Catalysis Communications 2 (2001) 81±87

www.elsevier.nl/locate/catcom

Based CoMo sulphided catalysts supported on hydroxyapatite:

Dimethyldisulphide (DMDS) hydrogenolysis
Y. Saih *, M. Ait Chaoui, A. Ezzamarty, M. Lakhdar
Facult
e des Sciences, Laboratoire de Catalyse H
et
erog
ene, Universit
e HASSAN II Aõn Chock, BP 5366 Ma^
arif, Casablanca, Morocco
Received 16 November 2000; received in revised form 14 February 2001; accepted 14 February 2001

Abstract
A series of Ca-de®cient and Co-containing hydroxyapatite samples, noted Ar and Cx , respectively, where r is the total
Ca/P molar ratio (r ˆ 1:46±1.62) and x the Co wt%, were prepared by precipitation in aqueous media. The catalytic
activities of CoMo/Ar and Mo/Cx sulphided catalysts have been examined for the S±S bond hydrogenolysis of di-
methyldisulphide (DMDS) under relatively mild operating conditions (200°C, 1 atm). The overall activity depends on
the Co depositing mode and the hydroxyapatite carrier Ca/P molar ratio. Depositing Co by impregnation on hy-
droxyapatite samples with low Ca/P molar ratios involves an increase of the catalytic activity until approaching that
corresponding to CoMo=Al2 O3 catalyst. This can be attributed probably to a better dispersion of the CoMo sulphided
catalysts on apatitic carrier with low Ca/P molar ratios. DMDS is selectively reduced to CH3 SH on the CoMo=A1;46
sulphided catalyst than on the CoMo=Al2 O3 one, even at conversions as higher as 100%. Ó 2001 Published by Elsevier
Science B.V.

1. Introduction utilisation in the ®rst step of the commercial

Thiochemistry is related to the synthesis of
about 30 compounds shared out between mer-
captans, sulphides, polysulphides, sulphones or
sulphoxides, thioacids, and thioesters. The sulphur
containing molecules are used in increasing quan-
tities in agrochemicals, pharmaceutical products,
petrochemicals, lubricants, cosmetics, and gas
odorants. Mercaptans are the most important be-
cause they are very often utilised as starting ma-
terials for the synthesis of the other
thiocompounds. Beside these applications, a large
amount of methanethiol is produced because of its
*
Corresponding author. Fax: +212-22-23-06-74.
E-mail address: youssef_19@hotmail.com (Y. Saih).
1566-7367/01/$ - see front matter Ó 2001 Published by Elsevier Science B.V.
PII: S 1 5 6 6 - 7 3 6 7 ( 0 1 ) 0 0 0 0 7 - 3
synthesis of methionine, an amino acid used as
poultry feed supplement. Industrially, methylmer-
captan is currently prepared by direct thiolation of
methanol over alkali metal salts or oxides sup-
ported on alumina and acidic catalysts [1]. Meth-
ylmercaptan is characterised by its obnoxious
odour, highly ¯ammable properties and its drastic
toxicity. This gas is shipped in various sizes of
pressure and copper free alloy vessels. In the fu-
ture, it could be expected that the transportation
of such hazardous compound will be faced with
increasing environmental requirements. For these
reasons, the transformation of CH3 SH into a safer
compound such as alkali mercaptides has been
already considered. Starting from this organic salt,
the back formation of CH3 SH requires only a
hydrolysis step in a slightly acidic media. However,
82 Y. Saih et al. / Catalysis Communications 2 (2001) 81±87
this step leads to the unavoidable formation of
alkali salts wastes. Another possibility would be to
convert CH3 SH into dimethyldisulphide (DMDS,
boiling point 383 K) by air oxidation in the pres-
ence of a base at room temperature. As DMDS is
already produced at a large scale for sulphiding
purposes, this alternative could be interesting only
when the selective catalytic hydrogenolysis of the
S±S bond could be achieved. So, the utilisation of
conventional reductive organic reagents such as
hydrides [2], trivalent phosphorus compounds [3],
hydroxides, cyanides ions [4], cannot be considered
in industrial plans. Recently, Calais et al. [5,6]
have reported that sulphided catalysts may cata-
lyse the reduction of aryl disulphides into their
corresponding thiols at a temperature as low as
433 K and under a hydrogen pressure of 2280
Torr.
Industrial hydrotreating catalysts are based on
a group VI metal such as molybdenum or tungsten
promoted with a group VIII metal (cobalt or
nickel) and often contain phosphorus to improve
their catalytic activity. Accordingly, it seems in-
teresting to study the use of phosphorus materials
and specially calcium phosphate ores that are
easily available and constitute a cheap source of
material, as sulphided catalysts carrier.
The aim of the present work, is to investigate
the use of hydroxyapatite as a carrier for CoMo
sulphided catalysts in the hydrogenolysis of
DMDS.
At ®rst, we studied the in¯uence of the cobalt-
depositing mode on the S±S bond cleavage of
DMDS and on the other hand, we investigated the
role of the Ca/P molar ratio of a series of Ca-de-
®cient hydroxyapatite carrier in the hydrogenoly-
sis of DMDS. Finally, we explored the ability of
the CoMo/Phosphate catalysts to transform se-
lectively DMDS into CH3 SH.
2. Experimental
2.1. Reagents
The DMDS was supplied by LABOSI pro-
duct (purity > 98%). The Co…NO3 †2 , 6H2 O and
Ca…NO3 †2 , 4H2 O, used as cobalt and calcium
sources in the preparation of the Ar and Cx
samples, were purchased from Riedel-de-Haen
(purity > 98%). The …NH4 †2 HPO4 , used in the
precipitation of hydroxyapatite, was purchased
from Riedel-de-Haen with 99±102% purity. The
NH4 OH was a Riedel-de-Haen product (25%
NH3 ). H3 PO4 , used in the preparation of hy-
droxyapatite by neutralisation, was supplied by
PANREAC (85%), whereas the Ca…OH2 † was
prepared by CaCO3 (Acros 98%) calcination at
900°C during 24 h.
2.2. Apparatus
Transmission IR spectra were recorded at room
temperature using a Nicolet MX1 FTNIR spec-
trophotometer in the wavenumber region 400±
4000 cm 1 ) with a 2 cm 1 resolution.
The powder X-ray di€raction was performed
using a Phillips 1710 apparatus with a radiation of
Ni-®ltered CuKa.
The textural properties were determined using
nitrogen adsorptiometry at )196°C on ASAP 2000
apparatus.
The catalytic experiments were performed in a
®xed-bed continuous ¯ow quartz reactor operated
at atmospheric pressure. The DMDS and products
of conversion were analysed with an on-stream gas
chromatograph (Varian 3700) equipped with a
FID detector and integrator (Varian SP 4270). The
columns used in the present study are OV 17 (2m)
and OV 101 (2m) mounted on serial.
The calcium, phosphorus, cobalt and molyb-
denum contents were assessed in the ``Centre de
Microanalyse de Vernaison''.
2.3. Preparation
2.3.1. Supports
Two series of phosphate supports were pre-
pared.
· The ®rst one, noted Cx (where x represents the
cobalt weight percent), was prepared by copre-
cipitation method as reported elsewhere [7].
· The second one, noted Ar (where r is the overall
Ca/P molar ratio), was prepared in the absence
of Co ions by coprecipitation in the same way
as for the Cx series, except for the A1;54 solid
 Y. Saih et al. / Catalysis Communications 2 (2001) 81±87
which was prepared by neutralisation according
to Bett's method [8] as reported below.
In a typical experimental precipitation of the A1:62
sample, 300 ml of a calcium solution, with a total
molarity of 0.26 M, was added dropwise to
1000 ml of re¯uxed diammonium hydrogeno-
phosphate solution (0.09 M). The pH of both the
Ca and phosphorus solutions was equal to 10 be-
fore mixing, and kept constant during the overall
precipitation process using concentrated ammo-
nia. After ®ltration, the white precipitate was wa-
shed using distillated water, then dried at 80°C for
12 h. Finally, the solid was treated at 400°C
(1.6°C min 1 ) for 4 h.
The pH of the precipitation process was varied
in order to prepare Ar hydroxyapatite samples
with di€erent Ca/P molar ratios.
The A1;54 solid was prepared by neutralisation
of a CaO slurry by an H3 PO4 solution. 4.141 g of
freshly prepared CaO oxide was dissolved in 3.5 l
of distillated water, then 5.872 g of an H3 PO4 so-
lution (85 wt%) were added during almost 1 h at
room temperature. Finally, the slurry was re¯uxed
for 15 h. After ®ltration, the white precipitate was
washed and dried in the same way as reported
above for the Ar compounds.
2.3.2. Catalysts
Two series of CoMo oxide precursors were
prepared.
· The ®rst one, noted Mo=Cx , was prepared by
pore ®lling impregnation of cobalt coprecipi-
tated hydroxyapatite supports Cx by a heptamo-
lybdate solution at pH 7. Finally, the solids were
dried at 80°C during 24 h, then treated at 400°C
(1.6°C min 1 ) for 4 h.
· The second series, noted CoMo=Ar , was pre-
pared by the successive pore ®lling impregnation
with an ammonium heptamolybdate solution at
pH 7, then after intermediate calcination at
400°C, with a cobalt nitrate solution at the same
pH. Finally, the solids were dried at 80°C during
24 h, then calcined at 400°C (1,6°C min 1 ) for
4 h.
The concentrations of the heptamolybdate and
cobalt nitrate solutions, used in the impregnation
process, were varied in order to prepare catalysts
with di€erent amounts of Co and Mo.
83
The same procedure was applied to an
d-alumina from Ketjen 000.1.5 E …220 m2 g 1 ;
3:6 cm3 g 1 † with a Mo coverage ca. 3 atm nm 2
and a Co=…Co ‡ Mo† ratio of 0.3.
2.4. Catalytic measurements
The CoMo solids, treated at 400°C, were sul-
phided in situ at 360°C and 1 atm during 3 h under
a ¯ow of 15% H2 S±85%H2 …0:08 mol h 1 †.
The DMDS reaction was studied at 200°C. The
products were CH3 SH and CH3 SCH3 identi®ed
using gas chromatography (GC). The steady-state
fractional conversion x was obtained after 2 h with
the phosphate catalysts. The catalytic activity was
evaluated at conversion lower than 10% after
changing when necessary the catalyst mass or
DMDS ¯ow rate. Thus, the speci®c activity is gi-
ven by the pseudo ®rst-order rate constant K,
Kˆ F ° ln…1 x†=WC°; in 1 h 1 g 1 ;
where F ° is the DMDS total ¯ow rate (1.8±
5.6 mmol h 1 ), C° is the total concentration of
DMDS in the reactor …0:83 mmol l 1 † and W is
the weight of the sulphided catalyst (0.02±0.1 g).
All the catalytic tests were conducted under a
dried atmosphere.
3. Results and interpretation
3.1. Characterisation of the supports
All the samples Ar exhibited a X-ray di€raction
diagram only with space group P63 =m up to 800°C
(typical spectrum is shown in Fig. 1 for the A1;46
sample dried at 80°C). Upon calcination at 900°C,
the patterns show apparition of a new peak at
2h ˆ 31:0° in addition to the apatitic ones. This
peak can be assigned to b-Ca3 …PO4 †2 …b-TCP†
produced probably by dehydroxylation of HPO24
ions replacing PO34 in the lattice of Ca-de®cient
hydroxyapatite [9]. This was con®rmed by IR
study. FT±IR spectra of all the solids Ar show the
presence of a band at 875 cm 1 (see the spectrum
shown in Fig. 2 for the A1;46 sample dried at 80°C),
assigned to the HPO24 groups substituting PO34 in
the lattice of Ca-de®cient hydroxyapatite [9,10].
84 Y. Saih et al. / Catalysis Communications 2 (2001) 81±87

balt excess form Co…OH†2 phase which is con-

verted to Co3 O4 oxide after calcination at 500°C
[7].

3.2. Catalytic activity

Fig. 1. XRD spectrum of the A1;46 sample dried at 80°C.
Fig. 2. FT±IR spectrum of the A1;46 sample dried at 80°C
(0.8 mg/250 mg KBr).
The overall Ca/P molar ratios of the solids Ar are
lower than 1.67 (Table 1) proving the formation of
Ca-de®cient hydroxyapatite compounds. The co-
balt substitution in the apatitic lattice was found to
be limited to up 8 wt%. Beyond this limit the co-
3.2.1. Mo=Cx
DMDS is totally converted into H2 S and CH4
at 360°C. Therefore, the sulphided CoMo/apatite
catalysts exhibit hydrodesulphurisation properties
as the conventional CoMo=Al2 O3 hydrotreating
catalyst.
Recent results dealing with the catalytic reduc-
tion of aryl disulphides suggested that the S±S
bond breakings require the presence of both SH
groups and coordinatively unsaturated metal ions
(CUS) [5,6]. This kind of sites is also involved in
the thiophene C±S bond hydrogenolysis [11,12]. A
mechanism in which the S±S hydrogenolysis may
proceed via the addition of Hd‡ species (®xed on a
sulphur anion) and of Hd adsorbed on a coord-
inatively sulphur-de®cient metal ion was reported
[5]. DMDS conversion onto the apatitic carrier (as
is the case for the Al2 O3 support) was found to be
negligible, under our operating conditions. It in-
dicates that the S±S bond cleavage takes place only
on the sulphided catalyst.
At 200°C, DMDS is selectively reduced to
CH3 SH with all the catalysts (conversion 6 10%†.
The addition of Mo increases the overall catalytic
activity up to a limiting coverage corresponding
probably to the formation of a Mo±S monolayer.
The catalytic activity remains constant beyond this
limit value (Fig. 3). The addition of cobalt ions
either by coprecipitation or impregnation im-

Table 1
Chemical composition and textural properties of Ar and Cx solids
Chemical analysis Adsorptiometrya
Support %wt Ca %wt Co %wt P Ca/P SBET (m2 g 1 ) Vp (cm3 g 1 ) Rp (nm)
A1;62 36.63 ± 17.42 1.62 81 0.324 7.2
A1;57 38.30 ± 18.80 1.57 83 0.320 7.7
A1;54 37.40 ± 18.80 1.54 78 0.334 7.0
A1:46 35.20 ± 18.60 1.46 64 0.360 6.2
C2;5 b 34.90 2.50 17.86 1.51 87 0.310 7.1
C6;2 b 30.40 6.18 16.20 1.45 116 0.330 5.7
a
Solids treated under vacuum at 400°C.
b
After [7].
 Y. Saih et al. / Catalysis Communications 2 (2001) 81±87 85

The Ca/P molar ratio of the surface apatitic

Fig. 3. Evolution of the catalytic activity for
Mo=C2;5 …r†; Mo=C6;2 …j† and Co2;5 Mo=A1;56 …N† sulphided
catalysts in the hydrogenolysis of DMDS at 200°C and 1 atm
versus Mo wt%.
proves the catalytic activity, which can be related
to the known cobalt promoting e€ect for the hy-
drogenolysis of the C±S and the S±S bonds using
the conventional alumina carrier. However, the
impregnated catalyst CoMo=A1;56 shows higher
speci®c activity than the coprecipitated ones
Mo=Cx for the same Co and Mo contents (Fig. 3).
This can be explained by a relatively easier cobalt
migration in the impregnated catalysts to form the
promoting sites for the S±S bond cleavage than in
the coprecipitated ones; where the Co ions are
®xed into the apatitic lattice. It seems therefore,
that the impregnated catalysts provide more labile
Co ions.
3.2.2. CoMo=Ar
The pseudo ®rst-order rate constant
K …l h 1 g 1 † for the Mo=Ar , CoMo=Ar , and
CoMo=Al2 O3 sulphided catalysts (with a Mo
coverage corresponding to ca. 3:5 atm nm 2 † at
200°C are summarised in Table 2.
layer is lower than the bulk one [13,14]. This result
indicates that the number of surface P±OH groups,
resulting from the protonation of surface PO34
species to compensate the relative Ca de®ciency
and the surface charge imbalance, increases with a
decrease of the Ca/P molar ratio. Assuming that
these surface P±OH species are the active sites for
the adsorption of the molybdenum entities in our
case, 31 P MASNMR studies of sulphided Mo,
NiMo, and CoMo supported on hydroxyapatite
are under investigation within our research team
to con®rm this suggestion, we can conclude that
the CoMo sulphided catalysts tend to be well dis-
persed on apatitic carrier with low Ca/P molar
ratio. Thus, the overall catalytic activity increases
with a decrease of the Ca/P molar ratio until ap-
proaching that corresponding to CoMo=Al2 O3
sulphided catalyst as is shown in Table 2.
In Fig. 4, we plotted the DMDS hydrogenolysis
pseudo ®rst-order rate constant K …l h 1 g 1 †
versus the atomic molar ratio a ˆ Co=…Co ‡ Mo†
for the CoMo=A1;46 sulphided catalyst, in order to
study the e€ect of the deposited metal atomic ratio
on the overall catalytic activity. The catalytic ac-
tivity increases with an increase of a up to a
maximum of 0.3, then it decreases with an increase
of a. This behaviour is similar to that observed for
the hydrodesulphurisation of thiophene-like mol-
ecules over supported sulphided catalysts. Pre-
sumably, for this value of a equal to 0.3 the entire
Co (or at least a constant fraction of it) is incor-
porated in the composition of the active centres
[15±17], similar to those responsible for the C±S
cleavage in the hydrodesulphurisation process [5].

Table 2
Pseudo ®rst-order rate constant K (l h 1 g 1 ) for the Mo/Ar , CoMo/Ar , and CoMo=Al2 O3 sulphided catalysts at 200°C
Catalysts atm Mo nm 2
a ˆ Co=…Co ‡ Mo† K …l h 1 g 1 †  1
Mo=A1;62 3.3 0 6
Mo=A1;57 3.1 0 5
Mo=A1;54 3.5 0 6
Mo=A1;46 3.3 0 7
CoMo=A1;62 3.3 0.28 8
CoMo=A1;57 3.1 0.28 10
CoMo=A1;54 3.5 0.28 16
CoMo=A1;46 3.3 0.32 26
CoMo=Al2 O3 3.4 0.29 33
86 Y. Saih et al. / Catalysis Communications 2 (2001) 81±87
Fig. 4. Dependence of the catalytic activity for the CoMo=A1;46
sulphided catalyst (3.3 atm Mo nm 2 ) on the atomic ratio
a ˆ Co=…Co ‡ Mo† in the DMDS hydrogenolysis at 200°C and
1 atm.
Fig. 5. Variation of CH3 SH selectivity onto the CoMo=A1;46
…a ˆ 0:28; 3:3 atm Mo nm 2 † and CoMo=Al2 O3 sulphided
catalysts for 50% and 100% DMDS conversions at 200°C and
1 atm.
In Fig. 5 we plotted the CH3 SH selectivity
versus DMDS conversion of 50% and 100% for
both the CoMo=A1;46 and CoMo=Al2 O3 sulphided
catalysts. It depicts higher selectivity towards
CH3 SH for the CoMo=A1;46 compared to the
CoMo=Al2 O3 catalyst even at conversions of
100%.
Assuming a reaction scheme as follows:
CH3 SSCH3 ‡ H2 ! 2CH3 SH
! CH3 SCH3 ‡ H2 S
the formation of DMS from the condensation of
CH3 SH, able to occur on the fraction of the sup-
port not covered by the sulphided phase [18], re-
quires the presence of combined strong acid and
medium basic lewis sites as it was suggested by
Mashkina et al. [19]. Therefore, the condensation
of CH3 SH into DMS cannot occur on the apatitic
supports, with weaker acid and basic lewis sites [8].
In contrary, the alumina carrier presents the ade-
quate acid-base lewis sites for the disproportion-
ation of CH3 SH to DMS.
4. Conclusion
To sum up, the reduction of DMDS into
CH3 SH can be selectively achieved under mild
conditions using hydroxyapatite, instead of the
conventional alumina carrier, supported sulphided
catalysts. This study points out the ability of hy-
droxyapatite to support transition metal sulphides
catalysts in reactions involving the conversion of
sulphur containing molecules without C±S bond
cleavage.
Acknowledgements
The authors wish to thank Mr. J. Leglise
(ISMRA, Caen) and Ms. N. Elazari® (Ph.D. stu-
dent, Fac des Sciences Ain Chock) for their help in
BET and IR analysis.
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