Ind. Eng. Chem. Res.

1998, 37, 3533-3539 3533

Synthesis of Active Hydrodesulfurization Carbon-Supported Co-Mo

Catalysts. Relationships between Preparation Methods and
Activity/Selectivity
Hamdy Farag,* D. D. Whitehurst, and Isao Mochida
Institute of Advanced Material Study, Kyushu University, Kasuga, Fukuoka 816-0811, Japan

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.

Introduction poisoning.10 Thus, carbon offers tremendous promise

Sulfides of transition metals are of great current
industrial interest as catalysts because they are widely
used in petroleum refining for hydroprocessing applica-
tions such as hydrodesulfurization and hydrodenitro-
genation. Generally, sulfide catalysts utilized in indus-
try are derived from oxides of elements of Group VIB
(Mo or W) and Group VIII (Co or Ni). Alumina is the
most widely used support material for commercial Co-
or Ni-promoted molybdenum hydrotreating catalysts.
Notable features of alumina supports are their ability
to disperse the active metal phase1 and good mechanical
properties. However, the results of intensive past
research2-7 showed that, in the final oxidic or precursor
state, various degrees of chemical interaction exist
between the amorphous alumina and the transition-
metal oxides. Some of the species formed are very stable
and resist complete sulfidation. As a consequence, an
industrial catalyst, when converted into its sulfided or
actual active state, very probably contains oxides as well
as sulfides. Moreover, it has been suggested that the
strong interactions of metal with alumina is undesirable
as it gives negative effect on the hydrodesulfurization
activity of sulfur-containing compounds.8 The quest for
superior support systems that avoid the main disad-
vantages of alumina has led researchers to explore
alternative support materials.
Carbon is one that has recently received much atten-
tion. This is due to the many attributes linked with it
such as a high surface area, availability of a large
variety of pore sizes, variable surface functional groups,
easy metal recovery by the burning of the support,
reduced coking propensity,9 and resistance to nitrogen
* To whom all correspondence should be addressed. Tel.: 81-
92-583-7801. Fax: 81-92-583-7798. E-mail: hamdymo@
isc.kyushu-u.ac.jp.
S0888-5885(98)00077-3 CCC: $15.00 1998 American Chemical Society
Published on Web 07/25/1998
as a support material. However, it is well-known that
the creation of a large number of active sites on the
surface of the catalysts is one of the essential goals for
those who work in catalyst development for hydrotreat-
ing. The method of preparation is one of the funda-
mental factors that plays an important rule in the
precursor structure and consequently in the activity of
hydroprocessing.
The aim of the present work is to explore the role of
the preparation method of Co and Mo supported on
carbon catalysts and its influence on the hydrodesulfu-
rization activity of dibenzothiophene and 4,6-dimethyl-
dibenzothiophene. These compounds were chosen as
model reactants as they represent the most refractory
sulfur compounds found in real petroleum feedstocks
oil to be desulfurized.11 The catalysts prepared have
been examined for activity and selectivity in the hy-
drodesulfurization of DBT and 4,6-DMDBT, and the
results were compared with the conventional Co-Mo/
Al2O3 commercial catalyst.
Experimental Section
(a) Chemicals. All chemicals were used as received
without further purification. Dibenzothiophene (DBT),
biphenyl, phenylcyclohexane, and decane were pur-
chased from Wako Chemical Co. 3,3-dimethylbiphenyl
was received from Aldrich Chemical Co. Cobalt acetyl-
acetonate, molybdenum acetylacetonate, ammonium
molybdate, cobalt nitrate, and cobalt acetate were
purchased from the Dojindo company. 4,6-Dimethyl-
dibenzothiophene was synthesized from DBT according
to ref 12.
(b) Carbon Support. In the present study, two
different carbon supports were used (i.e., carbon (A) and
carbon (B), having surface areas of 1350 and 3060 m2/g
and average pore volumes of 0.52 and 1.76 mL/g,
3534 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998

Table 1. Catalysts Preparation, Composition, and References

catalyst first metal molybdenum salt cobalt salt preparation
reference support salt added (Mo wt %) (Co wt %) method solvent
M-I(A) carbon (A) Mo acetylacetonate (10 wt %) Ib CH3OH
C-I(A) carbon (A) Co acetylacetonate (2 wt %) I CH3OH
MC-II(A)-1 carbon (A) Mo Mo acetylacetonate (10 wt %) Co acetylacetonate (1 wt %) IIc CH3OH
MC-II(A)-2 carbon (A) Mo Mo acetylacetonate (10 wt %) Co acetylacetonate (2 wt %) II CH3OH
MC-II(A)-3 carbon (A) Mo Mo acetylacetonate (10 wt %) Co acetylacetonate (4 wt %) II CH3OH
MC-II(A)-4 carbon (A) Mo Mo acetylacetonate (10 wt %) Co acetylacetonate (6 wt %) II CH3OH
MC-II(A)-5 carbon (B) Mo Mo acetylacetonate (10 wt %) Co acetylacetonate (2 wt %) II CH3OH
MC-II(A)-6 carbon (A) Mo Ammonium molybdate (10 wt %) Co nitrate hexahydrate (2 wt %) II CH3OH
MC-III(A)-1 carbon (A) Mo Mo acetylacetonate (10 wt %) Co acetylacetonate (2 wt %) IIId CH3OH
MC-III(A)-2 carbon (A) Mo Mo acetylacetonate (20 wt %) Co acetylacetonate (4 wt %) III CH3OH
MC-III(A)-3 carbon (A) Mo Mo acetylacetonate (15 wt %) Co acetylacetonate (2 wt %) III CH3OH
MC-III(B)-4 carbon (B) Mo Mo acetylacetonate (10 wt %) Co acetylacetonate (2 wt %) III CH3OH
CM-III(A)-1 carbon (A) Co Mo acetylacetonate (10 wt %) Co acetylacetonate (5 wt %) III CH3OH
MC-IV(A)-1 carbon (A) Mo Mo acetylacetonate Co acetate IVe C2H5OH/H2O (2:1)
MC-IV(A)-2 carbon (A) Mo Mo acetylacetonate Co acetate IV C2H5OH/H2O (2:1)
MC-IV(A)-3 carbon (A) Mo Mo acetylacetonate Co acetate IV C2H5OH/H2O (2:1)
CoMo/Al2O3a alumina MoO3 (13.7 wt %) CoO (3.2 wt %)
a Commercial catalyst. b Normal impregnation. c Successive impregnation. d Successive impregnation with sulfiding in between.
e Equilibrium adsorption.
respectively. Both of them were provided by Mitsubishi The precursor catalyst was placed in a desiccator
Chemical Co. and were used without further treatment. under vacuum at ambient temperature until further
(c) Catalysts Preparation. (1) Successive Im- use. Composition, the referred symbol, and physical
pregnation. A series of catalysts were prepared through properties of the prepared catalysts are summarized in
successive impregnation in which the required amount Table 1. A Co-Mo/Al2O3 conventional commercial
of molybdenum salt dissolved in either methanol, etha- catalyst was also examined for comparison. The nomi-
nol, or water was poured to the carbon support. This nal metal compositions of this catalyst were reported
slurry was exposed to ultrasonic vibration for 1 h to be 13.7% Mo and 3.22% Co supported on alumina.
followed by solvent evaporation in air over a water bath (d) Activity Measurements. The catalytic proper-
at 45 C with stirring (total time was about 4 h), ties were studied in a 100-cm3 autoclave reactor (mag-
thereafter drying in an oven overnight at 120 C. A netically stirred) charged with 2.9 MPa hydrogen pres-
dissolved solution of an appropriate concentration of sure. The reactor was loaded with appropriate weight
cobalt salt was added to this precursor. Then, the of sulfided base catalyst. Prior to the activity test, the
solution was treated using the same solvent removal catalyst was sulfided using 5% v/v H2S in hydrogen with
and drying procedure as above. a total flow rate of 60 cm3/min. The sulfidation process
(2) Successive Impregnation with Sulfidation in for all the present catalysts was done at 360 C. A
Between. Another series of catalysts were prepared solution of 1 wt % dibenzothiophene (DBT) in decane
as described above but with sulfidation of molybdenum and/or 0.1 wt % 4,6-dimethyldibenzothiophene (4,6-
precursors before the impregnation with cobalt salts. DMDBT) in decane were prepared. Then 10 g of either
One catalyst was prepared in which cobalt was intro- DBT or 4,6-DMDBT solution was charged in the reactor
duced first, thereafter sulfidation, and then addition of with 0.1 or 0.2 g of freshly sulfided catalyst, respectively.
the molybdenum precursor. The catalysts were sulfided The reactor was purged four times with hydrogen gas
by a stream of 5% v/v H2S/H2 at 360 C. After sulfida- before the experiment was started. In all the experi-
tion time (3 h), H2S/H2 gas was continually swept over ments, the stirring speed was kept constant at 1000
the catalyst while cooling to room temperature. rpm. The starting reaction time was assumed to be
(3) Equilibrium Adsorption for Impregnation. considered when the required temperature was reached.
Another set of catalysts was prepared by equilibrium This temperature was kept constant during the reaction.
adsorption of Co and Mo. Three different concentrations The same temperature program was used in each
of ethanolic solution of both molybdenum acetylaceto- experiment. At the end of reaction, the reactor with its
nate and cobalt acetate were prepared (i.e., 0.1 M, 0.22 contents, was rapidly cooled down to room temperature
M, and 0.44 M molybdenum acetylacetonate and 0.03 by being quenched it in a cold water bath. The sample
M, 0.06 M, and 0.12 M cobalt acetate). Each catalyst after reaction was filtered. The catalyst was washed
was prepared typically as follows: 1.5 g of carbon several times with toluene to remove any adsorbed
support was immersed in 50 mL of molybdenum acety- species that may be on the catalyst surface or within
lacetonate solution at ambient temperature and then the catalyst pores. Toluene was found to be the best
exposed to ultrasonic vibration for 1 h. After the solvent among ethanol, tetrahydrofuran, and acetone to
solution underwent magnetic stirring for 24 h at ambi- recover the reaction products from the surface of the
ent temperature, the carbon particles were filtered catalyst quantitatively.
(without washing) and dried in an oven at 120 C (e) Reaction Analysis. Reference material (4,4-
overnight. Next, the carbon containing the adsorbed diethylbiphenyl) of known concentration was added to
molybdenum precursor was sulfided at 360 C as the collected sample after reaction. Analysis of this
described previously. The precursor, after sulfidation, sample was accomplished with a Yanaco (G-3800) gas
was immersed in 50 mL of cobalt acetate solution at chromatograph equipped with a differential flame ion-
room temperature. This slurry was left under ultra- ization detector and linear temperature programming.
sonic vibration for 1 h, thereafter magnetically stirred A capillary column (OV-101; 0.25 mm 50 m) was used
for 24 h, and then filtered and dried in an oven at 120 and permitted good separation. Quantitative analysis
C overnight. of the chromatograms was obtained with the aid of an
 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998 3535

Table 2. Pseudo-First-Order Rate Constants of HDS of

DBT and 4,6-DMDBT (340 C and 2.9 MPa H2)
catalyst kDBTa k4,6-DMDBTa
CoMo/Al2O3 0.0055 0.0020
M-I(A) 0.0009
C-I(A) 0.0004
MC-II(A)-1 0.0024 0.0008
MC-II(A)-2 0.0125 0.0021
MC-II(A)-3 0.0036 0.0015
MC-II(A)-4 0.0033 0.0011
MC-II(A)-6 0.0023
MC-III(A)-1 0.0192 0.0038
MC-III(A)-2 0.0184 0.0027
MC-III(A)-3 0.0143 0.0023
CM-III(A)-1 0.0187 0.0017
MC-IV(A)-1 0.0063
MC-IV(A)-2 0.0130 0.0029
MC-IV(A)-3 0.0096 0.0013 Figure 1. Effect of cobalt content on the activity of HDS of DBT
and 4,6-DMDBT (series II catalysts) (340 C and 2.9 MPa H2).
MC-II(B)-5 0.0123 0.0012
MC-III(B)-4 0.0192 0.0018
MC-II(A)-2 0.0105 0.0021 in detail in the Experimental Section. The preliminary
MC-III(A)-1 0.0192 0.0038 sulfidation process is believed to provide a much better
coordinating site for the cobalt through sulfide linkage
a Rate constant, s-1gcat.-1.
on the MoSx edges. The catalyst MC-III(B)-4 showed
electronic integrator. The response factors were deter- much higher activity than catalyst MC-II(B)-5. These
mined on the basis of the reference. Qualitative analy- two catalysts were prepared using different kinds of
sis of the sample was obtained from the retention time carbon with very high surface area (i.e., more than 3000
of the standard sample and GC mass spectra. As the m2/g). Accordingly, the advantage of presulfiding is still
gaseous products have not been determined, the mass evident even with carbon of high surface area. There-
balance of each experiment was calculated according to fore, we can conclude that the improved activity of HDS
the same equation used in ref 13. of series III catalysts is probably very dependent on the
preliminary MoSx phase on the surface, whatever the
type of carbon support.
Results Table 2 also shows that catalysts prepared by equi-
(a) HDS of DBT. DBT and its derivatives were librium adsorption (series IV) exhibited high activity for
selected to be model compounds for HDS to evaluate HDS of DBT. The activity of these catalysts depended
the activity of the present series of carbon-supported with a large extent on the initial metal concentration
catalysts. Recently, it was confirmed that these kinds solution. The MC-IV(A)-2 catalyst had the maximum
of compounds are on one hand the most refractory sulfur activity of this series. It is interesting to note that the
compounds for HDS reaction and are major sulfur best catalysts in series II, III, and IV showed much
constituents in petroleum oils.14-16 Pseudo-first-order higher activity than the commercial catalyst, especially
rate expressions have been widely reported to be ap- series III catalysts which were more than twice as active
propriate for HDS of thiophenic compounds.17,18 This as the Co-Mo/Al2O3 catalyst.
kinetic form was found to be applicable to our experi- The effect of cobalt loading on the activity of HDS of
ments as well. All the catalysts were tested at 2.9 MPa DBT and 4,6-DMDBT of molybdenum-supported carbon
hydrogen pressure and 340 C, allowing a comparative catalysts is shown in Figure 1 and will be handled later.
study of the catalysts. Table 2 shows the catalytic (b) Kinetic Analysis of HDS of DBT. The products
activities of the various catalysts for HDS of DBT and detected during the HDS reactions of DBT were bi-
4,6-DMDBT. Obviously, the nature of catalyst treat- phenyl, phenylcyclohexane, tetrahydrodibenzothiophene,
ments and the arrangement of metal additions had a and H2S in accordance with other findings.22-24 Figure
great influence on the activity of HDS of both DBT and 2 shows typical product distributions versus time for
4,6-DMDBT. From Table 2, one can see that either an HDS reaction of DBT over an MC-II (A)-2 catalyst.
molybdenum or cobalt when loaded alone on carbon The reaction scheme based on our results can be
support gives considerably lower activity than when depicted as in Figure 3. For proper kinetic evaluation
both of them were provided together. This result is of the conversion selectivity, it is necessary to find
consistent with the pattern of activity reported in the means for distinguishing the relative contributions of
literature.19,20 Furthermore, the HDS activity of acetyl- the all pathways to the formation of products. The
acetonate precursor-derived catalysts are consistently relative rate constants are defined as follows:
higher than those of catalysts prepared using am-
monium molybdate, cobalt nitrate, and/or cobalt acetate. rate
constant reaction concerned
In a previous study using oxygen adsorption for such
catalysts Chary et al.21 concluded that the dispersion kD0 desulfurization without ring hydrogenation
kD1 desulfurization of 1 ring hydrogenated sulfur compound
of acetylacetonate-derived catalysts is much higher than kHS1 hydrogenation of one ring of the sulfur compound
those derived from common salts. kHP1 hydrogenation of one phenyl ring of desulfurized biphenyl
The series III catalysts exhibited very high activity kHS1 dehydrogenation of one ring of the sulfur compound
in comparison with those of the other methods. The
only difference between series III and II during their The values were calculated assuming first-order
preparation is the sulfidation of the molybdenum pre- expression for each step. The details of determining the
cursor before the addition of cobalt solution as described various rate constants and how to set reasonable
3536 Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998
Figure 2. Kinetics of HDS of DBT over MC-II(A)-2 catalyst (340
C and 2.9 MPa H2).
Figure 3. Scheme of HDS of DBT.
Figure 4. Selectivity of HDS of DBT over series I, II, III, and IV
catalysts (340 C and 2.9 MPa H2).
boundaries in order to achieve good matching between
experimental data and theoretically derived curves were
discussed elsewhere.25 Clearly, the hydrodesulfuriza-
tion of DBT (Figure 2) proceeds through two different
pathways, a hydrogenation route and a direct desulfu-
rization route. Figure 4 shows the selectivity of HDS
of DBT over all the catalysts of this study. It can be
seen that from a selectivity point-of-view, all catalysts
behave similarly and follow the reaction scheme of
Figure 3. Biphenyl was the main product, but a
significant amount of phenylcyclohexane was observed.
kHP1 was much smaller than kD0. So the phenylcyclo-
hexane is produced mainly from the subsequent hy-
drodesulfurization of tetrahydrodibenzothiophene. The
relative rate constant values shown in Table 3 indicate
that the main route of HDS of DBT proceeds via a direct
desulfurization route, independent in the catalyst prepa-
ration method.
Table 3. Relative Individual Rate Constants of HDS
Scheme of DBT over CoMo/C Catalysts (340 C and 2.9
MPa H2)a
catalyst kD0 kHS1 k-HS1 kD1 kHP1
series I, II, III, and IV 4 0.66 1 17 0.008
a All the rate constants abbreviations are defined in the text.
Figure 5. Kinetics of HDS of 4,6-DMDBT over MC-II(A)-2
catalyst (340 C and 2.9 MPa H2).
(c) HDS of 4,6-DMDBT. The HDS rate constants
of 4,6-DMDBT over the catalysts of this study at 340
C and 2.9 MPa hydrogen pressure are illustrated in
Table 2. The rate constants were calculated from
pseudo-first-order expressions as mentioned previously.
The reaction pathways are illustrated in Figure 5 where
3,3-dimethylbiphenyl, cis- and trans-3,3-dimethyl-
phenylcyclohexane, H2S, and 4,6-dimethyltetrahydro-
dibenzothiophene were the only products observed
under our experimental conditions. Table 2 shows that
series III catalysts exhibited the highest catalytic activi-
ties of HDS of 4,6-DMDBT, following the same ranking
as in HDS of DBT, although DBT was 2-4 times more
reactive than 4,6-DMDBT. A significant observation
was that Co-Mo catalysts prepared by an equilibrium
adsorption method (IV) exhibited considerable activity,
suggesting further studies with this approach as it
would lead to a better method of catalyst preparation.
The HDS selectivities in 4,6-DMDBT over the cata-
lysts can be divided into two groups, one is the series
prepared by method II and the other is prepared by
method III. The selectivity behavior of the two groups
is depicted in Figures 6 and 7. Thus, there was a clear
difference in the selectivity, regarding the preparation
method. The relative rate constants of the reaction
scheme are shown in Table 4. We can summarize the
observations as the following.
It is evident that the MC-III(A)-1 catalyst prepared
by method III, in which sulfidation of the molybdenum
precursor was performed before successive impregnation
of cobalt, showed very high activity (nearly 2-fold)
compared with the MC-II(A)-2 catalyst prepared by
method II (standard procedure).
It is also clear that the method of preparation has the
greatest impact on the hydrogenation rate constants.
All species were hydrogenated much faster over method
III preparations than over method II preparations.
This difference is attributed only to the sulfidation
step between impregnation since the metal contents of
these catalysts were the same (Table 1).
Surprisingly, the CM-III(A)-1 catalyst, prepared by
reversing the impregnation order of Mo and Co, also

Figure 6. Selectivity of HDS of 4,6-DMDBT over series II
catalysts (340 C and 2.9 MPa H2).
Figure 7. Selectivity of HDS of 4,6-DMDBT over series III
catalysts (340 C and 2.9 MPa H2).
Table 4. Individual Rate Constants of HDS Reaction
Scheme of 4,6-DMDBT over CoMo/C Catalysts (340 C and
2.9 MPa H2), k 10-4
catalyst kD0 kHS1 k-HS1 kD1 kHP1
series II 9 12 120 360 0.36
series III and IV 11 27 270 810 1.35
showed a comparable HDS activity. This is contrary
to activity preparation sequences reported in the lit-
erature.26 It is uncertain at this point why this is so.
(d) Influence of Metal Loading. The hydrodes-
ulfurization rate constants of DBT and 4,6-DMDBT as
a function of cobalt loading for series II preparations
are presented in Figure 1. Note that for all catalysts
the Mo load was held constant at 10 wt % as the cobalt
concentration was varied. It can be seen that the HDS
activities for both DBT and 4,6-DMDBT increased up
to a maximum at about 2 wt % cobalt and then
decreased with further increase of cobalt additions.
Thus, the Co/Mo ratio that provided the highest cata-
lytic properties was 0.326. Such a level is slightly lower
than that of the commercial catalyst.
The activity of HDS of both DBT and 4,6-DMDBT
over the MC-III(A)-1 catalyst was substantially en-
hanced. However, higher activity over this catalyst is
manifested mainly by enhancing the hydrogenation
route rather than the direct desulfurization (Tables 4
and 5). These results suggest that the relative ratio of
catalytic sites for direct desulfurization and hydrogena-
tion reactions may vary with the method of preparation.
If one assumes that there are two independent catalytic
Ind. Eng. Chem. Res., Vol. 37, No. 9, 1998 3537
Table 5. Effect of Preparation Method on the Activity of
HDS Reaction Scheme of 4,6-DMDBT over
CoMo-Supported Various Carbon Catalysts (340 C and
2.9 MPa H2)
catalyst kta kD0b kHS1b
MC-II(A)-2 0.0021 0.0009 0.0012
MC-III(A)-1 0.0038 0.0011 0.0027
MC-II(B)-5 0.0012 0.0005 0.0007
MC-III(B)-4 0.0018 0.0005 0.0013
a Overall rate constant of HDS, s-1gcat.-1. b Individual rate
constants of the reaction scheme.
active sites, then the enhanced activity of MC-III(A)-1
catalyst is largely attributed to the enhancement of
hydrogenation active sites in comparison with direct
desulfurization active sites, which were only slightly
increased as discussed previously.
Another sample MC-III(A)-2 of which the Mo and Co
contents were 20 and 4 wt %, respectively, double the
metal content of the catalyst MC-III(A)-1, was com-
pared. Note that the surface area of the carbon support
is quiet large (i.e., 1350 m2/g) and might be expected to
permit a good dispersion of increased amounts of metals.
However, the activity is slightly decreased in HDS of
DBT and considerably suppressed in the case of HDS
of 4,6-DMDBT, in comparison to the MC-III(A)-1 cata-
lyst as shown in Table 2.
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-
lysts are generally prepared from the oxides, the oxides
are readily converted to the sulfides in the presence of
sulfur compounds in the feedstocks. Therefore, MoS2
is generally considered to be important in the catalyti-
cally active phase.22,26-29 Vissers et al.,8 on the basis
of XPS studies on Mo/C catalysts, have pointed out that
the Mo in its oxidic phase was found to be monolayerlike
dispersed up to Mo/C atomic ratios of about 0.0039. On
the other hand, they attributed the deviation from the
theoretical monolayer coverage observed at higher Mo/C
ratios to the formation of three-dimensional particles.
Some sintering of the active phase was noticed during
sulfiding even at the low Mo loading, indicating a
certain mobility of the Mo phase during sulfiding. This
indicates the presence of weak interactions between the
active phase and carbon. It may be that the same
situation is possible for the present series of catalysts
and long time performance studies are warranted.
The results of the present study indicate that the HDS
of DBT and/or 4,6-DMDBT activities of carbon-sup-
ported Co-Mo catalysts strongly depend on the method
of preparation and metal-loading level. As shown in
Table 2, series III catalysts showed the highest activi-
ties. It was nearly twice as active as the conventional
commercial catalyst (Co-Mo/Al2O3). The only difference
between MC-II(A)-2 and MC-III(A)-1 catalysts during
their preparation is the sulfidation of the Mo precursor
before cobalt addition for the MC-III(A)-1 catalyst.
Indeed, this step does greatly improve the activity of
HDS. To interpret this behavior, it is worthwhile to
consider the phenomena involved in the sulfidation
process. Consequently, let us first follow the sulfidation
steps in detail. It is generally accepted30 that the
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
steps. At first, pure sulfidation takes place in which
successive O-S exchange to oxysulfides then is trans-
ferred to sulfido molybdenum complexes and finally to
MoS3-like species. The last precursor is reduced from
Mo(VI) to Mo(IV) through rupture of Mo(VI)-S bonds
with the formation of elemental sulfur. The elemental
sulfur produced adsorbs on the support surface and is
reduced with hydrogen to H2S. This mechanism has
been confirmed using many tools such as X-ray photo-
electron spectroscopy, temperature-programmed de-
sorption, and temperature-programmed sulfiding. Fur-
thermore, it is well-known that MoS2 is a relatively low
active catalyst that is modified in some way by the
promoter atoms (Co), producing much more active
catalyst. Topse and co-workers22,26,30 have proposed
the existence of the so-called Co-Mo-S phase in Co-
Mo/Al2O3 catalysts. The cobalt is thought to be located
on the edges of the MoS2 crystallites bonded to the Mo
through sulfide bridges and the high activity is really
associated with the promoter rather than the underlying
MoS2.
On the basis of the reactivity results of series II and
III catalysts, it is probable that in series II catalysts,
Mo-oxides-like species do not entirely convert to its
sulfidic state during the sulfidation process.20 This may
be due to the presence of cobalt that may shield the Mo
atoms from sulfurization. Even in the case of series III
(sulfidation before cobalt addition) catalysts, some Mo-
oxide phases may still remain after sulfidation. Perhaps
only the surface MoO3 crystals were converted to
sulfides. This surface phase is more important than the
bulk phase. Usually, the bulk phase is not accessible
during the reaction, since the reactant species will be
adsorbed only on the active exterior edges of the
crystallites. It might be reasonable to assume that
besides the Co-Mo-S phase structure there also may
be a Co-Mo-O phase. The latter one is most likely
catalytically inactive. This is in contrast to series III,
in which the Mo-sulfide phase is produced before cobalt
impregnation. The genesis of the Mo-sulfide phase on
the carbon surface is, therefore, of vital importance.
Independent of the type of carbon support, this effect is
still pronounced. This can be seen if we compare the
activity of HDS of MC-II(B)-5 and MC-III(B)-4 catalysts
in Table 2. These catalysts were prepared from a
different kind of carbon with a very high surface area
(3060 m2/g). The enhancement in activity of HDS of
MC-III(B)-4 catalyst can be noted from Table 2. The
improvement in HDS activity of both DBT and 4,6-
DMDBT is clear, although the enhancement of HDS of
4,6-DMDBT was again found to be mainly in the
hydrogenation route (i.e., Table 5).
(b) Effect of Order of Metal Addition. It is well-
recognized that the addition of cobalt to molybdenum
catalysts enhances the HDS activity. However, the
influence of the impregnation order of Co and Mo salt
is not obvious; in the literature, it has been reported
that the highest activity of HDS of Co-Mo catalysts is
obtained when Mo is impregnated first which leads to
good dispersion of cobalt.22,31,32 Most of these studies
have used Al2O3 as a support. To investigate this effect
in the case of the carbon support, catalyst CM-III(A)-1
was prepared in which Co salt was impregnated first,
then sulfidation, and thereafter addition of Mo salt as
summarized in Table 1. The catalytic activity for HDS
of DBT and 4,6-DMDBT is depicted in Table 2. It is
interesting to note that the HDS activity of CM-III(A)-1
is comparable with that of series III catalysts, especially
in the case of DBT. The impact of this observation is
presently being investigated.
While the proposed active phase in Co-Mo catalysts,
when molybdenum is impregnated first, is the Co-
Mo-S phase, it should be different when cobalt is
introduced first to the support. As mentioned above,
the MoS2-phase-like species acts as a support for the
cobalt sulfide phase if molybdenum is introduced first.
The same phenomena may also be applied in the
situation when cobalt is introduced first (i.e., the cobalt
sulfide phase serves as a support for the MoS2-phase-
like species). This would imply that either Mo sulfide
phases or cobalt sulfide phases can behave as a support
of each other. However, the recent observation that the
maximum activity is observed at a stoichiometry of
about 2Mo/1Co when the metals are coimpregnated may
indicate that the Co-Mo-S active site is a thermody-
namically stable species which is formed during sulfi-
dation by rearrangement of the various components.33,34
(c) Effect of Co and Mo Concentration. Figure 2
shows the impact of cobalt content on the activity of
HDS of both DBT and 4,6-DMDBT. Comparison of the
activity results of HDS over series II catalysts shows
that the maximum activity occurred at a Co/Mo atomic
ratio of 0.325. This is similar to that found in many
reported studies35 even over different support materials.
Chin and Hercules36 have shown that as the cobalt
concentration increased, a new phase is formed as
characterized by interactions between Co and Mo. This
species is produced up to a concentration of 5.5 wt %
Co. Above this level Co3O4 is formed. This species of
cobalt is undesirable because it has low activity for HDS.
Therefore, the homometallic phases such as Co3O4,
Co9O8, and MoS2 are of secondary catalytic importance
in Co/Mo catalysts.
The limitation of Mo dispersion with increasing
loading should be less critical for higher surface area
carbons since the support surface might be expected to
be able to accommodate it. As the MoS2 phase disper-
sion is increased, it is very probable that the cobalt
phases will also have a good chance to be found in a
high dispersion level, which consequently leads to high
HDS activity, as there is direct proportion between
dispersion and activity. Experimentally, the reverse
was found. The catalyst MC-III(A)-3 (15 wt % Mo and
2 wt % Co) exhibited lower activity than the catalyst
MC-III(A)-1 (10 wt % Mo and 2 wt % Co) in HDS of both
DBT and 4,6-DMDBT. The explanation of the observed
effect is uncertain. Pratt et al.20 on their study of the
morphology of Mo over ZrO2 and TiO2 have found that
after the formation of a complete monolayer of MoS2 on
ZrO2 and/or TiO2, the surface of the support is no longer
available to the reactants. In addition, they have
observed that the MoS2 surface species consists of what
they called raftlike structures, sitting flat on the sup-
port. At higher loading, the raft expands to coat the
support in a continuous layer, thus exposing only the
basal planes of the MoS2.
The lower HDS activity observed in the MC-III(A)-3
catalyst may possibly be attributed to fewer rims and
edge sites compared with those of the MC-III(A)-1
catalyst according to the model proposed by Daage and
Chianelli37 and/or Pratt et al.20
Another explanation of this observation may be
related to the sintering effect.8 The mobility of the Mo

phase is also expected since there is no strong interac-
tion between the active phase and the support. This
leads to a result that the agglomeration of Mo phases
is favored at high concentration of Mo, even with the
supports that have slightly strong interaction with it,
like Al2O3.
Conclusions
On the basis of the initial activity data, carbon
appears to be an effective support for hydrodesulfur-
ization catalysts. A synthesis of novel hydrotreating
Co-Mo catalysts has been achieved using different
preparation methods. The method of preparation and
the way of treatment of the catalysts were found to
strongly affect the activity. Sulfidation of the Mo
precursor before cobalt (promoter) addition was found
to greatly enhance the activity of HDS of DBT and 4,6-
DMDBT. The enhancement was more pronounced
through hydrogenation routes in the case of HDS of 4,6-
DMDBT. Moreover, the activity of this series is nearly
2-fold as active as the commercial Co-Mo/Al2O3 cata-
lyst. The enhancement in activity is believed to be due
to a more efficient production of the Co-Mo-S active
species from the MoS2 on the carbon surface.
The series prepared by equilibrium adsorption have
also comparable activity, which may lead to an improved
preparation method.
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Received for review February 9, 1998
Revised manuscript received May 21, 1998
Accepted June 8, 1998
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