removes the ligand and water
replaces it (eqs 2 and 3). The observed rate passed
S2– S– S2– O–
Mo5+ + H2O Mo5+ + H2S
S2– O– S2–
Mo5+ + CO Mo4+ + CO2
S2– S2–
O–
Mo4+ + H2O Mo5+ + H2
from ammonium heptamolybdate and from molybde-
num hexacarbonyl precursors. The latter were more
active, but this may largely be due to differences in the
percentage of Mo exposed. In the more active carbonyl-
based catalyst, the Mo(V) state was not detected via XPS
either in the catalyst as prepared or upon exposure to
water. (Hou et al. (1983) observed it in their catalysts
after sulfidation, i.e., even before exposure to reaction
conditions.) This suggests that a mechanistic scheme
like that above may not be operative over the zeolite
catalysts. Alternatively, Mo(V) could still be catalyti-
cally important, but it might only form under reaction
conditions or its concentration might be very small for
these highly dispersed catalysts.
Spillman (1988) also studied wgs kinetics over sul-
fided Mo/Al2O3 catalysts using a “spinning basket”, fully
mixed reactor. Since this study has only been reported
in the form of a Master’s thesis, it will be described here
in more detail than usual. The Mo/Al2O3 was prepared
by incipient wetness impregnation of Davidson γ-alu-
mina (ground to 20-60 mesh) with an aqueous solution
of ammonium heptamolybdate to produce a loading of
15 wt % (as MoO3). The impregnated catalyst was
vacuum dried at 80 °C for 3 h and subsequently calcined
at 500 °C in air for 6 h. In a typical experiment the
catalyst was pretreated in 14.6% H2S, balance H2, while
heating to 300 °C and then for an additional 2 h during
which the temperature was held constant. The reactor
was then purged with N2 for 1-h at the same temper-
ature. The feed composition was next adjusted while
bypassing the reactor, and the temperature was stabi-
(1) lized at the desired level. Temperatures of 250, 275,
and 300 °C and pressures of 5 and 15 atm were
employed. The gas hourly space velocity was 24 000 h-1
in each of the 72 experimental runs.
(2) During Spillman’s kinetic measurements the feed
always contained H2S; its concentration was 1% by
volume. The reactor would be run for 1-2 h at steady
state, and then the feed composition was changed. The
(3)
kinetics were described using rate expressions of the
power-law type given in eq 4. In eq 4 Kwgs represents

[ ]
through a maximum as the steam feed rate was PCO2PH2
increased. The authors noted that a simple Langmuir- r ) k0e-E/RTPCOaPH2ObPCO2c 1 - (4)
Hinshelwood mechanism involving competitive adsorp- KwgsPCOPH2O
tion of CO and H2O could explain this observation.
They did not totally reconcile this suggestion with the the equilibrium constant for the overall reaction, and
mechanism of eqs 2 and 3. The apparent activation Pi represents the partial pressure of species i. The data
energy over the catalyst was 12.8 kcal mol-1. at 5 atm were fit separately from those at 15 atm. Table
In another study (Laniecki and Zmierczak, 1991), 1 presents the values of the resulting power-law kinetic
sulfided, Mo-impregnated Y zeolite was prepared both parameters.
+ +
2532 Ind. Eng. Chem. Res., Vol. 35, No. 8, 1996
Table 1. Power-Law Kinetic Model Parametersa
catalyst (pressure) k0 E a b c
Mo/Al2O3 (5 atm) 6.3 5.27 0.7 0.14 0.0
Mo/Al2O3 (15 atm) 6.0 5.95 0.8 0.29 -0.07
a Parameters are defined by eq 4, k has units of mol h-1 g-1
0 reported. In another study using a supported catalyst
atm-(a+b+c), and E has units of kcal mol-1. All values are from
Spillman (1988).
In the present study Spillman’s data have been
reanalyzed using the microkinetic analysis method
suggested by Dumesic et al. (Dumesic et al., 1987, 1993).
The objectives of the study were, first, to determine
whether the previously mentioned mechanistic sugges-
tions remain valid at higher pressures (up to 15 atm
vs. 1 atm) and lower temperatures (∼550 K vs. ∼725
K); second, to analyze the resulting mechanistic net-
work; and, third, to establish a basis of comparison for
future microkinetic analysis of sulfided CoMo/Al2O3
catalysts for wgs.
Experimental Methods
Model Formulation. The suggestions by Hou et al.
(1983) form the basis of the mechanism investigated in
the present study. The mechanism incorporates a
regenerative (oxidation-reduction) process such as in
eqs 2 and 3, but via adsorbed species. For simplicity,
hereafter let * denote a vacant site which is envisioned
to be like the Mo(IV) species in eq 2 or eq 3. It is
assumed that adsorption takes place at the location of
the missing ligand so that *-S is equivalent to the
first species in eq 1 and *-O is equivalent to the
second.
The mechanism assumes that the catalyst is in a
sulfided state, but the spectroscopic data mentioned
previously suggest that the degree of surface sulfidation
may vary with conditions. Sulfhydryl groups are very
commonly observed on MoS2 (Maternová, 1982; Mater-
nová, 1983; Miciukiewicz et al., 1987). They are formed
by both the adsorption of H2S (Topsøe and Topsøe, 1993)
and the adsorption of H2 (Ratnasamy and Fripiat, 1970;
Massoth, 1975, 1978; Wright et al., 1980). Therefore,
the sulfidation pathway given in reactions (5) and (6)
H2S + * + *-S a 2*-SH
2*-SH a 2*-S + H2
is included to account for variations in the degree of
surface sulfidation as reaction conditions change. The
associative adsorption of H2S followed by its surface
dissociation could have been used in place of reaction
(5), but this would have introduced additional unknown
parameters. Furthermore, the molecular adsorption of
H2S is expected to be weak, and Spillman’s data (used
here in the kinetic modeling) were collected at a single
H2S level, making it difficult to justify the added
mechanistic complexity. It should be noted that reac-
tions (5) and (6) require a pair site for the adsorption of
H2S, limiting the applicability of the mechanism. In
particular, if a surface initially consisted of 100% vacant
sites, it could not become sulfided upon exposure to H2S
according to these reactions because there would be
none of the *-S sites that are necessary for reaction
(5). Thus, as already noted, the mechanism investigated
in this study assumes the catalyst is in a sulfided state.
The oxidative pathway was constructed largely by
analogy to the sulfidation pathway above. It is assumed
that adsorption of H2O will be similar to that of H2S.
hydroxyl signal associated with the support. In one
infrared study of unsupported MoS2 (Ratnasamy and
Fripiat, 1970), the adsorption of water did not affect the
frequency of the SH band, but adsorbed water or
hydroxyls are not mentioned and the spectrum is not
(Topsøe, 1980), it is noted that the hydroxyl absorption
band disappears as the MoS2 loading increases to the
point of monolayer coverage of the support. These
spectroscopic studies thus suggest that if hydroxyl
groups do exist on the sulfide (not the support), then
they must be present in very low concentrations since
they are not detectable by infrared spectroscopy. It will
be seen that the results of the present study also
indicate that surface hydroxyl groups are present in
very low concentration under reaction conditions. None-
theless, by analogy with the sulfidation steps above, the
oxidative pathway is represented by reactions (7)-(10).
In addition, reactions (11) and (12) are included to allow
for sulfidation of an oxidized catalyst.
H2O + * + *-S a *-SH + *-OH (7)
H2O + * + *-O a 2*-OH (8)
2*-OH a 2*-O + H2 (9)
*-OH + *-SH a *-O + *-S + H2 (10)
H2S + * + *-O a *-SH + *-OH (11)
*-S + *-OH a *-SH + *-O (12)
The formulation of the reductive pathway was guided
by the chemisorption behavior of the carbon oxides on
MoS2. CO is known to adsorb on MoS2 with a relatively
weak bond (Maugé and Lavalley, 1992). In fact, it has
been suggested that CO adsorption can be used to titrate
exposed MoS2 sites (Bachelier et al., 1981, 1984). The
low-temperature chemisorption of oxygen is more com-
monly used for this titration even though it has been
shown to be corrosive (oxidize into the bulk) at subam-
bient temperatures (Tauster and Riley, 1981; Zmierczak
et al., 1982; Kalthod, 1984; Muralidhar et al., 1984). The
(5) adsorption of NO is also commonly used for MoS2
titration (Topsøe and Topsøe, 1983; Miciukiewicz et al.,
(6) 1987), but again there is some concern that this process
may be corrosive (Prins et al., 1989). CO2, on the other
hand, does not chemisorb on MoS2 (Zmierczak et al.,
1987). Indeed, since CO2 does adsorb on Al2O3, one
method for measuring the fraction of the support
covered by the sulfide uses the difference between the
uptake on the catalyst and the uptake on the support
only.
In constructing a reductive pathway, it is difficult to
simultaneously satisfy the observations that CO adsorbs
while CO2 does not adsorb. Ultimately, a Langmuir-
Hinshelwood reductive pathway, reactions (13)-(15),
was used in the model with the expectation that the
concentration of adsorbed CO2 (and probably adsorbed
CO, too) would be small. While formates have also been
CO + * a *-CO (13)
*-CO + *-O a *-CO2 + * (14)
*-CO2 a * + CO2 (15)
reported as intermediates in wgs over some catalysts
+ +
Figure 1. Reaction network used to model the water-gas shift
reaction. Surface species are indicated by rounded rectangles.
Locations where gaseous species enter the network are denoted
by ovals, and equation numbers for reaction steps are given in
parentheses.
these species were not added to the mechanism since
there is no spectroscopic evidence for their existence on
sulfides and they would introduce additional unknown
parameters to the kinetic model. The mechanistic
network is summarized in Figure 1.
Microkinetic Analysis. The microkinetic analysis
involved several steps (Dumesic et al., 1993). First,
heats and entropies of formation of all species as if they
existed in the gas phase were determined at a reference
temperature of 500 K (Chase et al., 1985). For surface
species the strengths of their bonds to the surface, Ei-s,
were introduced as adjustable model parameters as
given in eq 16. It was assumed in the present study
∆Hf(surf)-i ) ∆Hf(gas)-i - Ei-s (16)
that adsorption caused the loss of all translational
entropy so that the entropy of formation of surface
species was given by eq 17. (The entropy values
∆Sf(surf)-i ) ∆Sf(gas)-i - Strans-i
[ ( )]
5 (2πmkBT)3/2v
) ∆Sf(gas)-i - R + ln (17)
2 h3
estimated in this way were only used to calculate the
reverse preexponential factors once the forward preex-
ponentials had been selected. This is done simply to
ensure that the reaction rate predicted by the model will
equal zero at equilibrium at the reference temperature.)
Having heats and entropies of formation of all species
(gas and surface), the heats and entropy changes for
each reaction in the mechanism were calculated.
For each step j in the reaction mechanism four kinetic
parameters are needed: a preexponential factor and an
activation energy for both the forward and reverse
reactions. The forward preexponential factors, Aj-forward,
were estimated on the basis of transition state theory
(Zhdanov et al., 1988; Dumesic et al., 1993). If no
assumptions are made regarding the ideality of the gas
phase, the rate expression for adsorption steps can take
the form of eq 18,where θv denotes the fraction of surface
dθi/dt ) kadsfiθv (18)
Ind. Eng. Chem. Res., Vol. 35, No. 8, 1996 2533
Table 2. Estimated Preexponential Factors Used in the
Microkinetic Modelinga
reaction Aforward (s-1) Areverse (s-1)
H2S + * + *-S a 2*-SH 1.0 × 106 2.55 × 1012
2*-SH a 2*-S + H2 1.0 × 1013 5.17 × 108
H2O + * + *-S a *-SH + *-OH 1.0 × 106 5.44 × 1011
H2O + * + *-O a 2*-OH 1.0 × 106 1.08 × 1012
2*-OH a 2*-O + H2 1.0 × 1013 1.30 × 108
*-OH + *-SH a *-O + *-S + H2 1.0 × 1013 2.59 × 108
H2S + * + *-O a *-SH + *-OH 1.0 × 106 5.08 × 1012
*-S + *-OH a *-SH + *-O 1.0 × 1013 5.02 × 1012
CO + * a *-CO 1.0 × 106 2.16 × 1013
*-CO + *-O a *-CO2 + * 1.0 × 1013 1.47 × 1014
*-CO2 a * + CO2 1.0 × 1013 2.35 × 105
a If ideal gas behavior is assumed, the preexponential factors
for adsorption steps may be taken to have units of atm-1 s-1; with
this assumption the fugacity in eq 18 should be replaced with the
partial pressure in units of atm.
i adsorbed on them, k is the rate coefficient, and fi is
the fugacity of gas phase species i. This is the form for
which the preexponential factors were estimated; in this
form they have units of reciprocal seconds. The reverse
preexponential factors, Aj-reverse, were then calculated
by application of the equilibrium criterion (eq 19), evalu-
Aj-reverse ) Aj-forward exp(-∆S0j /R) (19)
ating ∆S0j at the reference temperature of 500 K. In
the present investigation the preexponentials were not
varied from these initial guesses, which are listed in
Table 2.
Other adjustable model parameters, Rj and βj, were
introduced to calculate the activation energies. The
activation energy for step j in the exothermic direction,
Ej-exothermic, was calculated using the Evans-Polanyi
kinetic correlation (eq 20). The activation energy in the
Ej-exothermic ) Rj + βj∆Hj (20)
endothermic direction was then calculated using eq 21.
Ej-endothermic ) Ej-exothermic - ∆Hj (21)
One set of Evans-Polanyi parameters, Rox and βox,
was used for all the steps in both the oxidative and
sulfidation pathways, reactions (5)-(12). A second set
of Evans-Polanyi parameters, Rred and βred, was used
for the reductive pathway, reactions (13)-(15). The
parameter β is typically near 0.5; here it was con-
strained to lie between 0.2 and 0.8 because values
outside this range lead to unreasonable values for the
kinetic parameters. In total there were 10 adjustable
model parameters: Rred, Rox, βred, βox, and the surface
bond strengths for S, SH, O, OH, CO, and CO2.
Once the kinetic parameters were calculated for each
mechanistic step, the reactor analysis was performed.
The reactor was assumed to be perfectly mixed and to
be operating at steady state. For any one kinetic
experiment the set variables, i.e., the total inlet volu-
metric flow rate (sccm), νin; the inlet mole fractions, φin-i,
of all gas-phase species i (i ) 1 through NG where NG
is the number of gas-phase species); the mass of catalyst
in the reactor (g), mcat; the site density of the catalyst
(sites/g), Fsites; the temperature (K), T; and the pressure
(atm), P, were known. (The site density was taken to
be 1.34 × 1019 g-1 based upon low-temperature oxygen
chemisorption on a catalyst prepared in the same
manner as Spillman’s (Kalthod, 1984).) The outlet mole
fractions, xi, of all gas-phase species i (i ) 1 through
+ +

2534 Ind. Eng. Chem. Res., Vol. 35, No. 8, 1996

species (i ) NG + 1 through NS, where NS is the total
number of species in the mechanismsincluding vacant
sites); and the outlet total volumetric flow rate needed
to be calculated. These response variables (the outlet
flow rate was used in dimensionless form, xNS+1 ) νout/
νin) were calculated from mole balances on all but one
gas-phase species (eq 22), mole balances on all but one
surface species (eq 23), and a total mole balance (eq 24)
and the requirements that the sum of the mole fractions
by unity (eq 25) and the sum of the surface coverages
be unity (eq 26).
of its value, so in such cases the value was changed to
1 kcal/mol.) This sensitivity analysis was performed for
each model parameter that was adjustable for the
purpose of fitting; it was also performed for every kinetic
parameter (preexponential factors and activation ener-
gies). A sensitivity factor for a particular parameter j,
Sj, was then calculated according to eq 29, where ψ0 is
Sj ) |
ψj - ψ0
ψj | (29)

mcatFsitesVstp the value of the objective function with all parameters

0 ) xixNS+1 - φin-i - rnet-i 1eie at their “best” values and ψj is its value when parameter
Nνin j is changed as described above. Sj will approach 0 when
NG - 1 (22) parameter j has little impact upon the value of ψ, and
it will approach unity when the quality of the fit is
0 ) rnet-i NG + 1 e i e NS - 1 (23) highly sensitive to parameter j.
A “network analysis” was also performed on the
mcatFsitesVstp NG mechanistic scheme. For this analysis representative
0 ) xNS+1 - 1 -
Nνin
∑
( rnet-i) (24) reaction conditions were selected. The absolute forward
i)1 rate and the absolute reverse rate of each step in the
mechanistic scheme were calculated at these reaction
NG
conditions. If the net rate of any one step was less than
0)( ∑
i)1
xi) - 1 (25) 1% of the smaller of the forward and reverse absolute
rates, that step was identified as being at quasi-
NS
equilibrium. If the net rate of any one step was greater
∑
than 99% of the larger of the forward and reverse
0)( xi) - 1 (26) absolute rates, that step was identified as being ir-
i)NG+1
reversible in that direction. If both the forward and
The net rate with respect to species i, rnet-i, appearing reverse absolute rates for any one step were less than
in eqs 22-26 is defined in eq 27, where νij is the the average of the net rates of all steps by 4 orders of
magnitude or more, that step was identified as being
NR NS NS kinetically insignificant. The absolute rates of the
rnet-i ) ∑
j)1
(νij[kj1Porj1( ∏
ν <0
xi-νij) - kj2Porj2(∏
ν >0
xiν )])
ij
individual steps were also used to calculate the absolute
rate of generation of each species and the absolute rate
ij ij
i)1 i)1 of consumption of each species. For intermediates in
(27)
the mechanistic scheme the absolute rate of generation
stoichiometric coefficient of species i in reaction j should equal the absolute rate of consumption (i.e., the
(negative for reactants and positive for products), kj1 and net rate of generation is zero). For stable species the
kj2 are the forward and reverse rate coefficients, respec- net rates of generation must be consistent with stoichi-
tively, P is the total pressure, and orj1 and orj2 are the ometry.
forward and reverse gas-phase reaction orders, respec-
tively. Equations 22-26 were solved using a globally Results
convergent Newton-Raphson method (Press et al.,
1992). Spillman originally fit power-law models to the data
For each experimental run k, solving eqs 22-26 used herein; the value of the sum of the squares of the
yielded the outlet CO mole fraction predicted by the errors (eq 28) was 2.06 × 10-3. The value for the
model, yCOp-k. An objective function ψ (eq 28) was microkinetic model is nearly the same, 3.14 × 10-3. The
fit using the microkinetic model is very good. Over a
Ndata total of 72 data, the largest absolute difference between
ψ) ∑ (yCO
k-1
m-k
- yCOp-k)2 (28) the predicted outlet CO mole fraction and the measured
value was 0.022 (0.413 vs 0.435). The largest relative
difference was 11.2% (0.0913 vs 0.0811).
defined as the sum over all Ndata experimental runs of The values of the model parameters and their sensi-
the squares of errors between the measured outlet mole tivity factors (eq 29) resulting from the fitting process
fractions of CO, yCOm-k, and the mole fraction predicted are given in Table 3. The parameters listed can be used
by the microkinetic model, yCOp-k. The model was fit to to calculate the activation energies given in Table 4
the data by varying the adjustable model parameters along with their sensitivity factors. Even though the
(surface bond strengths, R’s, and β’s) so as to minimize preexponential factors were not varied for the purpose
ψ. A downhill simplex method (Press et al., 1992) was of fitting the model to the data, sensitivity factors were,
used to find the minimum. All calculations were nonetheless, calculated for the preexponential factors.
performed on a PowerMacintosh 7100 personal com- The largest sensitivity factor was 0.0292, indicating that
puter. the model is not highly sensitive to any of these
When fitting was completed, a “sensitivity analysis” parameters. This, in part, justifies not varying the
was conducted to determine which parameters were preexponential factors during the fitting process.
most critical to the quality of the fit. The sensitivity to The fit of the model is most sensitive to the values of
a particular parameter was assessed by reducing that the O and OH surface bond strengths. In fact, all the
one parameter to 95% of its initial value and recomput- model parameters associated with the oxidative path-
ing the value of ψ. (A bond strength or activation way, except perhaps βox, have high sensitivity factors.
+ +

Ind. Eng. Chem. Res., Vol. 35, No. 8, 1996 2535

Table 3. Model Parameter Values and Sensitivities
Resulting from Fitting the Microkinetic Model to the
Experimental Data
parameter value sensitivity
objective function, ψ 0.00314
Rox (kcal/mol) 17.52 0.5898
βox 0.800a 0.2949
Rred (kcal/mol) 14.88 0.7020
βred 0.606 0.0500
*-S bond strength (kcal/mol) 73.8 0.6154
*-SH bond strength (kcal/mol) 49.6 0.8823
*-O bond strength (kcal/mol) 126.1 0.9925
*-OH bond strength (kcal/mol) 71.6 0.9356
*-CO bond strength (kcal/mol) 8.6 0.0007
*-CO2 bond strength (kcal/mol) 3.2 0.0436
a Value of the upper limit of the constrained range.
sensitivity factors for βred and the surface bond strengths
of CO and CO2 are low.
Discussion
Network analyses were performed for a feed consist-
ing of 33% CO, 67% H2O, and 1% H2S and using 2.0 g
of catalyst and a feed rate of 1500 sccm. Temperatures
of 250, 275, and 300 °C were analyzed at pressures of 5
and 15 atm for each temperature. In addition, analyses
were conducted at 300 °C and 15 atm with the same
feed and catalyst charge, but varying the feed rate
between 1000 and 3000 sccm so as to sample a range of
conversions. While there were systematic changes and
differences over this range of conditions, the relative
magnitude of surface coverages did not change, and the
same reactions were found to be equilibrated or ir-
reversible. Therefore, the reaction network will be
discussed in terms of the simulation at 275 °C and 15
atm using 2.0 g of catalyst and 1500 sccm of a feed
containing 33% CO, 67% H2O, and 1% H2S.
The surface coverages are reported in Table 5. It was
previously noted that for consistency with published
findings the fractional coverage of OH, CO, and CO2
should be small. The table shows that this requirement
has been satisfied by the model. Adsorbed oxygen
covers the largest fraction of the surface, and most of
the remainder is vacant. Adsorbed sulfur and sulfhy-
dryl groups cover on the order of 1% of the surface
according to the model. It should be noted, however,
that the data used in fitting the model all had the same
gas-phase H2S concentration. It would have been
preferable to have data where the H2S level was varied.
Table 6 provides the results of the network analysis
for the same reaction conditions. It can be seen from
the table that the net formation rate of each intermedi-
ate species is zero, as it must be. Also the net rates
with respect to the reactants and products are consistent
with the overall stoichiometry of the reaction. The
analysis indicates that H2S is equilibrated with the
surface at all the reaction conditions studied (reactions
(5), (11), and (12) are at quasi-equilibrium). In addition,
the adsorption of water via reactions (7) and (8) is
irreversible at all conditions studied. In most cases the
surface reaction between the carbon oxides, reaction
(14), is at a quasi-equilibrium; using the definition given
earlier there are a few situations (lower pressure and
lower temperature) where quasi-equilibrium is not
realized; however, the reaction remains highly revers-
ible in these situations.
The mechanism used here is basically the same as
that suggested by Hou et al. based upon experiments
at ca. 723 K and 1 atm. The present results show that
it can describe kinetics at significantly lower tempera-
tures (∼550 K) and higher pressures (up to 15 atm). Hou
et al. also observed, first, that the conversion of CO
increased monotonically as the concentration of H2S
increased and, second, that the CO conversion passed
through a maximum as the concentration of H2O was
increased. The microkinetic model was tested to see if
it was able to predict such phenomena.
Figure 2 shows a comparison between Hou et al.’s
data and a microkinetic simulation using the same
conditions. The simulation exhibits the proper trend,
with conversion increasing at greater H2S mole frac-
tions. The model underpredicts the experimental data
by a factor of 2-3, but this really is not bad considering
extrapolation involved. Specifically, the model has been
extrapolated over 150 K, 5 atm, and 5000 ppm H2S. In
addition, it was necessary to assume that the number
of active sites per gram was the same as for Spillman’s
catalyst. It should be noted that in this situation the
model is making predictions about the effect of changing
a variable (the H2S level) that was held constant during
the fitting process.
When a simulation was performed using the condi-
tions (733 K, 1 atm, and 2500 ppm H2S) where Hou et
al. saw a maximum in conversion while varying the
steam concentration, the average conversion level was
underpredicted by a factor of 2-4. Again, this agree-
ment is not bad considering the range of extrapolation.
However, the model predicted a monotonically increas-
ing CO conversion and not a maximum as was observed
experimentally. As a consequence, a number of simula-
tions were conducted at a variety of conditions. Figure
3 presents the results of three simulations, all at 548 K
and 5 atm, using 2.0 g of catalyst and 1500 sccm of a
feed containing 2.5% CO. The plots show the effect of
varying the inlet H2O mole fraction at three H2S levels.
The figure also replots Hou et al.’s data as an insert.
The results indicate that the appearance of a maximum
in the conversion while varying H2O level is also
dependent upon H2S level. The simulation using 5000
ppm H2S results in a curve with a shape quite remi-
niscent of Hou et al.; in contrast, by 2500 ppm the
maximum has nearly disappeared, and it is not seen at
1000 ppm.

Table 4. Activation Energies Calculated from the Model Parameters

Eforward (kcal/mol) sensitivity Ereverse (kcal/mol) sensitivity
H2S + * + *-S a 2*-SH 3.23 3.49 × 10-2 21.1 6.41 × 10-1
2*-SH a 2*-S + H2 20.7 6.22 × 10-1 4.703 7.59 × 10-2
H2O + * + *-S a *-SH + *-OH 7.93 1.98 × 10-1 19.9 2.95 × 10-3
H2O + * + *-O a 2*-OH 17.5 2.41 × 10-2 17.5 1.66 × 10-4
2*-OH a 2*-O + H2 11.2 1.49 × 10-2 19.1 8.73 × 10-3
*-OH + *-SH a *-O + *-S + H2 18.3 8.25 × 10-3 14.3 3.74 × 10-3
H2S + * + *-O a *-SH + *-OH 12.8 1.14 × 10-2 18.7 6.89 × 10-3
*-S + *-OH a *-SH + *-O 7.93 7.83 × 10-3 19.9 8.91 × 10-2
CO + * a *-CO 9.65 6.84 × 10-1 18.3 8.58 × 10-1
*-CO + *-O a *-CO2 + * 16.4 8.61 × 10-1 12.5 7.49 × 10-1
-1 -1
+ +

2536 Ind. Eng. Chem. Res., Vol. 35, No. 8, 1996

Table 5. Predicted Surface Coveragesa

fractional fractional
species surface coverage species surface coverages
S 1.18 × 10-3 CO 1.23 × 10-4
SH 1.54 × 10-2 CO2 6.76 × 10-7
O 7.27 × 10-1 vacant 2.56 × 10-1
OH 7.93 × 10-5
a Based upon a simulation at 275 °C and 15 atm using 2.0 g of

catalyst and 1500 sccm of a feed containing 33% CO, 67% H2O,
and 1% H2S.

Figure 3. Simulation showing the effect of steam level upon CO

conversion at 548 K and 5 atm for three different H2S levels. The
inlet CO mole fraction is 2.5%, and the balance is inert; the catalyst
mass is 2.0 g, and the total flow is 1500 sccm. The inset replots
results from Hou et al. (1983) at 733 K and 1 atm.

compete for the same sites on the surface. Figure 4

shows the coverages calculated as a function of inlet
steam level for the conditions of the 5000 ppm H2S
simulation. Since a network analysis did not indicate
any single step as rate determining, it is difficult to offer
a precise kinetic explanation for this effect: it is the
Figure 2. Effect of H2S level upon CO conversion as observed by
Hou et al. (1983) at 723 K and 1 atm compared to the prediction result of the interplay among all the mechanistic steps.
of the microkinetic model at the same conditions. The results in Figure 3 are also interesting in that
they predict that the effect of increasing the H2S level
Hou et al. attributed the maximum to competition for upon catalytic activity can invert if the amount of steam
sites between steam and carbon monoxide. It should is changed. The author is not aware of any reports to
be noted that according to the model both steam and this effect in the literature. It is, however, similar to
CO require a vacant site for adsorption; steam also effects observed when promoters are added to sulfided
requires an adjacent oxidized or sulfided site to allow CoMo/Al2O3 wgs catalysts (Spillman, 1988). When the
its dissociation into hydroxyl/sulfhydryl groups. Since promoter is added, the catalyst becomes more active
oxidized sites comprise most of the surface, it may be under some conditions but less active under others.
expected that virtually all vacant sites will have an The microkinetic model that has been generated in
adjacent oxidized site. Hence, steam and CO will indeed this investigation will serve as a basis for studying the
Table 6. Rates of Generation and Consumption of Species with Percentages Attributable to the Mechanistic Stepsa
percentage of rate via reaction
species type of rate rate (s-1) (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)
CO abs. generation 135.7 100.0
abs. consumption 137.6 100.0
net formation -1.97
H2O abs. generation 0.0083 91.53 8.47
abs. consumption 1.98 91.55 8.45
net formation -1.97
CO2 abs. generation 2.47 100.0
abs. consumption 0.494 100.0
net formation 1.97
H2 abs. generation 15.8 82.04 14.15 3.81
abs. consumption 13.8 82.10 14.09 3.81
net formation 1.97
H2S abs. generation 2.57 91.53 8.47
abs. consumption 2.57 91.55 8.45
net formation 0.0
*-S abs. generation 671 0.35 3.86 0.00 0.09 95.70
abs. consumption 671 0.35 3.38 0.27 0.08 95.92
*-SH abs. generation 673 0.70 3.36 0.27 0.08 0.03 95.56
abs. consumption 673 0.70 3.84 0.00 0.09 0.03 95.34
*-O abs. generation 903 0.00 0.49 0.07 0.02 71.24 28.17
abs. consumption 903 0.02 0.43 0.06 0.02 71.08 28.39
*-OH abs. generation 649 0.28 0.05 0.60 0.08 0.03 98.96
abs. consumption 649 0.00 0.00 0.69 0.09 0.03 99.18
*-CO abs. generation 392 35.10 64.90
abs. consumption 392 34.60 65.40
*-CO2 abs. generation 257 99.81 0.19
abs. consumption 257 99.04 0.96
* abs. generation 397 0.59 0.00 0.00 0.05 34.16 64.57 0.62
abs. consumption 397 0.59 0.46 0.04 0.05 34.65 64.08 0.12
a Based upon a simulation at 275 °C and 15 atm using 2.0 g of catalyst and 1500 sccm of a feed containing 33% CO, 67% H2O, and 1%
+ +
Figure 4. Predicted surface coverages for the simulation at 5000
ppm H2S shown in Figure 3.
effect of promoting sulfided Mo/Al2O3 wgs catalysts, first
by adding Co and then by additionally introducing K
or Pr. The approach that has been used may provide
some interesting interpretations of the effects of pro-
moters based upon changes in surface bond strengths.
Conclusions
A simple form of the kinetic scheme illustrated in
Figure 1 and given by eqs 5-15 was originally proposed
to explain wgs kinetics over sulfided Mo/Al2O3 catalysts.
Here it has been shown that such a mechanism can
explain the kinetics at significantly lower temperatures
and higher pressures than used in that original work.
The result also extrapolates back to the conditions used
in the study where the scheme was originally proposed
with reasonable accuracy. It is quantitatively off by a
factor of 2-4, but it captures the reported trends even
though data from that original study were not used here
in fitting the model. In capturing the essential kinetic
behavior observed upon varying steam and H2S levels,
the model further suggests that the interplay between
the two may be more complicated than previously
recognized. Under typical experimental conditions, the
catalyst surface is equilibrated with gas-phase H2S and
the adsorption of H2O is irreversible. Kinetics alone
cannot establish the model as correct, of course, and it
provides predictions of unreported kinetic behavior as
well as surface coverages under reaction conditions that
could be used in its further refinement.
Acknowledgment is made to the donors of the
Petroleum Research Fund, administered by the ACS,
for partial support of this research. The author ac-
knowledges Professor J. A. Dumesic (University of
WisconsinsMadison) for numerous helpful comments
and suggestions. Discussion with and comments by
Professor S. W. Weller and his students Dr. N. Srivatsa,
Dr. K. Keeler, and Mr. D. Spillman are also gratefully
acknowledged.
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Received for review October 4, 1995
Accepted May 17, 1996X
IE950608U
X Abstract published in Advance ACS Abstracts, July 1,
1996.