Hydrotreatmentand Hydrocrackingof Oil Fractions

B. Delmon,G.F.Fromentand P. Grange(Editors)
9 1999ElsevierScienceB.V.All rightsreserved. 327

Theoretical Study of benzothiophene hydrodesulfurization on MoS2

S. Cristol 1, J.F. Paul 1, E. Payen 1, D. Bougeard 2 J. Hafner 3 and F. Hutschka 4

1Laboratoire de Catalyse H6t6rog6ne et Homog6ne. CNRS / U P R E S A 8010, F-

59655 Villeneuve d'Ascq.

2Laboratoire de Spectroscopie Infra-rouge et Raman. CNRS / UMR 8516, F-59655

Villeneuve d'Ascq.

3Institut fiir Theoretische Physik. Technische Universit~it Wien, A-1040 Wien.

4Total Raffinage Distribution, CERT, BP 27, F-76700 Harfleur.

Abstract
Benzothiophene (BT) and methylbenzothiophene (MBT) desulfurization on
the catalytically active MoS2 edge has been studied using density functional
theory. The calculation of the stability of the (100) surface as a function of sulfur
coverage indicates two potential active sites. The adsorption energies of BT, MBT
and hydrogen molecules on these sites were calculated. The calculation of the
binding energies of the various hydrogenated intermediates allow us to the build
of energy profiles of BT and MBT desulfurization. It appears that the most
endothermic step is the site regeneration (creation of the vacancy).

1. I N T R O D U C T I O N

The hydrodesulfurization (HDS) is industrially performed on CoMo/A1203 or

NiMo/A1203 catalysts which consist of MoS2 nanocrystallites well dispersed on an
alumina support and promoted by Co or Ni atoms [1,2]. It is well admitted t h a t
the active sites are located at the edges of these disulfide crystallites.
Most of the theoretical work published on HDS is devoted to thiophene
desulfurization. Neurock and Van Santen [3] proposed on the basis of DFT
calculations on small nickel sulfide clusters that the thermodynamic limiting step
is the C-S bond scission. Raybaud [4] showed from a periodic MoS2 model t h a t the
most endothermic step is the creation of the vacancy on the catalyst surface.
328

These results can explain the promoting effect of nickel or cobalt as discussed in
ref. 4, but they do not take into account the existence of steric effects that are
known to be important in deep desulfurization. Finally, DBT has a much more
pronounced aromatic character than thiophene and we have to assess how this
point affects the reaction path.
In this work, we report density functional calculations of the adsorption of
benzothiophene (BT), methylbenzothiophene (MBT) and their hydrogenated
derivatives on various MoS2 surfaces. These molecules could be good models to
estimate the differences between substituted and unsubstituted molecules and so
between DBT and DMDBT.

2. C O M P U T A T I O N A L M E T H O D

The periodic DFT calculations were performed with the Vienna Ab-initio
Simulation Package (VASP) based on plane waves [5,6] which allows a good
description of the MoS2 surface, by using large supercells (9.48x20x12.294 A~). As
shown in a previous study [7], a model containing two layers along the z
direction, three rows in the x direction and four in the y direction (Fig.l) is
suitable to give a good description of the electronic and structural properties of
the perfect (100) MoS2 surface. All over this work, we used a cut-off energy of Ecut
= 210 eV, a Methfessel-Paxton [8] smearing with a - 0.1 eV and F point for
Brillouin zone integration. The two upper rows and the adsorbed molecules were
allowed to relax during the calculation while the two lower ones were kept fixed
at the bulk geometry. In order to calculate reliable adsorption energies, the non-
local functional using generalized gradient corrections (GGA) of Perdew et al [9]
was applied. With these settings, the error on the adsorption energies is less t h a n
0.1 eV.

F i g u r e 1 (perfect surface) F i g u r e 2 (most stable surface)

dark balls: Mo; light balls: S.
 329

3. S U L F U R C O V E R A G E AND CATALYTIC S I T E S

Figure 1 is a representation of the perfect (100) surface showing

alternative rows of molybdenum (metallic edge) and sulfur atoms (sulfur edge).
Industrial conditions involve the presence of H2 and H2S in the gas/liquid phase,
which implies t h a t the surface could be sulfur rich or sulfur deficient. The nature
of the surface in the operating conditions therefore depends on the relative
chemical potential of H2 and H2S [10]. The energy of the S addition or S removal
on both edges can be calculated according to the reactions (1) and the relative
stabilities of the various surfaces can then be deduced.

Surface 1 + H2 ~-> Surface 2 + H2S (1)

Our calculations showed, in agreement with a previous study [4] that, in

the sulfiding conditions, the most stable surface is obtained by adding three
sulfur atoms on the metallic edge (Fig. 2). This surface should be catalytically
inactive because the Mo atoms exposed at the surface are saturated. Adsorption
of molecules can only proceed on lacunary structures obtained by removing sulfur
according to reaction (1). Different coordinately unsaturated sites (CUS) can be
created on both edges. The first kind of potential catalytic site is obtained by
removing one (site 1) or two (site 2) sulfur atom from the metallic edge of the
stable surface. The second one is obtained by removing sulfur atoms 1, 2 and 3
from the sulfur edge of the stable surface (site 3). Other CUS can be created on
each edge of the surface, but we only discuss in this work the more stable ones.
Table 1 summarizes the creation energy of each selected site calculated according
to reaction (1) the stable surface (Fig. 2) being taken as reference.

Table1
Stability of different possible catalytic sites.
Surface Site 1 Site 2 Site 3
Energy (eV) 1.3 3.4 2.89

4. A D S O R P T I O N O F M O L E C U L E S

The adsorption of BT and MBT was studied starting from different

configurations: 111 (S) adsorption is possible on each of the aforementioned sites
while ~5 (thiophene) and ~16 (benzene) are only possible on site 2. Figures 3 to 6
show the adsorption geometries and the corresponding energies are reported in
table 2. It appears that the methyl group does not affect the flat adsorption of
MBT whereas it induces a lowering of the energy of the ~ 1 adsorption. This is due
330

to the steric hindrance between the methyl group and the neighboring layer of
the MoS2 surface. This steric interaction is more important on site 3 t h a n on the
other ones.

Figure 5 Figure 6
BT adsorbed 1"11on site 3 MBT adsorbed 111 on site 3

Table 2
Adsorption energies of BT and MBT on different sites.
Eads (eV)
BT MBT
Site 1 111 (S) 0.5 0.4
111 (S) 1.1 0.9
Site 2 ~5 (thiophene) 1.5 1.5
116 (benzene) 1.2 1.2
Site 3 111 (S) 0.8 0.4
 331

5. E N E R G Y P R O F I L E S FOR BT A N D MBT D E S U L F U R I Z A T I O N

Different mechanisms of desulfurization of BT have been proposed in the

literature. Different reaction pathways are thus possible as presented on figure 7.
The final product of BT hydrodesulfurization is ethylbenzene (EB). This
compound can be produced either by styrene (STY) hydrogenation or by 2,3-
dihydrobenzothiophene (DHBT) desulfurization. Most of the authors detected
DHBT during the experiments so they deduced that hydrogenation of the double
bond is followed by hydrogenolysis of the C-S bonds [11,12]. On the other hand,
on the basis of kinetic measurements, it has also been proposed t h a t BT
desulfurization could be the result of two parallel routes, one involving DHBT as
intermediate, the other one involving STY [13,14]. In these studies, it was
proposed t h a t STY was not detected because its hydrogenation is too fast. This
was supported by experiments showing that in the hydrodesulfurization
conditions, styrene yielded 100% EB. The mechanism for MBT desulfurization is
likely the same, with an overall rate constant three times less t h a n BT [2].
However there are very few literature data on MBT desulfurization.
We have investigated the various reaction pathways for benzothiophene
desulfurization reported on figure 7. Other intermediates are also possible but
they are less stable and they will be discussed elsewhere. Assuming t h a t H atoms
are coming from adsorbed H2 molecule on the surface, the hydrogenation steps
are investigated in the form of successive atomic H additions. On site 2, H2
dissociates as one S-H and one Mo-H while on site 3 and site 1, only S-H are
present. In all cases, H2 dissociation is exothermic (0.3 to 0.7 eV). For the clarity
of figure 7, BT or the intermediates are always shown in an ~1 position, but for
each step a full geometry optimization was performed.
The first hydrogenation produces intermediate 1 (I1). This intermediate is
stabilized by flat adsorption on site 2 whereas it is not when the hydrogenation
proceed on site 3. This implies the existence of an endothermic step on site 3 t h a t
does not appear on site 2. The stabilization is so important on site 2 t h a t
isomerization to form orthostyrenethiolate (OSTY) is athermic. Ring opening
seems therefore possible only on site 3. In this case, the last step is the C-S bond
scission to produce styrene. In the other reaction path, I1 is further hydrogenated
to give DHBT. Desulfurization of DHBT can then proceed through two
intermediates: orthoethylbenzenethiolate (OEBT) or 2-phenylethanethiolate
(PET). There is no difference on a thermodynamic point of view between these
two intermediates. Both C-S bond scissions are highly exothermic as is the last
one to produce ethylbenzene.
332

Figure 7
Reaction path for BT desulfurization

All the results are summarized on diagram 1 and 2, which give the energy
profile, including site creation from the most stable (fig.2) surface. Whatever the
reaction pathway, the overall reaction is exothermic. On the molybdenum edge,
creation of site 2 is assisted by BT adsorption on site 1. However, the final sulfur
removal to create the CUS is more endothermic (1.61 eV) on this edge t h a n on
the sulfur edge (1.33eV).
 333

3.50

3.00 uxt, x., u

2.50

2.00

1.50 _

1.00
~ ~ - : N~,:site 3+S+STY
0.50 [
DHBT ~ %
0.00 ,
! DHB'I' + H2
Stable Surface
-0.50

-1.00
site 3+S+EB
-1.50
: BT path 1 --'--BT path 2 -~-MBT1
Diagram 1
Energy profile for BT and MBT desulfurization on the sulfur edge (site 3)

3.00
BT q 1 on site 2
2.50

2.00 101e V~BT~5 BT + H2

1.50
DHBTns~
1.00
DHBT+H2
BT site 1 DHBT 111 ~ --T
0.50

0.00 \
Stable surface
-0.50

-1.00 Site I+EB

-1.50

Diagram 2
Energy profile for BT desulfurization on molybdenum edge (site2)
334

F r o m t h e s e results, it can be deduced t h a t d e s u l f u r i z a t i o n of BT a n d MBT

is possible on both edges of the MoS2 slab. The direct d e s u l f u r i z a t i o n to produce
s t y r e n e is likely to occur on the sulfur edge while h y d r o d e s u l f u r i z a t i o n to produce
e t h y l b e n z e n e t h r o u g h d i h y d r o b e n z o t h i o p h e n e could occur on both edges. On
d i a g r a m 1 are r e p o r t e d the r e s u l t s o b t a i n e d with MBT, u s i n g t h e s a m e
i n t e r m e d i a t e s , which also correspond to the most stable ones. On t h e
m o l y b d e n u m edge, the e n e r g y profile of MBT d e s u l f u r i z a t i o n is a l m o s t t h e s a m e
as BT desulfurization. A difference is found in the reaction proceed on the sulfur
edge, w h e r e the a d s o r p t i o n e n e r g i e s of the various i n t e r m e d i a t e s are less
i m p o r t a n t t h a n for BT ones. The lower d e s u l f u r i z a t i o n r a t e of s u b s t i t u t e d
molecules s e e m s to be due to a lower a d s o r p t i o n constant. The sulfur r e m o v a l to
produce the catalytic site is always the m o s t e n d o t h e r m i c step.

6. C O N C L U S I O N

Different CUS on the surface of the MoS2 crystallites h a v e b e e n e v i d e n c e d

on which BT a n d MBT d e s u l f u r i z a t i o n can proceed. It a p p e a r s t h a t both edges
can p a r t i c i p a t e to the reaction a n d the limiting t h e r m o d y n a m i c step is the
r e g e n e r a t i o n of the CUS. The e n e r g y cost of this step will d e p e n d on the c h e m i c a l
p o t e n t i a l of H2 a n d H2S. Studies are in p r o g r e s s to t a k e this point into account by
a c h e m i c a l p o t e n t i a l analysis.

Acknowledge me nts
This w o r k h a s b e e n p e r f o r m e d w i t h i n the g r o u p e m e n t de R e c h e r c h e
E u r o p 6 e n " D y n a m i q u e mol6culaire q u a n t i q u e appliqu6e h la catlyse,
l ' a d s o r p t i o n et h l'absorption", s u p p o r t e d by the I n s t i t u t F r a n ~ a i s du P6trole, the
C e n t r e N a t i o n a l de la Recherche Scientifique, Total and TU Wien.

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