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Characterization of Sulphided Molybdenum-Containing

Hydroprocessing Catalysts By Oxygen and Hydrogen
Chemisorption

Article  in  Journal of the Chemical Society Faraday Transactions 1 · January 1985

DOI: 10.1039/f19858101655

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J. Chem. SOC.,Faraday Trans. 1, 1985,81, 1655-1667

Characterization of Sulphided Molybdenum-containing

Hydroprocessing Catalysts by Oxygen and Hydrogen
Chemisorption
BY BENJARMMAHIPAL
REDDY,KOMANDUR
V. R. CHARY
AND VARANASI
SURYASUBRAHMANYAM*
Catalysis Section, Regional Research Laboratory, Hyderabad 500 007, India
AND NABINK. NAG*
Department of Fuels Engineering, University of Utah, Salt Lake City, Utah 841 12, U.S.A.

Received 22nd August, 1984

Low-temperature oxygen (- 78 "C) and hydrogen (300 "C) chemisorption have been applied
to characterize a series of sulphided Mo/Al and Co-Mo/Al hydroprocessing catalysts
containing up to 12% Mo. Three commercial Co-Mo/Al catalysts have also been studied.
Attention has been focussed mainly on the merit of oxygen chemisorption as a surface-specific
probe for characterizing hydroprocessing catalysts. From the results it appears that while
oxygen chemisorbed at - 78 "C can titrate the number of coordinately unsaturated sites (CUS)
irrespective of the nature of the support they are on, it cannot distinguish between two CUS
with different intrinsic hydrodesulphurization (HDS) activity (arising either because of
carrier-catalyst interaction or because of the influence of a promoter) or between a hydrogenation
(HYD) and a HDS site.
Hydrogen-chemisorption results are also found to throw some light on the structural growth
of MoS, crystallites on the support. The results strongly indicate that hydrogen first dissociates
on the CUS on the edge planes of MoS, prior to its migration to the basal planes where it
remains as SH groups. There is also evidence that the van der Waals gap between two MoS,
' sandwiches' cannot accommodate hydrogen.

Oxygen chemisorption at temperatures ranging from - 78 to 60 "Chas recently been

applied to characterize sulphided Mo-containing hydroprocessing ~ata1ysts.l-l~ In
these studies advantage has been taken of the surface-specific adsorption behaviour
of oxygen on the edge planes of MoS, crystallites14to determine a correlation (or
otherwise) between the amount of oxygen chemisorbed and the hydrodesulphurization
(HDS) or hydrogenation (HYD) activities of these catalysts. Chemisorption of
hydrogen and hydrogen sulphide at higher temperatures has also been applied to
elucidate the structure of Mo and W sulphide c a t a l y s t ~ . While
~ ~ - ~ some
~ workers'. **6 ,
found a correlation between oxygen chemisorption (presumably occurring on the edge
planes of MoS, crystallites) and HDS activity, otherss7 failed to do so. Even the basic
concept that HDS reactions occur on the edge planes, rather than on the basal planes,
has been the subject of considerable debate.22-24 The difficulty encountered in unifying
the oxygen chemisorption results of various workers, as referred to above, and coming
to a definite conclusion regarding the merit of the technique as a surface-specificprobe
is the lack of uniformity in the techniques applied to generate the data. For instance,
oxygen chemisorption has been performed by static12 or dynamic flow9 and pulse
methods1? 5 * l2 and at temperatures varying between - 78 and 60 "C.Additionally,
49 6v

1655
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1656 SULPHIDED Mo-CONTAINING CATALYSTS

catalysts with various compositions including pure MoS, and pre-sulphided supported
(sometimes with different support materials) Co-Mo and Ni-Mo have been used in
these studies. Lastly, different catalyst treatment procedures have also added to the
~ - ~the Mo loading been varied
difficulties mentioned above. Only in a few s t ~ d i e s has
systematically on the same support and oxygen chemisorption on these catalysts has
been applied to correlate with HDS activity.
The present work was undertaken against this background. The major purpose was
to evaluate the merit of oxygen chemisorption as a surface-specific probe by
conducting chemisorption of oxygen on a series of catalysts based on the same support
and at a sufficiently low temperature that oxygen would not attack the bulk of MoS,
crystallites. Any secondary effect arising through carrier<atalyst interaction and
leading to a possible change in the intrinsic activities of the HDS and HYD sites was
eliminated by this procedure. Attention was also focussed on the surface structure of
the catalysts derived from the hydrogen chemisorption data.

EXPERIMENTAL
CATALYSTS
A series of Mo/Al catalysts with Mo loadings ranging from 2 to 12% was prepared by
incipient wetting of y-alumina (precalcined at 540 "C for 16 h) with solutions (at pH 8) of
appropriate concentrations of ammonium heptamolybdate. The impregnated samples were
dried in air at 120 "C for 16 h and then calcined in air at 540 "C for 16 h. The Co-promoted
catalysts were prepared from the oven-dried 8 % Mo/Al catalyst by impregnation with cobalt
nitrate solutions of appropriate concentration in an identical manner, drying at 120 "C followed
by calcining at 540 "C, both for 16 h. Three commercial catalysts were also used in this
investigation. The compositions and the physicochemical properties of all the catalysts are given
in table 1.

CHEMISORPTION MEASUREMENTS
A conventional high-vacuum system was modified in order to be able to sulphide the catalysts
in situ prior to chemisorption measurements. The details of the set-up have been given
el~ewhere.,~ In a typical experiment ca. 0.5 g of catalyst was placed in the catalyst chamber and
heated to 100 "C in a flow of nitrogen. Sulphiding was then carried out using a mixture of CS,
and H, as follows. A stream of H, (40cm3min-', pretreated by Pd 'Deoxo' and 4A
molecular-sieve zeolite) saturated with CS, vapour at 25 "C was passed through the catalyst
bed and the temperature was raised to 400 "C at a rate of 4 "C min-'. Sulphiding was continued
for 2 h at 400 "C, after which the sulphiding gas flow was stopped and the system was evacuated
at 400 "C for 4 h at lop6Torr. The catalyst chamber was then cooled to -78 "C by a dry-ice+
acetone bath and the evacuation Torr) was continued at this temperature for 1 h. The
catalyst was now ready for oxygen chemisorption, which was carried out as follows. Oxygen
from a reservoir, connected to the high-vacuum manifold, was allowed to enter the catalyst
chamber with known dead space. An initial quick fall in the pressure was followed by a levelling
off within ca. 10 min and the equilibrium pressure was noted. This process was repeated with
different initial pressures and the first adsorption isotherm, representing both the chemisorbed
and physisorbed oxygen, was generated. After this the catalyst was evacuated at -78 "C for
3 h at Torr to remove the physisorbed oxygen, and the second isotherm, representing only
the physisorbed oxygen, was generated in an identical manner. From these two linear and
parallel isotherms the amount of chemisorbed oxygen was determined by the method of Parekh
and Weller.26The adsorption equilibrium pressure varied between 200 and 400 Torr.
A fresh sample was used to determine the uptake of hydrogen in an identical manner. In
this case, however, a higher temperature of adsorption, namely 300 "C, was to be applied in
order to obtain appreciable chemisorption. After the chemisorption experiment the B.E.T.
surface area of the catalyst was determined by N, adsorption at - 196 "C by taking 0.162 nm2
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B. M. REDDY, K. v. R. CHARY, v. s. SUBRAHMANYAM AND N. K. NAG 1657

Table 1. Composition and the B.E.T. surface areas of various catalysts

composition B.E.T. surface area

(wt %I" /m2 g-l

fresh sulphidedb
catalyst Mo Co SiO, catalyst catalyst

1 2.0 - - 199.0 181.0

2 4.0 - - 191.0 187.0
3 6.0 - - 184.0 189.0
4 8.0 - - 175.0 189.0
5 10.0 - - 169.0 170.0
6 12.0 - - 162.0 158.0
7 8.0 3.O - 171.0 168.0
8 8.0 5.0 - 169.0 157.0
Ketjenfine-124 7.7 2.44 1.16 267.0 249.0
Ketjenfine-742 10.0 3.34 0.91 253.0 239.0
Harshaw-HT-400 10.0 2.36 - 200.0 187.0

a The balance was A1,03. The B.E.T. surface area of the calcined alumina (Harshaw
Al-1 11-61) which was used to prepare catalysts 1-8 was 204 m2 g-l. Measured after the oxygen
chemisorption experiment.

as the area of cross-section of N,. The B.E.T. surface areas of the fresh and sulphided catalysts
are given in table 1.
ACTIVITY MEASUREMENTS
A differential flow microreactor, operating under normal atmospheric pressure and interfaced
to a gas chromatograph by a six-way gas-sampling valve, was used to measure the activities
of the catalysts. In a typical experiment ca. 0.2 g of a catalyst sample was secured between two
plugs of Pyrex glass wool inside the glass reactor (Pyrex glass tube, 0.5 cm i.d.) and was
sulphided at 400 "C for 2 h following the procedure described in the previous section. After
sulphidation the reactor temperature was adjusted to 400 "C for thiophene HDS and 350 "C
for cyclohexene HYD. The sulphiding gas mixture was then replaced by nitrogen and the reactor
was flushed by N, at the reaction temperature for 0.5 h. At this stage the catalyst was contacted
with the reaction mixture, which consisted of a stream of hydrogen saturated with thiophene
(Fluka, 99 % ) or cyclohexene (Merck-Schuchrdt) at 25 "C. The partial pressures of thiophene
and cyclohexene were 80.0 and 85.0 Torr, respectively.All rates were measured under steady-state
conditions and in the absence of any diffusion effects with the help of the equation
x = r(W/F)
where r is the rate in mol h-l g-' catalyst, x is the fractional conversion, W is the weight of
catalyst in g and F is the total flow rate of gas in mol h-l. The conversion was maintained
below 10% and a straight line was obtained by plotting x against W / F for each catalyst. The
rate was calculated from the slope of this line.
ANALYSIS
The HDS products of thiophene were butene and butane and were analysed by gas
chromatography with the help of a 2 m stainless-steel column packed with 10% OV-17,
maintained at 100 "C. Cyclohexane was the only product found for the HYD of cyclohexene
under the experimental conditions and was analysed with 20% PEG-1500 ( 2 m column
maintained at 90 "C). A carrier-gas (nitrogen) flow of 40 cm3 min-l and an FID were used in
both cases.
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1658 SULPHIDED Mo-CONTAINING

CATALYSTS

-200 -100 0 100

temperature of chemisorption/'C
Fig. 1. Oxygen uptake plotted as a function of the temperature of chemisorption. Data are taken
from various sources: 0, this work; 0 , ref. (6); V, ref. (7); A,ref. (8); and 0 , ref. 9. All
points represent CQ. 8% Mo on alumina (sulphided) with comparable catalyst surface area.

RESULTS
OXYGEN AND HYDROGEN CHEMISORPTION
The choice of the temperature at which oxygen chemisorption could give useful
information on the surface structure of the catalysts was deemed crucial. Zmierczak
et aL9 have found that -78 "C is the most suitable temperature for oxygen
chemisorption, and that at higher temperatures the state of oxygen could be uncertain.
Bodrero and Bartholomew,12 from extensive studies on supported and unsupported
MoS, catalysts, have come to a similar conclusion and have advocated - 78 "C as the
most realistic temperature for chemisorption of oxygen as a surface-selective probe for
characterizing sulphided hydroprocessing catalysts. As noted by Parekh and Weller,26
we observed that even at 0 "C the pressure of oxygen in contact with the catalysts
showed a continuous and slow decrease with time (indicative of the slow chemical
interaction of oxygen with the MoS, bulk), whereas at -78 "C the adsorption
equilibrium was attained within a few minutes. By conducting chemisorption at
- 196 "C (with evacuation at -78 "C between two isotherms) it was found that the
amount of chemisorbed oxygen was virtually equal to that obtained at -78 "C. In
order to appreciate the temperature effect fig. 1 has been drawn from the results
obtained by various w ~ r k e r s . ~
The
- ~ oxygen-uptake values shown in fig. 1 correspond
to ca. 8 % Mo on A1,0,. The effect of the temperature of chemisorption on the amount
of oxygen uptake is clearly seen. The sharp rise in oxygen uptake above -78 "C is
probably due to the attack of the bulk of MoS,, thus stressing the fact that a
temperature higher than -78 "C should be cautiously used to draw any conclusions
about the surface structure of the catalysts. In view of these facts all our oxygen
chemisorption experiments were carried out at -78 "C and under static conditions.
The oxygen-uptake values as a function of catalyst composition are given in fig. 2.
Oxygen uptake per gram of catalyst is found to level off at an Mo loading of ca. l o % ,
and the results pertaining to all the catalysts, including the unpromoted, promoted
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B. M. REDDY, K. V. R. CHARY, V. S. SUBRAHMANYAM AND N . K. NAG 1659

catalysts; 0 ,3 : 8 Co-Mo/Al;v,5 : 8 Co-Mo/Al; .,

Fig. 2. Oxygen uptake at -78 "C plotted as a function of catalyst composition: 0,

A,Harshaw HT-400.
Mo/Al
Ketjenfine-124; 4, Ketjenfine-742 and

and commercial ones, fall approximately on the same curve. Pure y-Al,O, was found
by an independent experiment to chemisorb some oxygen under our experimental
conditions. Therefore, the amount of chemisorbed oxygen corresponding to the
amount of alumina present in each catalyst was subtracted from the oxygen-uptake
values of the catalysts before reporting the results.
Chemisorption of hydrogen on dichalcogenides like MoS, is an activated p r o c e s ~ , ~ ~ - ~ ~
and a higher temperature, 300 "C,was necessary to obtain appreciable chemisorption.
The results are given in fig. 3. Unlike the case of oxygen, a sharp maximum in hydrogen
uptake is observed at a loading of ca. 8% Mo on A1,0,. Wright et aL.l5have also noted
that hydrogen uptake at 300°C increases with increasing Mo loading and passes
through a maximum for supported MoS, catalysts. This, and their other observation
that the promoter does not lead to a higher hydrogen uptake, are in accord with our
results. Hydrogen uptake by a pure alumina support under identical experimental
conditions was taken into account to make necessary corrections for the hydrogen-
uptake data of all the catalysts.

OXYGEN CHEMISORPTIONversus HDS AND HYD ACTIVITIES

HDS activity of the catalysts, reported as the steady-state rate of HDS of thiophene,
has been plotted as a function of oxygen uptake in fig. 4. There is a good correlation
between oxygen uptake and HDS activity for the unpromoted catalysts, at least up
to a certain level of Mo loading. This level corresponds to an Mo loading that is
generally reported to give the monolayer c ~ v e r a g of e ~the
~ ~support
~~ surface. At
higher oxygen uptakes the activity seems to level off. Similarly, the promoted catalysts
show a rough correlation amongst themselves [fig. 4 (B)]. Note that the correlation
line representing the promoted catalysts has a 3-4 times higher slope than that
representing the unpromoted catalysts. This implies that the activity per oxygen atom
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1660 SULPHIDED Mo-CONTAINING

CATALYSTS

20

x
; V
"
-
I
M
0

3
Y
10
a

5iE
'p
c
x

Mo on A1203 (wt %)
Fig. 3. Hydrogen uptake at 300 "C plotted as a function of catalyst composition. Symbols as
fig. 2.

40

2c

0
0 20 40
oxygen uptake at -78 'C/pmol g-' catalyst
Fig. 4. HDS activity at 400 "C of various catalysts plotted as a function of oxygen uptake at
-78 "C. Symbols as fig. 2.
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B. M. REDDY, K. v. R. CHARY, v. s. SUBRAHMANYAM AND N. K . NAG 1661

oxygen uptake at -78 'C/pmol g-I catalyst

Fig. 5. HYD activity at 350 "C of various catalysts plotted as a function of oxygen uptake at
-78 "C. Symbols as fig. 2.

0 100 2 00
hydrogen uptake at 300 "C/pmol g-' catalyst
Fig. 6. HDS activity at 400 "C of various catalysts plotted as a function of hydrogen uptake
at 300 "C. Symbols as fig. 2.

chemisorbed on the promoted catalysts is 3-4 times higher than that on the
unpromo ted catalysts.
The hydrogenation activity of the catalysts as a function of oxygen uptake is shown
in fig. 5 . Unlike the case of the HDS reaction, both the promoted and unpromoted
catalysts fall on the same correlation line.
HYDROGEN CHEMISORPTION uersus HDS AND HYD ACTIVITIES
HDS and HYD activities of the various catalysts are plotted as a function of
hydrogen uptake in fig. 6 and 7, respectively. It is observed from fig. 6 that the
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1662 SULPHIDED Mo-CONTAINING

CATALYSTS

hydrogen uptake at 300 'C/pmol g-' catalyst

Fig. 7. HYD activity at 350 "C of various catalysts plotted as a function of hydrogen uptake
at 300 "C. Symbols as fig. 2.

unpromoted catalysts show an initial linear increase in HDS activity that levels off
beyond a certain limit of hydrogen uptake [fig. 6(A)]. The promoted catalysts do not
show any correlation with the unpromoted catalysts. However, with the exception of
the laboratory-made 5 : 8 Co-Mo/Al, a reasonable correlation similar to that observed
for the unpromoted catalysts is observed amongst the promoted catalysts. The
promotional effect of Co on the HDS reaction is again reflected by the data presented
in fig. 6.
The correlation between HYD activity and hydrogen uptake is shown in fig. 7. All
the laboratory-made catalysts, including the promoted ones, show a good correlation
between HYD activity and hydrogen uptake. The commercial catalysts show some
scatter, probably owing to the diversity of their source and slight differences in the
composition of the support. The promoted catalysts do not show any significantly
higher HYD activity than the unpromoted catalysts.

DISCUSSION
CATALYST COMPOSITION versus OXYGEN AND HYDROGEN CHEMISORPTION
All the oxygen chemisorption studies, as referred to earlier,l-13 are based on two
very important ideas: first that oxygen chemisorbs selectively on the edge planes of
MoS, crystallites and secondly that the active sites for HDS and HYD reactions are
also located on the edge planes'l 2v 279 29 as coordinately unsaturated Mo ions. Although
the second premise, especially in connection with HDS reactions, has been the subject
of some c o n t r o ~ e r s y , ~ ~the
- ~ importance
* of the edge planes, where sulphur anion
vacancies are automatically formed in order to maintain the electrical neutrality of
small MoS, c r y ~ t a l l i t e scan
, ~ ~ hardly be overemphasized. Therefore, surface-specific
oxygen chemisorption should, in principle, offer the opportunity to evaluate critically
the merit of this technique for correlating the activity of the sulphided catalysts with
the edge-plane area (or more precisely, the oxygen area).
As shown in fig. 2, a good correlation is observed between Mo loading and oxygen
uptake up to a loading of ca. 10% (a loading which corresponds to monolayer
coverage). This linear correlation can be explained in the light of the structural model
of sulphided Mo catalysts as proposed by T o p s ~ l eThe . ~ ~model, based on Mossbauer
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B. M. REDDY, K. v. R. v. s. SUBRAHMANYAM AND N . K. NAG

CHARY, 1663
emission spectroscopy, EXAFS and other studies, depicts the catalyst as a highly
dispersed two-dimensional MoS,-like structure which remains on the support surface
as small patches (10 A) of one ‘sandwich’ of MoS,. The promoter, Co or Ni, does
not alter this basic structure, but substitutes for Mo and/or occupies a neighbouring
interstitial position on the edge planes. This combination has been identified as a
separate phase (the Co-Mo-S phase) by MES spectroscopy and is claimed to be
responsible for the HDS-associated reactions.,’ Under the tenet of this model we
envisage that with increasing Mo loading the number, and not the size, of such
crystallites increases on the freely available alumina surface with a concomitant
increase in the edge surface for oxygen chemisorption. As our results indicate, this
goes on up to an Mo loading of ca. 10% (fig. 2) and explains the linear correlation
between oxygen uptake and Mo loading in this region. However, above this Mo level
the uptake of oxygen levels off. This is probably due to the increase in size of the
individual MoS, patches in the crystallographic a-direction (i.e. parallel to the basal
plane). This growth in size of the small patches, rather than in number, is expected
not to add to the edge surface area per unit Mo as a function of Mo loading.
In order to rationalize the hydrogen chemisorption results, as shown in fig. 3, it
is necessary to understand the way hydrogen binds with MoS, under the experimental
conditions. From studies on MoS, and WS, catalysts by inelastic neutron-scattering
spectroscopy, Wright et al.159l6 have considered the possibility that hydrogen first
dissociates on the exposed metal atoms on the edges and corners (which, incidentally,
are also the sites for oxygen chemisorption) and then migrates (possibly via a
spillover mechanism) to the basal planes, whefe it binds with S atoms and remains as
SH groups. Chadwick and Breysse22made a similar proposal while rationalizing some
HDS results in another context. The important point to note here is that although
the edge planes of MoS, are indirectly involved in the hydrogen-chemisorption
process, it is the basal planes which are the actual ‘seat’ of hydrogen. Therefore, the
sharp rise in hydrogen uptake can be explained by the corresponding increase in the
basal-plane area generated by the increase in the number of two-dimensional MoS,
patches. However, unlike the case of oxygen, the maximum hydrogen uptake occurs
at a slightly lower Mo loading, namely 8 % . One plausible explanation for this
phenomenon could be that at this level a multilayer growth of MoS, crystallites sets
in along the crystallographic c-direction (i.e. perpendicular to the basal plane). This
results in a drastic decrease in the exposed basal-plane area without much affecting
the edge-plane area. So, although new edge planes are created in the range &lo%
loading, as indicated by the uninterrupted increase in oxygen uptake in this range (fig.
2), the basal-plane area per unit Mo loading starts to decrease from 8% loading owing
to multilayer growth. This decline may be confirmed by plotting (not shown) hydrogen
uptake per mol of Mo against Mo loading, when a maximum is again observed at
a loading of 8% Mo. This decline in the basal-plane area results in a decrease in the
hydrogen-uptake value. Topsare and Tops0e31have given evidence for the formation
of three-dimensional MoS, under certain experimental conditions. We failed to detect
any X.r.d. lines due to large MoS, crystallites even with 12% Mo/Al catalyst, although
this does not rule out the ossibility of formation of up to 6-7 layers of MoS,
K
corresponding to the ca. 40 limit of the detection capability of the X.r.d. technique.
The departure of 5 : 8 Co-Mo/Al (laboratory-made) and Ketjen- 124 catalysts from
the correlation curve might stem from their higher Co and SiO, contents, respectively.
OXYGEN CHEMISORPTION versus HDS AND HYD ACTIVITIES
The correlation between oxygen uptake and HDS activity of the unpromoted
catalysts is found to be linear and quite strong, as shown in fig. 4(A). The promoted
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1664 SULPHIDED Mo-CONTAINING CATALYSTS

catalysts, both laboratory-made and commercial, also show a similar trend amongst
themselves [fig. 4(B)]. By comparing the results shown by curves (A) and (B) of fig. 4
it is observed that the promoted catalysts are associated with about four times higher
activity per unit of chemisorbed oxygen, as compared with the unpromoted catalysts.
A similar conclusion is inherent in the results of Zmierzcak et where the promoted
catalysts showed ca. 5-6 times higher activity than showed by the unpromoted ones.
This is a clear indication that the role of promoter is primarily to increase the intrinsic
activity of the HDS sites and not to increase their number. This observation is in accord
with other reported 9p 32
As discussed earlier, a difference of opinion exists, however, as to whether the
amount of oxygen chemisorbed at low temperatures around -78 "C does correlate
with HDS activity. Zmierzcak et aL9 found only a rough correlation between oxygen
uptake (at - 78 "C) and HDS activity of a series of catalysts containing 8 % Mo and
8 % Mo plus 3 % Co on various supports, including y-Al,03, SiO,, 10-75 % SiO,-AI,O,,
Zn-doped Al,O, and TiO,. They ascribed the appreciable scatter in their correlation
curve to different degrees of the promoting effect of Co for different catalysts. In
general, carrier-catalyst interactions can lead to a change in the dispersion as well as
in the intrinsic activity of the active sites when the same catalyst is supported on
different carriers.33The findings of Tops0e31that Mo has a lower electron density when
supported on SiO, than when supported on Al,03 is a case in point. Since supports
with widely differing acidities were used in the study by Zmierzcak et aL9 it is quite
likely that the latter's failure to find a smooth correlation was due to the non-uniformity
in the intrinsic activity of the sites assokiated with different supports. It is known that
oxygen chemisorbs at low temperatures on the coordinately unsaturated (CUS) Mo
sites located on the edge but there is no reason to believe that while doing
so it should 'see' any difference between CUS (which are also the HDS sites) with
different intrinsic HDS activity. The HDS rate, on the other hand, is a function of
both the number and the intrinsic activity of the sites. The monotonic decrease in the
oxygen-uptake capacity of Mo and Co-Mo catalysts with increasing SiO, content of
the SO,-Al,O, supports [ref. (9), table 2, first 5 catalysts] is thus a dispersion effect,
whereas the decrease in HDS activity of the same catalysts [ref. (9), fig. 4(A) and 5(A)]
is partly due to dispersion and partly due to the change in the intrinsic activity
stemming from the carrier-catalyst interaction. Therefore, we recommend that the
secondary effects arising due to carrier-catalyst interaction should be carefully
considered while correlating oxygen chemisorption data with HDS activity of
hydroprocessing catalysts. By doing this, we observe a good linear correlation (fig. 4)
between oxygen uptake and HDS activity of the catalysts.
The correlation between oxygen uptake and H Y D activity, as shown in fig. 5, agrees
well with other Both the promoted and unpromoted catalysts conform to the
same correlation line, thus showing that unlike HDS in the case of HDS sites, the
promoter does not alter the intrinsic activity of the HYD sites. This enables a direct
correlation to be obtained between hydrogen uptake and H Y D activity of all the
catalysts, promoted or unpromoted.
The results discussed above are significant and stimulate further thoughts concerning
the active sites. The current notion about the nature of different functionalities of
hydroprocessing catalysts is that HDS and H Y D sites are structurally different.32 It
is also believed that these sites are located on the edge planes of MoS,-like
structures27~2g~32~37 as CUS. The necessary condition for oxygen to be able to
chemisorb on the catalysts at -78 "C is the presence of CUS on the edge planes. As
long as these are available oxygen cannot distinguish between two CUS with different
intrinsic HDS activities or one with HDS and the other with HYD activity. In view
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B. M. REDDY, K. v. R . CHARY, v. s. SUBRAHMANYAM AND N . K . NAG 1665

of the results discussed above we propose that both HDS and HYD sites are
indistinguishable, geometrically speaking. However, when the question of functionality
of these sites (CUS in general) arises, the HYD activity appears to be a function of
only the extensive property (i.e.the number of sites) and is subject to only a dispersion
effect, whereas the HDS activity appears to be a function of both an extensive and
an intensive property (i.e. the intrinsic activity that is sensitive to the carrier<atalyst
interaction). Co as a promoter changes the intrinsic activity of the HDS sites by
altering the electron density3' around Mo. Therefore, the promoted catalysts have a
higher HDS activity per site (CUS) than the unpromoted catalysts. This is the reason
why HDS activities of the promoted catalysts do not correlate with those of the
unpromoted catalysts. This change in the intrinsic activity of the HDS sites is also
envisaged for Mo catalysts supported on different materials, which is indeed observed
in p r a ~ t i c eIn
. ~contrast, the universal curve correlating oxygen uptake and the HYD
activities (fig. 5 ) of promoted, unpromoted and commercial catalysts implies that the
HYD reaction is less sensitive, if at all, to the intensive property (intrinsic activity)
of the catalysts. This difference in sensitivity of HDS and HYD reactions towards the
intensive property of the CUS is quite significant and can be understood properly only
when the mechanisms of these reactions are fully understood. However, it is worth
remembering that since the HDS reactions involve C-S bond scission they are more
demanding than the HYD reactions, which require the saturation of double bonds.
HYDROGEN CHEMISORPTION versus HDS AND HY D ACTIVITIES
In the light of the hydrogen chemisorption mechanism, as proposed by Wright et
l6 and elaborated in the text, the initial increase and subsequent levelling off in
HDS activity as a function of hydrogen uptake [fig. 6(A)] indicate that only a fraction
of chemisorbed hydrogen takes part in HYD reactions. It is possible that only those
H atoms that are bound as SH groups in the immediate neighbourhood of the edge
planes (where the HDS sites are also located) actually take part in the reaction, while
a large fraction of hydrogen remains unavailable owing to its location on the distant
part of the basal planes. In the case of the promoted catalysts the correlation [fig. 6(B)],
with the exception of the 5 % Co-Mo/Al sample, shows a definite trend similar to
that observed with the unpromoted catalysts. The higher intrinsic HDS activity of the
promoted catalysts is again demonstrated by the hydrogen chemisorption data, as
depicted in fig. 6.
Fig. 7 shows a reasonable correlation between hydrogen uptake and HYD activities
of the catalysts. Unlike in the case of HDS, all the chemisorbed hydrogen, irrespective
of its location on the basal plane, correlate with the HYD activity. This implies that
the role of hydrogen is different for the HDS and HYD reactions. A similar approach
has recently been applied by Nag38 to understanding the HDS-associated reactions,
where the reactions have been envisaged as occurring via two independent routes.
Nevertheless, the real significance of these results is not clear at this stage.
RELATIONSHIP BETWEEN OXYGEN AND HYDROGEN CHEMISORPTION SITES
In the earlier part of our discussion it was speculated that certain sites (CUS) on
the edges of MoS, act as centres for the initial dissociation of hydrogen prior to its
migration to the basal plane. Recalling also the fact that oxygen too chemisorbs on
these sites, interesting information can be derived by plotting hydrogen-uptake values
against oxygen-uptake data. This has been done in fig. 8. Two important features are
worth noting: the first is a very sharp rise in hydrogen uptake at an oxygen uptake
of ca. 25 pmol g-l catalyst and an equally sharp decrease in hydrogen uptake beyond
this level, and the second is that all the catalysts, unpromoted, promoted and
55 FAR 1
Published on 01 January 1985. Downloaded by Indian Institute of Chemical Technology (IICT), Hyderabad on 24/10/2015 06:48:51. View Article Online

1666 SULPHIDEDMo-CONTAINING
CATALYSTS

200

4a

oxygen uptake at -78 OCIpmol g-l catalyst

Fig. 8. Hydrogen uptake at 300 "C plotted as a function of oxygen uptake at - 78 "C. Symbols
as fig. 2.

commercial, conform to the volcano-shaped curve. We have also noted earlier that
this maximum in hydrogen uptake occurs just before the three-dimensional multilayer
growth of MoS, sets in. This leads to a decrease in the exposed basal-plane area
without affecting the edge-plane area. The sharp fall in hydrogen-uptake capacity as
a function of oxygen-uptake capacity then indicates that hydrogen can only be
accommodated on the basal planes which are exposed; the van der Waals gap between
two MoS, layers cannot accommodate hydrogen.
In conclusion, we stress that oxygen chemisorption at low temperatures can be used
as a valuable surface-specific probe for characterizing sulphided hydroprocessing
catalysts, provided care is taken to eliminate the complications arising owing to
carrier-catalyst interaction or owing to the inclusion of the promoters such as Co.
When this is done, oxygen uptake can be correlated directly with HDS activity of the
catalysts. This restriction does not apply to HYD reactions, where the oxygen
chemisorption data can directly be correlated with the HYD activity of all the catalysts
irrespective of the vigour of the carrier-catalyst interaction or the electronic changes
brought about by the promoter on the CUS. Finally, hydrogen chemisorption can
also be exploited to derive some valuable information on the structure of the sulphided
catalysts.

We thank Drs G. Thyagarajan, R. Vaidyeswaran and E. R. Saxena, all of the

Regional Research Laboratory, Hyderabad, India for their support and encourage-
ment. Thanks are also due to Dr B. Rama Rao for his help in obtaining the X.r.d. data.
Constructive suggestions by the referees are gratefully acknowledged.
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