Catal Lett

DOI 10.1007/s10562-016-1754-1

Sulfiding of Unsupported Metal Sulfide Catalysts

for Hydrodesulfurization
Teh C. Ho1

Received: 8 April 2016 / Accepted: 22 April 2016

Ó Springer Science+Business Media New York 2016

Abstract Sulfiding medium strongly affects the perfor-
mances of unsupported metal sulfide hydrodesulfurization
catalysts. A gas-sulfided CoMo unsupported catalyst has
about the same activities for desulfurizing dibenzothio-
phene and 4,6-diethyldibenzothiophene. Its liquid-sulfided
counterpart desulfurizes 4,6-diethyldibenzothiophene
much faster than it desulfurizes dibenzothiophene. By
contrast, 4,6-diethyldibenzothiophene desulfurizes far
more slowly than dibenzothiophene on Al2O3-supported
sulfide catalysts. The implications of these results are
discussed.
Graphical Abstract
30
25
First-order rate constant
Keywords Deep hydrodesulfurization  Unsupported
metal sulfide catalysts  Gas and liquid presulfiding 
Stacked-bed reactor  Dibenzothiophene 
4,6-Diethyldibenzothiophene
1 Introduction
The ever-tightening sulfur specifications in hydrocarbon
fuels speak volumes for the importance of hydrodesulfur-
ization in petroleum refining. Most industrial hydrodesul-
furization catalysts are alumina-supported CoMo and
NiMo metal sulfides [1]. In hydrodesulfurization of middle
distillates (200–300 °C boiling range) such as diesel and
Liquid heating oil, a fairly high desulfurization level can often be
attained once the vast majority of dibenzothiophene and its
alkyl-substituted derivatives are desulfurized. The problem

S of central concern in ultra-deep hydrodesulfurization has

20
been the removal of sulfur atoms from 4-substituted and
4,6-disubstituted dibenzothiophenes. As an example, the
15
S relative desulfurization rates of dibenzothiophene,
4-methyldibenzothiophene, and 4,6-dimethyldibenzothio-
Gas Gas
10
phene are 100, 9.3, and 6.9, respectively, over a sulfided
CoMo/Al2O3 catalyst at 300 °C and 10.5 MPa [2]. On a
5
sulfided NiMo/Al2O3 catalyst at 300 °C and 5 MPa, the
Liquid relative desulfurization rates of dibenzothiophene, 4,6-
dimethyldibenzothiophene, 4,6-diethyldibenzothiophene,
0
4,6-dibuytldibenzothiophene, and 4,6-dipropyldibenzoth-
iophene are 100, 15.9, 11.9, 6.3, and 2.3, respectively [3].
These reactivity trends show that steric crowding has a
strong negative effect on the desulfurization reactivities of
& Teh C. Ho alkyldibenzothiophenes over supported catalysts. As a
tehcho@gmail.com
result, 4-substituted and 4,6-disubstituted dibenzothio-
1
Hydrocarbon Conversion Technologies, Bridgewater, phenes have been perceived as ‘‘refractory’’ sulfur species.
NJ 08807, USA The present study shows that an unsupported (or bulk)

123

CoMo sulfide catalyst, depending on the sulfiding medium (gas
vs. liquid), gives rise to strikingly different reactivity trends. The
reactivity of 4,6-diethyldibenzothiophene can be much lower,
comparable to, or much higher than that of dibenzothiophene.
The implications of these findings are discussed.
The active sites on transition metal sulfide hydrodesulfur-
ization catalysts can be broadly categorized as two types:
hydrogenation and hydrogenolysis [1]. A laboratory test was
developed for quantifying the intrinsic hydrogenation activi-
ties of supported or unsupported metal sulfide catalysts [4].
The hydrogenation function plays a more important role than
the hydrogenolysis function in the hydrodesulfurization of
4-substituted and 4,6-disubstituted dibenzothiophenes [4–6].
This is so because sulfur removal from these molecules prefers
pre-hydrogenation of at least of one phenyl ring, resulting in
4-substituted and 4,6-disubstituted cyclohexylbenzenes as the
major hydrodesulfurization products. In contrast, the
hydrogenolysis function plays a more important role in
dibenzothiophene hydrodesulfurization. Here biphenyl is the
dominant product because direct C-S bond cleavage is a facile
reaction, obviating the need of pre-hydrogenation of a phenyl
ring [1]. The NiMo/Al2O3 catalyst generally has a higher
hydrogenation activity than the CoMo/Al2O3 catalyst.
To achieve deep hydrodesulfurization of middle distillates,
great strides have been made in developing new hydrodesul-
furization catalysts and processes including two-stage process
options [6]. Alumina-supported Co/Ni–Mo/W sulfide cata-
lysts are more selective toward hydrogenolysis mainly due to
the acidic sites on the support [4, 7]. Unsupported metal sul-
fides in general have higher volumetric hydrogenation activ-
ities and selectivities than Al2O3-supported catalysts [7, 8].
They generally have much lower surface areas than supported
catalysts. There is a good review of the development and
commercialization of an unsupported metal sulfide catalyst
for hydroprocessing processes [9].
2 Catalyst Preparation
The precursors of the bulk catalysts are called metal amine
molybdates with the general formula Mx M01x ðenÞ3 MoO4
(0 B x B 1 and en is ethylenediamine) in which M and M0 can
be Co, Ni, Fe, and Mn [7, 8]. A heterometallic metal oxygen
coordination compound of this type may be called self-pro-
moted in that the primary and promoter metals are all in a
single compound. This compound can be prepared by reacting
metal chloride hydrates with ammonium paramolybdate in
excess ethylenediamine which serves as a chelating ligand
[10]. The products are insoluble in en-H2O solutions con-
taining 50 % or more by volume of amine. They are recovered
by filtration followed by washing with dry acetone.
Specifically, the unsupported catalyst used in this study
was prepared from tris(ethylenediamine) cobalt molybdate,
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T. C. Ho
Fig. 1 Coordinative structure of Co(en)3MoO4
or Co(en)3MoO4. As shown in Fig. 1, its structure is an
example of hybrid inorganic–organic framework materials
with zero dimensionality with respect to both organic and
inorganic connectivity [11]. Presumably, the intimacy
between Co and the Mo–O moieties would generate an
environment conducive to the Co-promotion effect along the
MoS2 edge planes. A closely related family of catalyst
precursors has been identified as sub-stoichiometric metal
amine molybdates which yield highly active hydrodesulfu-
rization catalysts [7]. An example is [Co(en)3]0.75Q0.25MoO4
where Q can be [H2(en)3]2?, [H2(en)]2?, [H2(en)2]2? and
mixtures thereof.
2.1 Catalyst Sulfiding and Activity Tests
The hydrodesulfurization activity tests were conducted
using the same steady-state flow reactor system and pro-
cedures reported previously [4]. With dodecane as the
carrier solvent, two model-compound feed mixtures were
used. One contains 1.5 wt% dibenzothiophene, while the
other contains 0.8 wt% 4,6-diethyldibenzothiophene. The
reaction conditions were 265 °C, 1.83 MPa H2, 6 cc/min
H2, and 0.05 cc/min liquid feed. The catalyst particles were
compressed to wafers, then crushed and sized to 60–80
mesh granules to ensure an adequate particle-to-reactor
diameter ratio. The liquid products were identified and
quantified by GC/MS and GC.
Prior to activity tests, the catalyst precursor Co(en)3MoO4
was thermally decomposed under flowing nitrogen at
370 °C for 3 h followed by sulfiding with a sulfur-bearing
stream. One portion of the decomposed precursor was sul-
fided with the 10 % H2S-in-H2 gas mixture at 400 °C for
2 h. The other portion was cooled to room temperature in
flowing nitrogen and then passivated with 1 % O2-in-He
overnight. This was followed by sulfiding with 3 wt%
dimethyl disulfide in dodecane at 1.9 MPa according to the
following sequence of steps: (1) heated the catalyst bed to
66 °C and maintained at 66 °C for 6 h with a liquid flow
rate of 0.13 cc/min; (2) introduced H2 at 30 cc/min while
maintaining the same liquid flow rate at 232 °C for 18 h; (3)
raised reactor temperature to 332 °C and held for 12 h; and
Sulfiding of Unsupported Metal Sulfide Catalysts for Hydrodesulfurization
30 Liquid
25
First-order rate constant
S
20
S
15
Gas Gas
10
5
Liquid
0 zothiophene-to-dibenzothiophene reactivity ratio on a sul-
Fig. 2 Reactivities of dibenzothiophene and 4,6-diethyl-dibenzoth-
iophene on gas-sulfided and liquid-sulfided bulk Co–Mo catalyst;
265 °C, 1.83 MPa
(4) switched to the hydrodesulfurization reaction feed at the
desired rate, temperature, and pressure. Dimethyl disulfide
was converted to H2S during sulfiding. Frizi et al. reported
that the presence of an organic chelating ligand in liquid-
phase sulfidation could enable simultaneous sulfidation of
Co and Mo atoms for Al2O3-supported CoMo catalysts [12].
3 Results and Discussion
Figure 2 shows the test results in terms of pseudo-first-order
rate constants (cc liquid feed/g catalyst/h). The desulfuriza-
tion reactivities of dibenzothiophene and 4,6-diethyldiben-
zothiophene are comparable over the gas-sulfided bulk
CoMo catalyst, indicating that here the effect of steric
crowding is insignificant. This stands in sharp contrast to the
case with alumina-supported CoMo and NiMo catalysts on
which dibenzothiophene and 4,6-diethyldibenzothiophene
exhibit hugely different reactivities as mentioned earlier. A
plausible explanation is that the hydrodesulfurization path-
ways observed with the unsupported catalyst primarily
involve the p-adsorption [13]. That is, the initial contact of
dibenzothiophene or 4,6-diethyldibenzothiophene with the
catalyst surface favors a side-on configuration involving the
aromatic ring (parallel to the catalyst surface) instead of the
sulfur heteroatom (r-adsorption).
Turning to the liquid-sulfided bulk CoMo catalyst in Fig. 2,
one notices that the unsupported catalyst has a far higher
activity for desulfurizing 4,6-diethyldibenzothiophene than
its gas-sulfided counterpart. More significantly, 4,6-di-
ethyldibenzothiophene desulfurizes much faster than diben-
zothiophene. Here the two ethyl substituents appear to facilitate
hydrodesulfurization electronically via the p-adsorption—
rather than sterically hindering the hydrodesulfurization rate
via the r-adsorption. These results indicate that liquid sulfiding
is much more effective in boosting unsupported catalyst’s
hydrogenation function than gas sulfiding. Under the favorable
hydrogenation environment, a reactivity reversal occurs: a
‘‘refractory’’ sulfur species such as 4,6-diethyldibenzothio-
phene becomes highly reactive.
To get a rough quantitative feel for the reactivity reversal,
the 4,6-diethyldibenzothiophene-to-dibenzothiophene reac-
tivity ratios over the liquid- and gas-sulfided bulk CoMo
catalyst are 28.4/2.2 & 13 and 9.8/10.0 = 0.9, respectively.
As alluded to earlier, the diethyldibenzothiophene-to-diben-
zothiophene reactivity ratio over a sulfided NiMo/Al2O3
catalyst is 11.9/100 = 0.12 [3]. The 4,6-dimethyldiben-
fided CoMo/Al2O3 catalyst is 6.9/100 = 0.07 [2]. Here one
sees that the reactivity ratio spans three orders of magnitude.
Sulfiding is an exothermic reaction. A significant dif-
ference between the gas- and liquid-sulfiding processes for
bulk metal sulfides is that the former is accompanied by a
much larger heat effect, far more so than that observed with
supported catalysts [14, 15]. During sulfiding the catalyst is
much hotter than the gas and can become starved of H2S.
To help develop optimum sulfiding procedures, a mathe-
matical model of gas sulfiding was developed for calcu-
lating the maximum temperature rise and capturing the
spatiotemporal behavior of H2S concentration. The speed
of the travelling thermal wave predicted for the bulk cat-
alyst is an order of magnitude slower than that predicted for
a supported catalyst [14, 15]. A detailed comparison of the
gas sulfiding behaviors of supported and unsupported cat-
alysts can be found elsewhere [15]. Since liquid is a heat
sink, liquid sulfiding is accompanied by a much smaller
temperature rise compared to gas sulfiding.
A viable deep hydrodesulfurization catalyst requires a
high resilience to inhibition by heterocyclic organonitrogen
species [16, 17]. The organonitrogen inhibitors can be
divided into two structural types: those which have a six-
membered pyridinic ring (e.g., acridine) and those which
have a five-membered pyrrolic ring (e.g., carbazole). The
former can be regarded as basic, whereas the latter non-
basic [18]. Characterization of deeply hydrodesulfurized
liquid products indicates that alkylcarbazoles are the most
potent inhibitors [17]. And hydrogenation is the rate-de-
termining step in the hydrodenitrogenation of alkylcar-
bazoles [18]. The organonitrogen inhibitory effect is more
severe on hydrogenation sites than on hydrogenolysis sites
[4, 5, 19, 20]. Unsurprisingly, unsupported sulfide catalysts
in deep hydrodesulfurization are more vulnerable to
organonitrogen inhibition than supported catalysts [4, 21
and references therein].
Thus, developing an ultra-deep hydrodesulfurization
process comes down to balancing two conflicting require-
ments: high hydrogenation function and high resilience to
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organonitrogen inhibition [4, 16, 17]. In this respect,
unsupported and supported catalysts complement each
other [7, 19]. The ‘‘hydrogenation vs. inhibition’’ dichot-
omy can be resolved by using a properly configured
stacked-bed reactor containing both unsupported and sup-
ported catalysts [22]. The upstream section of the reactor
comprises a conventional supported catalyst followed by
an unsupported catalyst in the downstream. This hybrid
system plays the strengths of the two catalysts, thereby
generating an activity synergy. The genesis of the synergy,
simply put, is that it pays to do some hydrodenitrogenation
over a supported catalyst. Even a modest hydrodenitro-
genation level in the upstream zone goes a long way toward
boosting the downstream bulk catalyst’s activity for
desulfurizing 4-substituted and 4,6-disubstituted diben-
zothiophenes. An added advantage of this stacked bed is
that it provides a way of mitigating heat release in oper-
ating commercial adiabatic reactors containing a catalyst
with high hydrogenation activity.
Recent developments in analytical chemistry have made
it possible to perform molecular speciation analyses on
petroleum feedstocks. Information on the concentration
distributions of different sulfur types in the feedstock may
be used to optimize sulfiding procedure and stacked-bed
configuration.
4 Concluding Remarks
The activity and selectivity of unsupported metal sulfide cat-
alysts for deep hydrodesulfurization of middle distillates are
quite sensitive to the presulfiding protocol used. The nature
and morphology of the liquid-sulfided unsupported catalyst
123
T. C. Ho
should be very different from those of the gas-sulfided cata-
lyst. Further studies are needed to gain a predictive under-
standing of the structures of active sites resulting from liquid
and gas sulfiding of bulk hydrodesulfurization catalysts. Such
studies should also include catalysts prepared from sub-stoi-
chiometric metal amine molybdates.
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