Several series of Co-Mo-based carbon catalysts series were synthesized using three methods,
successive impregnation, successive impregnation with sulfidation in between, and equilibrium
adsorption methods. Co/C and Mo/C were also prepared by impregnation. The activities of
sulfided catalysts for hydrodesulfurization of dibenzothiophene (DBT) and 4,6-dimethyldibenzo-
thiophene (4,6-DMDBT) as models of the most refractory sulfur-containing compounds found in
petroleum oil were studied using an autoclave reactor operating at 2.9 MPa hydrogen pressure.
The activity results were found to be highly dependent on the method of preparation. The series
that was prepared by impregnation but with the sulfidation step before the cobalt addition
exhibited superior activities for hydrodesulfurization (HDS) of DBT and 4,6-DMDBT. The
activity results were compared with that of the conventional commercial Co-Mo/Al2O3 catalyst.
Co-Mo/C catalysts had about twice the activity of the commercial catalyst. It was found that
the activity of HDS depends on the metal loading as well as the order of metal addition during
preparation. The highest synergetic effect between Co and Mo for HDS activity was observed
at a Co/Mo atomic ratio of 0.325.
Discussion
(a) Effect of Sulfidation during Successive Ad-
dition. The influence of the preparation method on the
catalytic properties of Co-Mo/C catalysts may be in-
terpreted with respect to metal sulfides. Though cata-
Figure 7. Selectivity of HDS of 4,6-DMDBT over series III lysts are generally prepared from the oxides, the oxides
catalysts (340 C and 2.9 MPa H2). are readily converted to the sulfides in the presence of
sulfur compounds in the feedstocks. Therefore, MoS2
Table 4. Individual Rate Constants of HDS Reaction is generally considered to be important in the catalyti-
Scheme of 4,6-DMDBT over CoMo/C Catalysts (340 C and
2.9 MPa H2), k 10-4
cally active phase.22,26-29 Vissers et al.,8 on the basis
of XPS studies on Mo/C catalysts, have pointed out that
catalyst kD0 kHS1 k-HS1 kD1 kHP1 the Mo in its oxidic phase was found to be monolayerlike
series II 9 12 120 360 0.36 dispersed up to Mo/C atomic ratios of about 0.0039. On
series III and IV 11 27 270 810 1.35 the other hand, they attributed the deviation from the
theoretical monolayer coverage observed at higher Mo/C
showed a comparable HDS activity. This is contrary ratios to the formation of three-dimensional particles.
to activity preparation sequences reported in the lit- Some sintering of the active phase was noticed during
erature.26 It is uncertain at this point why this is so. sulfiding even at the low Mo loading, indicating a
(d) Influence of Metal Loading. The hydrodes- certain mobility of the Mo phase during sulfiding. This
ulfurization rate constants of DBT and 4,6-DMDBT as indicates the presence of weak interactions between the
a function of cobalt loading for series II preparations active phase and carbon. It may be that the same
are presented in Figure 1. Note that for all catalysts situation is possible for the present series of catalysts
the Mo load was held constant at 10 wt % as the cobalt and long time performance studies are warranted.
concentration was varied. It can be seen that the HDS The results of the present study indicate that the HDS
activities for both DBT and 4,6-DMDBT increased up of DBT and/or 4,6-DMDBT activities of carbon-sup-
to a maximum at about 2 wt % cobalt and then ported Co-Mo catalysts strongly depend on the method
decreased with further increase of cobalt additions. of preparation and metal-loading level. As shown in
Thus, the Co/Mo ratio that provided the highest cata- Table 2, series III catalysts showed the highest activi-
lytic properties was 0.326. Such a level is slightly lower ties. It was nearly twice as active as the conventional
than that of the commercial catalyst. commercial catalyst (Co-Mo/Al2O3). The only difference
The activity of HDS of both DBT and 4,6-DMDBT between MC-II(A)-2 and MC-III(A)-1 catalysts during
over the MC-III(A)-1 catalyst was substantially en- their preparation is the sulfidation of the Mo precursor
hanced. However, higher activity over this catalyst is before cobalt addition for the MC-III(A)-1 catalyst.
manifested mainly by enhancing the hydrogenation Indeed, this step does greatly improve the activity of
route rather than the direct desulfurization (Tables 4 HDS. To interpret this behavior, it is worthwhile to
and 5). These results suggest that the relative ratio of consider the phenomena involved in the sulfidation
catalytic sites for direct desulfurization and hydrogena- process. Consequently, let us first follow the sulfidation
tion reactions may vary with the method of preparation. steps in detail. It is generally accepted30 that the
If one assumes that there are two independent catalytic transformation of the supported molybdate into dis-
3538 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998
persed MoS2 is achieved by sulfidation and reduction interesting to note that the HDS activity of CM-III(A)-1
steps. At first, pure sulfidation takes place in which is comparable with that of series III catalysts, especially
successive O-S exchange to oxysulfides then is trans- in the case of DBT. The impact of this observation is
ferred to sulfido molybdenum complexes and finally to presently being investigated.
MoS3-like species. The last precursor is reduced from While the proposed active phase in Co-Mo catalysts,
Mo(VI) to Mo(IV) through rupture of Mo(VI)-S bonds when molybdenum is impregnated first, is the Co-
with the formation of elemental sulfur. The elemental Mo-S phase, it should be different when cobalt is
sulfur produced adsorbs on the support surface and is introduced first to the support. As mentioned above,
reduced with hydrogen to H2S. This mechanism has the MoS2-phase-like species acts as a support for the
been confirmed using many tools such as X-ray photo- cobalt sulfide phase if molybdenum is introduced first.
electron spectroscopy, temperature-programmed de- The same phenomena may also be applied in the
sorption, and temperature-programmed sulfiding. Fur- situation when cobalt is introduced first (i.e., the cobalt
thermore, it is well-known that MoS2 is a relatively low sulfide phase serves as a support for the MoS2-phase-
active catalyst that is modified in some way by the like species). This would imply that either Mo sulfide
promoter atoms (Co), producing much more active phases or cobalt sulfide phases can behave as a support
catalyst. Topse and co-workers22,26,30 have proposed of each other. However, the recent observation that the
the existence of the so-called Co-Mo-S phase in Co- maximum activity is observed at a stoichiometry of
Mo/Al2O3 catalysts. The cobalt is thought to be located about 2Mo/1Co when the metals are coimpregnated may
on the edges of the MoS2 crystallites bonded to the Mo indicate that the Co-Mo-S active site is a thermody-
through sulfide bridges and the high activity is really namically stable species which is formed during sulfi-
associated with the promoter rather than the underlying dation by rearrangement of the various components.33,34
MoS2. (c) Effect of Co and Mo Concentration. Figure 2
On the basis of the reactivity results of series II and shows the impact of cobalt content on the activity of
III catalysts, it is probable that in series II catalysts, HDS of both DBT and 4,6-DMDBT. Comparison of the
Mo-oxides-like species do not entirely convert to its activity results of HDS over series II catalysts shows
sulfidic state during the sulfidation process.20 This may that the maximum activity occurred at a Co/Mo atomic
be due to the presence of cobalt that may shield the Mo ratio of 0.325. This is similar to that found in many
atoms from sulfurization. Even in the case of series III reported studies35 even over different support materials.
(sulfidation before cobalt addition) catalysts, some Mo- Chin and Hercules36 have shown that as the cobalt
oxide phases may still remain after sulfidation. Perhaps concentration increased, a new phase is formed as
only the surface MoO3 crystals were converted to characterized by interactions between Co and Mo. This
sulfides. This surface phase is more important than the species is produced up to a concentration of 5.5 wt %
bulk phase. Usually, the bulk phase is not accessible Co. Above this level Co3O4 is formed. This species of
during the reaction, since the reactant species will be cobalt is undesirable because it has low activity for HDS.
adsorbed only on the active exterior edges of the Therefore, the homometallic phases such as Co3O4,
crystallites. It might be reasonable to assume that Co9O8, and MoS2 are of secondary catalytic importance
besides the Co-Mo-S phase structure there also may in Co/Mo catalysts.
be a Co-Mo-O phase. The latter one is most likely The limitation of Mo dispersion with increasing
catalytically inactive. This is in contrast to series III, loading should be less critical for higher surface area
in which the Mo-sulfide phase is produced before cobalt carbons since the support surface might be expected to
impregnation. The genesis of the Mo-sulfide phase on be able to accommodate it. As the MoS2 phase disper-
the carbon surface is, therefore, of vital importance. sion is increased, it is very probable that the cobalt
Independent of the type of carbon support, this effect is phases will also have a good chance to be found in a
still pronounced. This can be seen if we compare the high dispersion level, which consequently leads to high
activity of HDS of MC-II(B)-5 and MC-III(B)-4 catalysts HDS activity, as there is direct proportion between
in Table 2. These catalysts were prepared from a dispersion and activity. Experimentally, the reverse
different kind of carbon with a very high surface area was found. The catalyst MC-III(A)-3 (15 wt % Mo and
(3060 m2/g). The enhancement in activity of HDS of 2 wt % Co) exhibited lower activity than the catalyst
MC-III(B)-4 catalyst can be noted from Table 2. The MC-III(A)-1 (10 wt % Mo and 2 wt % Co) in HDS of both
improvement in HDS activity of both DBT and 4,6- DBT and 4,6-DMDBT. The explanation of the observed
DMDBT is clear, although the enhancement of HDS of effect is uncertain. Pratt et al.20 on their study of the
4,6-DMDBT was again found to be mainly in the morphology of Mo over ZrO2 and TiO2 have found that
hydrogenation route (i.e., Table 5). after the formation of a complete monolayer of MoS2 on
(b) Effect of Order of Metal Addition. It is well- ZrO2 and/or TiO2, the surface of the support is no longer
recognized that the addition of cobalt to molybdenum available to the reactants. In addition, they have
catalysts enhances the HDS activity. However, the observed that the MoS2 surface species consists of what
influence of the impregnation order of Co and Mo salt they called raftlike structures, sitting flat on the sup-
is not obvious; in the literature, it has been reported port. At higher loading, the raft expands to coat the
that the highest activity of HDS of Co-Mo catalysts is support in a continuous layer, thus exposing only the
obtained when Mo is impregnated first which leads to basal planes of the MoS2.
good dispersion of cobalt.22,31,32 Most of these studies The lower HDS activity observed in the MC-III(A)-3
have used Al2O3 as a support. To investigate this effect catalyst may possibly be attributed to fewer rims and
in the case of the carbon support, catalyst CM-III(A)-1 edge sites compared with those of the MC-III(A)-1
was prepared in which Co salt was impregnated first, catalyst according to the model proposed by Daage and
then sulfidation, and thereafter addition of Mo salt as Chianelli37 and/or Pratt et al.20
summarized in Table 1. The catalytic activity for HDS Another explanation of this observation may be
of DBT and 4,6-DMDBT is depicted in Table 2. It is related to the sintering effect.8 The mobility of the Mo
Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998 3539
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Hydrodesulfurization Pathway of 4,6-Dimethyldibenzothiophene
Through Isomerization over Y-Zeolite Containing CoMo/Al2O3 Received for review February 9, 1998
Catalysts. Energy Fuels 1996, 10, 1078. Revised manuscript received May 21, 1998
(14) Ma, X.; Sakanishi, K.; Isoda, T.; Mochida, I. Quantum Accepted June 8, 1998
Chemical Calculation of the Desulfurization Reactivities of Het-
erocyclic Sulfur Compounds. Energy Fuels 1995, 9, 33. IE980077K