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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- from ammonium heptamolybdate and from molybde-
lysts that are used commercially: high-temperature num hexacarbonyl precursors. The latter were more
catalysts (typically oxides of iron and chromium) and active, but this may largely be due to differences in the
low-temperature catalysts (typically copper and zinc percentage of Mo exposed. In the more active carbonyl-
based). It is also well established that supported, based catalyst, the Mo(V) state was not detected via XPS
promoted molybdenum sulfides are active shift catalysts either in the catalyst as prepared or upon exposure to
(Newsome, 1980). This paper describes a microkinetic water. (Hou et al. (1983) observed it in their catalysts
model for the catalytic activity of sulfided Mo/Al2O3 after sulfidation, i.e., even before exposure to reaction
catalysts for water-gas shift. Sulfur-tolerant water- conditions.) This suggests that a mechanistic scheme
gas shift (wgs) catalysts are very similar to catalysts like that above may not be operative over the zeolite
used for hydrodesulfurization, so that mechanistic catalysts. Alternatively, Mo(V) could still be catalyti-
knowledge about water-gas shift over these catalysts cally important, but it might only form under reaction
may provide some insight into hydrodesulfurization conditions or its concentration might be very small for
catalysis. The present results will also provide a basis these highly dispersed catalysts.
for future comparison to sulfided CoMo/Al2O3 catalysts Spillman (1988) also studied wgs kinetics over sul-
for wgs. fided Mo/Al2O3 catalysts using a “spinning basket”, fully
There are few published studies of wgs using sulfided mixed reactor. Since this study has only been reported
Mo/Al2O3 as a catalyst. Hou et al. (1983) found that in the form of a Master’s thesis, it will be described here
the catalyst was inactive in the oxide form. ESCA in more detail than usual. The Mo/Al2O3 was prepared
analysis of sulfided catalysts revealed that the Mo(V) by incipient wetness impregnation of Davidson γ-alu-
to Mo(IV) ratio changed as the ratio of H2S to H2 was mina (ground to 20-60 mesh) with an aqueous solution
varied. As the mole fraction of H2S present in the feed of ammonium heptamolybdate to produce a loading of
was increased, the catalytic activity also increased (over 15 wt % (as MoO3). The impregnated catalyst was
the range up to 5000 ppm H2S). This led the authors vacuum dried at 80 °C for 3 h and subsequently calcined
to suggest that one sulfur ligand could rapidly exchange at 500 °C in air for 6 h. In a typical experiment the
for an oxygen ligand as in eq 1. The oxygen ligands catalyst was pretreated in 14.6% H2S, balance H2, while
so-generated were then proposed to participate in a heating to 300 °C and then for an additional 2 h during
redox cycle wherein CO removes the ligand and water which the temperature was held constant. The reactor
replaces it (eqs 2 and 3). The observed rate passed was then purged with N2 for 1-h at the same temper-
ature. The feed composition was next adjusted while
S2– S– S2– O– bypassing the reactor, and the temperature was stabi-
Mo5+ + H2O Mo5+ + H2S (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
S2– O– S2–
in each of the 72 experimental runs.
Mo5+ + CO Mo4+ + CO2 (2) During Spillman’s kinetic measurements the feed
always contained H2S; its concentration was 1% by
S2– S2– volume. The reactor would be run for 1-2 h at steady
O–
state, and then the feed composition was changed. The
Mo4+ + H2O Mo5+ + H2 (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.
+ +
Table 1. Power-Law Kinetic Model Parametersa hydroxyl signal associated with the support. In one
catalyst (pressure) k0 E a b c infrared study of unsupported MoS2 (Ratnasamy and
Fripiat, 1970), the adsorption of water did not affect the
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 frequency of the SH band, but adsorbed water or
hydroxyls are not mentioned and the spectrum is not
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).
(Topsøe, 1980), it is noted that the hydroxyl absorption
band disappears as the MoS2 loading increases to the
In the present study Spillman’s data have been point of monolayer coverage of the support. These
reanalyzed using the microkinetic analysis method spectroscopic studies thus suggest that if hydroxyl
suggested by Dumesic et al. (Dumesic et al., 1987, 1993). groups do exist on the sulfide (not the support), then
The objectives of the study were, first, to determine they must be present in very low concentrations since
whether the previously mentioned mechanistic sugges- they are not detectable by infrared spectroscopy. It will
tions remain valid at higher pressures (up to 15 atm be seen that the results of the present study also
vs. 1 atm) and lower temperatures (∼550 K vs. ∼725 indicate that surface hydroxyl groups are present in
K); second, to analyze the resulting mechanistic net- very low concentration under reaction conditions. None-
work; and, third, to establish a basis of comparison for theless, by analogy with the sulfidation steps above, the
future microkinetic analysis of sulfided CoMo/Al2O3 oxidative pathway is represented by reactions (7)-(10).
catalysts for wgs. In addition, reactions (11) and (12) are included to allow
for sulfidation of an oxidized catalyst.
Experimental Methods H2O + * + *-S a *-SH + *-OH (7)
Model Formulation. The suggestions by Hou et al.
(1983) form the basis of the mechanism investigated in H2O + * + *-O a 2*-OH (8)
the present study. The mechanism incorporates a
regenerative (oxidation-reduction) process such as in 2*-OH a 2*-O + H2 (9)
eqs 2 and 3, but via adsorbed species. For simplicity,
hereafter let * denote a vacant site which is envisioned *-OH + *-SH a *-O + *-S + H2 (10)
to be like the Mo(IV) species in eq 2 or eq 3. It is
assumed that adsorption takes place at the location of H2S + * + *-O a *-SH + *-OH (11)
the missing ligand so that *-S is equivalent to the
first species in eq 1 and *-O is equivalent to the *-S + *-OH a *-SH + *-O (12)
second.
The mechanism assumes that the catalyst is in a The formulation of the reductive pathway was guided
sulfided state, but the spectroscopic data mentioned by the chemisorption behavior of the carbon oxides on
previously suggest that the degree of surface sulfidation MoS2. CO is known to adsorb on MoS2 with a relatively
may vary with conditions. Sulfhydryl groups are very weak bond (Maugé and Lavalley, 1992). In fact, it has
commonly observed on MoS2 (Maternová, 1982; Mater- been suggested that CO adsorption can be used to titrate
nová, 1983; Miciukiewicz et al., 1987). They are formed exposed MoS2 sites (Bachelier et al., 1981, 1984). The
by both the adsorption of H2S (Topsøe and Topsøe, 1993) low-temperature chemisorption of oxygen is more com-
and the adsorption of H2 (Ratnasamy and Fripiat, 1970; monly used for this titration even though it has been
Massoth, 1975, 1978; Wright et al., 1980). Therefore, shown to be corrosive (oxidize into the bulk) at subam-
the sulfidation pathway given in reactions (5) and (6) bient temperatures (Tauster and Riley, 1981; Zmierczak
et al., 1982; Kalthod, 1984; Muralidhar et al., 1984). The
H2S + * + *-S a 2*-SH (5) adsorption of NO is also commonly used for MoS2
titration (Topsøe and Topsøe, 1983; Miciukiewicz et al.,
2*-SH a 2*-S + H2 (6) 1987), but again there is some concern that this process
may be corrosive (Prins et al., 1989). CO2, on the other
is included to account for variations in the degree of hand, does not chemisorb on MoS2 (Zmierczak et al.,
surface sulfidation as reaction conditions change. The 1987). Indeed, since CO2 does adsorb on Al2O3, one
associative adsorption of H2S followed by its surface method for measuring the fraction of the support
dissociation could have been used in place of reaction covered by the sulfide uses the difference between the
(5), but this would have introduced additional unknown uptake on the catalyst and the uptake on the support
parameters. Furthermore, the molecular adsorption of only.
H2S is expected to be weak, and Spillman’s data (used In constructing a reductive pathway, it is difficult to
here in the kinetic modeling) were collected at a single simultaneously satisfy the observations that CO adsorbs
H2S level, making it difficult to justify the added while CO2 does not adsorb. Ultimately, a Langmuir-
mechanistic complexity. It should be noted that reac- Hinshelwood reductive pathway, reactions (13)-(15),
tions (5) and (6) require a pair site for the adsorption of was used in the model with the expectation that the
H2S, limiting the applicability of the mechanism. In concentration of adsorbed CO2 (and probably adsorbed
particular, if a surface initially consisted of 100% vacant CO, too) would be small. While formates have also been
sites, it could not become sulfided upon exposure to H2S
according to these reactions because there would be CO + * a *-CO (13)
none of the *-S sites that are necessary for reaction
(5). Thus, as already noted, the mechanism investigated *-CO + *-O a *-CO2 + * (14)
in this study assumes the catalyst is in a sulfided state.
The oxidative pathway was constructed largely by *-CO2 a * + CO2 (15)
analogy to the sulfidation pathway above. It is assumed
that adsorption of H2O will be similar to that of H2S. reported as intermediates in wgs over some catalysts
+ +
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.
[ ( )]
sulfidation pathways, reactions (5)-(12). A second set
5 (2πmkBT)3/2v of Evans-Polanyi parameters, Rred and βred, was used
) ∆Sf(gas)-i - R + ln (17) for the reductive pathway, reactions (13)-(15). The
2 h3
parameter β is typically near 0.5; here it was con-
estimated in this way were only used to calculate the strained to lie between 0.2 and 0.8 because values
reverse preexponential factors once the forward preex- outside this range lead to unreasonable values for the
ponentials had been selected. This is done simply to kinetic parameters. In total there were 10 adjustable
ensure that the reaction rate predicted by the model will model parameters: Rred, Rox, βred, βox, and the surface
equal zero at equilibrium at the reference temperature.) bond strengths for S, SH, O, OH, CO, and CO2.
Having heats and entropies of formation of all species Once the kinetic parameters were calculated for each
(gas and surface), the heats and entropy changes for mechanistic step, the reactor analysis was performed.
each reaction in the mechanism were calculated. The reactor was assumed to be perfectly mixed and to
For each step j in the reaction mechanism four kinetic be operating at steady state. For any one kinetic
parameters are needed: a preexponential factor and an experiment the set variables, i.e., the total inlet volu-
activation energy for both the forward and reverse metric flow rate (sccm), νin; the inlet mole fractions, φin-i,
reactions. The forward preexponential factors, Aj-forward, of all gas-phase species i (i ) 1 through NG where NG
were estimated on the basis of transition state theory is the number of gas-phase species); the mass of catalyst
(Zhdanov et al., 1988; Dumesic et al., 1993). If no in the reactor (g), mcat; the site density of the catalyst
assumptions are made regarding the ideality of the gas (sites/g), Fsites; the temperature (K), T; and the pressure
phase, the rate expression for adsorption steps can take (atm), P, were known. (The site density was taken to
the form of eq 18,where θv denotes the fraction of surface be 1.34 × 1019 g-1 based upon low-temperature oxygen
chemisorption on a catalyst prepared in the same
dθi/dt ) kadsfiθv (18) manner as Spillman’s (Kalthod, 1984).) The outlet mole
fractions, xi, of all gas-phase species i (i ) 1 through
+ +
species (i ) NG + 1 through NS, where NS is the total of its value, so in such cases the value was changed to
number of species in the mechanismsincluding vacant 1 kcal/mol.) This sensitivity analysis was performed for
sites); and the outlet total volumetric flow rate needed each model parameter that was adjustable for the
to be calculated. These response variables (the outlet purpose of fitting; it was also performed for every kinetic
flow rate was used in dimensionless form, xNS+1 ) νout/ parameter (preexponential factors and activation ener-
νin) were calculated from mole balances on all but one gies). A sensitivity factor for a particular parameter j,
gas-phase species (eq 22), mole balances on all but one Sj, was then calculated according to eq 29, where ψ0 is
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).
Sj ) |
ψj - ψ0
ψj | (29)
catalyst and 1500 sccm of a feed containing 33% CO, 67% H2O,
and 1% H2S.
Topsøe, N.-Y.; Topsøe, H. FTIR Studies of Mo/Al2O3-Based Cata- Zmierczak, W.; Qader, Q.; Massoth, F. E. Studies on Molybdena-
lysts. II. Evidence for the Presence of SH Groups and Their Alumina Catalysts. XII. MoS2 Surface Coverage from CO2
Role in Acidity and Activity. J. Catal. 1993, 139, 641-651. Adsorption. J. Catal. 1987, 106, 65-72.
Wright, C. J.; Sampson, C.; Fraser, D.; Moyes, R. B.; Wells, P. B.
Hydrogen Sorption by Molybdenum Sulphide Catalysts. J. Received for review October 4, 1995
Chem. Soc., Faraday Trans. 1 1980, 76, 1585-1598. Accepted May 17, 1996X
Zhdanov, V. P.; Pavlı́cek, J.; Knor, Z. Preexponential Factors for
Elementary Surface Processes. Catal. Rev.-Sci. Eng. 1988, 30 IE950608U
(4), 501-517.
Zmierczak, W.; MuraliDhar, G.; Massoth, F. E. Studies on Mo-
X Abstract published in Advance ACS Abstracts, July 1,
lybdena Catalysts. XI. Oxygen Chemisorption on Sulfided
Catalysts. J. Catal. 1982, 77, 432-438. 1996.