Applied Catalysis A: General 278 (2005) 143–172

www.elsevier.com/locate/apcata

Review

On the hydrodesulfurization of FCC gasoline: a review

Sylvette Bruneta, Damien Meya, Guy Pérota,*, Christophe Bouchyb, Fabrice Diehlb
a
UMR CNRS 6503, Catalyse en Chimie Organique, Université de Poitiers, Faculté des Sciences
Fondamentales et Appliquées 40, avenue du Recteur Pineau, 86022 Poitiers Cedex, France
b
Institut Français du Pétrole, IFP-Lyon, BP 3, 69390 Vernaison, France
Received 20 July 2004; received in revised form 11 October 2004; accepted 13 October 2004
Available online 23 November 2004

Abstract

The possible origins of sulfur impurities in FCC gasoline are reviewed and discussed. Their mechanism of formation during the FCC
process as well as their mechanism of transformation on hydrotreating catalysts are also examined.
The article focuses on the desulfurization of FCC gasoline by means of catalytic processes considering the fact that deep desulfurization
must be achieved (in accordance with new regulations) while preserving octane rating of the fraction. The various parameters (presence of a
promoter, nature and modification of the support, additives and poisons) which may influence the selectivity in hydrodesulfurization (HDS)
versus olefin hydrogenation are also discussed. Existing and potential processes for the HDS of FCC gasoline with octane preservation are
described.
# 2004 Elsevier B.V. All rights reserved.

Keywords: FCC gasoline; Selective hydrodesulfurization; Sulfur impurities

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144

2. Sulfur impurities and olefins in FCC gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144

2.1. Nature of the sulfur impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
2.2. The olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

3. Origin of sulfur impurities in FCC gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

3.1. Main sulfur impurities in FCC feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.2. Formation of sulfur compounds in FCC gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
3.2.1. The various possibilities (general scheme) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
3.2.2. Reactivity of sulfur compounds under FCC conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
3.2.3. Recombination of H2S with olefins and diolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
3.2.4. Reaction scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

4. The HDS of FCC gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 152

4.1. Studies regarding reaction mechanisms and catalytic centers involved in the hydrogenation of olefins and HDS of
thiophene and related compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4.1.1. The HDS of thiophene and related compounds: reaction products and mechanism . . . . . . . . . . . . . . . . . . . 152
4.1.2. Reaction of thiophene and hydrogenation of olefins: kinetics and poisoning studies . . . . . . . . . . . . . . . . . . 153
4.1.3. Hydrogenation of olefins over sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154

* Corresponding author. Tel.: +33 549 453 674; fax: +33 549 453 899.
E-mail address: guy.perot@univ-poitiers.fr (G. Pérot).

0926-860X/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.10.012
144 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172

4.2. The HDS of real feeds and of model FCC gasoline factors influencing the HDS/HYDO selectivity . . . . . . . . . . . . . 154
4.2.1. Designing a test reaction to evaluate catalysts for the HDS of FCC gasoline . . . . . . . . . . . . . . . . . . . . . . . 154
4.2.2. Effect of the promoter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
4.2.3. Effect of the nature of the support and of various additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
4.3. Existing desulfurization processes and technologies—practical aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
4.3.1. Selective HDS processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
4.3.2. HDS processes with octane recovery or compensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
4.3.3. Other processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170

1. Introduction options being the hydroprocessing of the feed and reducing

The exhaust gases from motor vehicles contribute to a
large extent to air pollution through their content in NOx and
SOx. Moreover, sulfur is a well-known poison for catalytic
converters [1]. This led the governments of numerous
countries to adopt new regulations which aim at a drastic
reduction of sulfur emissions by imposing a very low
concentration of this element in fuels (50 ppm or less by
2005; 10 ppm or less by 2009) [2–5 and references therein].
Commercial gasoline is made up of different fractions
coming from reforming, isomerization and fluid catalytic
cracking (FCC) units. Those coming from the reforming and
isomerization units are produced from distillation cuts, and
consequently contain little or no sulfur because (i) the sulfur-
containing compounds present in crude petroleum have
generally high boiling points [6] and (ii) the feedstocks used
in the isomerization and reforming units are generally
hydrotreated. On the opposite, the atmospheric residues or
the vacuum distillates which constitute FCC feedstocks
contain significant amounts of sulfur, 0.5–1.5 wt.% gen-
erally. Consequently FCC gasoline, which represents 30–
40% of the total gasoline pool, is by far the most important
sulfur contributor in gasoline, up to 85–95% [2–5,7 and
references therein]. In the recent years a large number of
articles dealing with the sulfur distribution in FCC effluents
have been published [1,8–15]. The most important class of
sulfur compounds present in FCC gasoline is made of
thiophene and its light alkyl derivatives in addition to
benzothiophene [16–18]. Most of these compounds are not
present in FCC feedstocks. They could either result from the
direct transformation of the sulfur compounds present in
the feedstock or come from the recombination of FCC
products. Whatever their origin, the new regulations make it
necessary to remove these sulfur organic compounds from
the FCC gasoline almost completely and as we will see a
great deal of research has also been devoted recently to this
important issue.
In this review we will focus on gasoline hydrodesulfur-
ization which is, together with non-catalytic sulfur
elimination processes, one of the three main options to be
considered in order to produce pure gasoline (the other two
the sulfur content during the FCC process [7,15]). Another
possibility is the fractionation of the FCC gasoline in order
to blend the heavier fraction which contains most of the
sulfur and less olefins into the gasoil fraction [7 and
references therein]. The aim of these operations is to reduce
the amount of the sulfur compounds in the gasoline and/or to
change their nature in order to facilitate their subsequent
elimination. However, FCC gasoline contains also a great
quantity of olefins (20–40 wt.%), which provides it with a
fairly good octane number [19]. Therefore the challenge is
to eliminate a maximum of the sulfur impurities with a
minimum olefin saturation.
In the following sections, we will examine successively:

the nature of the olefins present in FCC gasoline and of the
sulfur impurities;

the possible origin of the latter;

the possibility of designing a simple test reaction to
evaluate the ‘‘HDS/olefin hydrogenation’’ (HDS/HYDO)
selectivity of hydrotreating catalysts;

studies on the HDS of FCC gasoline;

the existing desulfurization processes.
Reaction mechanisms of both the formation of sulfur
impurities during FCC and of the transformation of these
compounds and of olefins on HDS catalysts will also be
discussed.
2. Sulfur impurities and olefins in FCC gasoline
2.1. Nature of the sulfur impurities
The main sulfur components of FCC gasoline are thiols,
sulfides, thiophene and alkylthiophenes, tetrahydrothio-
phene, thiophenols and benzothiophene [11,17 and refer-
ences therein, 18]. Alkylthiophenes which are typically in
the boiling range of gasoline include three and four carbon
atoms-substituted thiophenes (C3- and C4-thiophenes) but it
is difficult to tell whether these are polymethylated or longer
chain-substituted thiophenes. Recent data reported by Xia and
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172 145

Table 1 Table 2
Gas chromatographic analysis of thiophene derivatives in FCC naphtha [21] Distribution of sulfur impurities in three different FCC feedstocks (data
Compounds Percent ratio of Sulfur content from Ref. [17])
total thiophenes in naphtha (mg/g) Feed A Feed B Feed C
(sulfur %) Mercaptans and sulfides 7 12 26
Thiophene 6.3 69.2 Thiophenes 59 56 42
2-Methylthiophene 10.0 109.8 Benzo and multiring thiophenes 30 17 29
3-Methylthiophene 13.8 152.6 Oxidic sulfur 4 15 3
Dimethylthiophenes 35.4 389.8
Unknown thiophene 4.0 43.9
Iso-propylthiophene 2.4 26.4 FCC gasoline should have an internal di-, tri- or
Methyl ethylthiophene 4.2 46.1
tetrasubstituted double bond. Actually, the analysis of
Trimethylthiophene 5.6 61.5
Unknown thiophene 1.6 17.6 FCC fractions shows that terminal olefins represent about
Trimethylthiophene 4.1 45.0 25 wt.% only of the total olefin fraction, most of them
4-Carbons-alkylthiophene 10.5 116.4 having a branched skeleton [11,19].
Unknown thiophene 2.1 23.0

coworkers [20,21] confirm that thiophene sulfur represents a
large fraction of the total sulfur content in FCC gasoline
(60 wt.% and over). By using gas chromatography they
detected more than 20 different kinds of thiophenes among
which a certain number (di- and trimethyl-, ethyl-,
ethylmethyl-, di- and triethyl-, iso-propyl-, tertiobutyl-) could
be identified by GC/MS analysis (Table 1).
2.2. The olefins
The main reaction involved in catalytic cracking is the
transformation of long chain paraffins through b-scission of
intermediate carbenium ions (Scheme 1). The consequence
of this is that catalytic cracking should produce equal
amounts of olefins and of paraffins. This is not the case
because of H-transfer phenomena which take place during
the process and which convert olefins and for instance
cycloparaffins into paraffins and aromatics [22]. On the
other hand, the reaction takes place mainly via the most
stable tertiary carbenium ions which result from a
rearrangement of the normal paraffins contained in the feed
so that the primary cracking products and the olefins in
particular are expected to have a branched skeleton.
Moreover, under the conditions of catalytic cracking, olefins
are expected to isomerize very readily and since internal
olefins are thermodynamically more stable than terminal
(methylenic) olefins, a large fraction of the olefins present in
3. Origin of sulfur impurities in FCC gasoline
3.1. Main sulfur impurities in FCC feedstocks
In order to identify the origin of the sulfur impurities in
FCC gasoline, it is essential to know what are the sulfur
compounds present in FCC feedstocks. The potential sulfur
components in these feedstocks are thiophene, benzothio-
phene, dibenzothiophene, polyaromaticthiophenes and their
alkylated derivatives as well as thiols and sulfides. By
combining the results obtained from various methods which
were available in the literature, including XPS and mass
spectral analysis, Cheng et al. [17] reported a semiquanti-
tative distribution of sulfur species in various feedstocks
(Table 2). From this study, it appears that the main
sulfur components are thiophenes. This is not in accordance
with earlier studies by Wollaston et al. [23] who reported
that the main sulfur components in various feedstocks
were dibenzothiophenes and heavier compounds. In fact,
FCC feedstocks contain generally very small amounts of
thiophene and thiophene derivatives [24] although in certain
cases polyalkylated thiophenes or long alkyl chain
thiophenes were mentioned as possible constituents of
FCC feedstocks [23]. However if we except these
compounds, thiophene or thiophene derivatives are rather
in the gasoline than in the gas oil or residue boiling
ranges [17].

Scheme 1. Simplified reaction path for the catalytic cracking of n-hexadecane through isomerization and b-scission of an intermediate carbenium ion.
146 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172

3.2. Formation of sulfur compounds in FCC gasoline
3.2.1. The various possibilities (general scheme)
As already mentioned, most of the sulfur impurities
present in FCC gasoline (mainly thiophene and short alkyl
chain thiophenes) are not present in the FCC feedstocks.
Therefore, several possibilities (in fact two main routes a
priori) have to be considered to account for the formation
of the ‘‘organic sulfur compounds’’ of the gasoline boiling
range during the FCC process [25].
They could be produced through the cracking of heavier
alkyl thiophenes or of other heavy sulfur-containing
molecules which are present in the feedstock (Scheme 2a).
However, as indicated by Cheng et al. [17], 35–45% of the
feed sulfur is converted into H2S so that another possibility is
the addition of H2S to the olefins or the diolefins produced
through hydrocarbon cracking followed by a cyclization into
tetrahydrothiophenic compounds which can in turn dehy-
drogenate into thiophenic compounds (Scheme 2b).
3.2.2. Reactivity of sulfur compounds under FCC
conditions
Quite a number of studies have dealt with the trans-
formation of thiophene on FCC type catalysts [26–29].
However, as will be shown below, thiophene itself is rather
unreactive under the conditions of FCC and the mechanism
of its decomposition on pure acidic materials is still not well
understood. In fact most of the recent relevant studies deal
with other sulfur compounds like alkylthiophenes, tetra-
hydrothiophene, benzothiophene [15,17,25,30].

Scheme 2. Possible ways of formation of sulfur-containing compounds present in FCC gasoline: transformation of heavy sulfur compounds contained in the
feed (a); reaction of H2S (produced by desulfurization of sulfur impurities of the feed) with olefins or diolefins resulting from the catalytic cracking of the
hydrocarbons of the feed (b); cyclization of long chain alkylthiophenes formed during the process (c).
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Scheme 3. Mechanism of C–S bond cleavage in thiophene and desorption of the intermediate enethiol over a pure acidic zeolite in the absence of hydrogen [29].
3.2.2.1. Thiophene. Early studies on the reactivity of
thiophene on acid catalysts were in fact related to
hydrocracking [26–28]. They showed that the reactivity
of thiophene was indeed very low on the pure acidic
materials used as supports for hydrocracking catalysts.
Nevertheless the results indicated that thiophene could be
decomposed on these materials although deactivation was
very fast. In their study on the adsorption and reaction of
thiophene on ZSM-5 zeolites, Garcia and Lercher [31]
confirmed that C–S bonds of thiophene could be broken on
pure acidic zeolites, which led to unsaturated thiols as
primary products. The latter were supposed to transform
subsequently into aromatic sulfur compounds and even-
tually into coke. Later on, Welters et al. [28] found also that
pure acidic supports had a substantial activity in thiophene
desulfurization and that the activity increased linearly with
the increasing acidity of the materials. They concluded that
the reactivity of thiophene on pure zeolites could not be
explained on the basis of the generally accepted mechanisms
involved in the HDS of thiophene on sulfide catalysts. They
suggested a direct desulfurization mechanism involving H+
and leading to butadiyne (which was supposed to
polymerize) plus H2S through b-elimination. This inter-
pretation was supported by a subsequent theoretical study
from the same group [29]. Actually, in their study involving
DFT calculations the authors considered two possible
mechanisms in order to account for the desulfurization of
thiophene on acid catalysts. The first mechanism (Scheme 3)
is a process which does not involve hydrogen. Each of the
two C–S bond cleavages in adsorbed thiophene leading to
desulfurization occur in two steps. The first step consists in
the displacement of the sulfur by a nucleophilic surface
oxygen atom; the second is a b-elimination process
involving another surface oxygen anion (with a basic
Scheme 4. Mechanism of C–S bond cleavage in thiophene and desorption of the intermediate enethiol over a pure acidic zeolite in the presence of hydrogen
[29].
147
character?) which leads to the formation of a triple bond.
This overall process repeated twice affords butadiyne and
H2S as proposed earlier by Welters et al. [28]. We may notice
that each of the C–S bond cleavages could as well occur
directly in one step through a b-elimination process
involving the b-hydrogen and the protonated sulfur atom.
The second mechanism was considered by the authors as a
mechanism with prehydrogenation, which is not really the
case. Actually according to this mechanism which leads to
butadiene and H2S, both C–S bonds in thiophene are broken
through the same process which again involves two steps, in
fact two consecutive nucleophilic displacement reactions.
The first step is actually the same as in the previous
mechanism (Scheme 3) and leads to a vinylic enethiol
adsorbed at a surface oxygen atom. The second step involves
the displacement of the oxygen by a hydride ion provided by
dihydrogen adsorbed on another adjacent oxygen with a
basic character (Scheme 4). This process repeated twice
makes it possible to desorb butadiene and H2S. Again we
may notice that the elimination process could as well
occur directly through the displacement of the protonated
sulfur atom by the hydride, despite the fact that this can be
regarded as rather difficult (as is the case with any
displacement occurring at a sp2 carbon atom). Nevertheless,
the calculations show that the process involving hydrogen is
easier. This is quite sensible and expected. However, the
scope of this interesting study is to a certain extent limited
since the authors did not examine the possibility of the
decomposition of thiophene via tetrahydrothiophene,
which is considered as the main route over FCC catalysts
[15,17,25,30].
Several other reports pointed out the importance of
hydrogen sources for the transformation of thiophene over
acid catalysts. Yu et al. [32–34] observed that the conversion
148 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Scheme 5. Decomposition of thiophene through disproportionation [32].
of thiophene into H2S was multiplied by about 10 when
propane (about 20 mol/mol) was added to the feed. Their
interpretation was that desulfurization occurred through
disproportionation according to Scheme 5. However,
they observed an excess in H2S with respect to benzothio-
phene so that they supposed that an alternate path for the
desulfurization of thiophene such as the one leading to
butadiene existed [29]. Butadiene could then transform into
aromatic hydrocarbons, which is known to occur readily on
HZSM-5 [35]. As we will see another possibility which
would also explain the beneficial role of a hydrogen source
would be the transformation of thiophene into butadiene via
tetrahydrothiophene [12,15,18,25,30].
This hypothesis is supported by a more recent study by
Zhu et al. [36] who also pointed out that the decomposition
of thiophene on acidic catalysts was greatly favored by the
use of a H-donating solvent such as tetraline. Zhu et al. found
that on FCC catalysts with strong acid sites, thiophene was
apparently converted directly into hydrocarbons plus H2S
but was also transformed through three other parallel
reactions:

the hydrogenation into tetrahydrothiophene;

alkylation via electrophilic substitution;

polymerization.
On this type of catalyst the conversion of thiophene into H2S
was enhanced in the presence of a H-donating solvent. A-
gain, as will be shown in the next section, this suggests that
thiophene was probably converted in a first step through
hydrogen transfer to give tetrahydrothiophene which is e-
xpected to be highly reactive under FCC conditions and can
decompose rapidly through an acid-catalyzed process. This
is also in accordance with the fact that the catalysts which
have a low H-transfer activity yield more sulfur in gasoline
than the catalysts which have a high H-transfer activity [18].
When the acidity of the catalyst was lower, the conversion of
thiophene was also lower but the general trends and reaction
scheme remained apparently the same. However, not much
detail was given regarding the hydrocarbons which were
formed initially as well as concerning the desulfurization
mechanism. Desulfurization of thiophene was supposed to
occur directly through proton catalysis. On the other hand,
the formation of tetrahydrothiophene was supposed to in-
volve the addition of protons of the zeolite and the partic-
ipation of metal active centers which would be oxidized. The
authors did not consider the possibility of hydride transfer
which is often put forward regarding catalytic cracking r-
eactions. Actually, Fu et al. [12] carried out a similar study in
which they concluded that the formation and decomposition
of tetrahydrothiophene was the key step in the decomposi-
tion of thiophene and that cyclohexane was the best hydr-
ogen-donor hydrocarbon compared to n-octane and iso-
octane in the presence of HY zeolite.
3.2.2.2. Comparison of the reactivities under FCC condi-
tions of various sulfur impurities. Several reports [15,17,
25,30] account for the reactivities of the main sulfur
impurities of FCC gasoline under conditions similar to those
of the process. They agree on most of the observations and
interpretations. Only a few conclusions differ from one work
to the other.
Harding et al. [30] studied the kinetics and reaction
scheme of the transformation of various sulfur compounds
(thiophene, tetrahydrothiophene, 2-ethylthiophene, 2-n-
hexylthiophene, 3-n-hexylthiophene) over a USY and over
a REY-zeolite-based catalyst in a FCC unit. They compared
the reactivities of these various sulfur compounds by using
binary mixtures of each of them with n-hexadecane, the
reactivity of which was taken as a standard. By this
technique, they found that in desulfurization thiophene was
about 10 times less reactive than n-hexadecane; 2-
ethylthiophene had approximately the same reactivity as
n-hexadecane while tetrahydrothiophene was more than 10
times as reactive as n-hexadecane, which means that the
reactivity of tetrahydrothiophene was about two orders of
magnitude greater than that of thiophene under the same
conditions. Therefore, they concluded that the main
mechanism of removal of sulfur from thiophene-type
molecules present in gasoline was their transformation into
tetrahydrothiophene with subsequent ring opening to form
H2S. This is in accordance with other recent studies
[12,15,18,25]. Regarding 2- and 3-n-hexylthiophenes, the
authors encountered some difficulties caused by the
isomerization of these two reactants into each other.
Nevertheless they found that 2- and 3-n-hexylthiophenes
were about 4 times as reactive as n-hexadecane (and
consequently as 2-ethylthiophene). They found also that the
reactivity in cracking of these two compounds was
approximately the same and concluded that it did not
depend on the position of the alkyl chain with respect to the
S-atom. In fact, this is not necessarily true. Actually as
shown in a recent report [25] these two compounds
isomerize so easily into each other that it is their equilibrium
mixture which decomposes. It was therefore impossible to
reach the actual reactivity of each of them under the
experimental conditions which were used. On the other
hand, Harding et al. [30] conclude that the H-transfer
capacity of the catalyst did not affect the reactivity of the
sulfur compounds, which is apparently in disagreement with
other studies [18].
Corma et al. [14,15] did more or less the same study by
using a different technique. They used an automated MAT unit
to study the transformation of a heavy vacuum gas oil
(HVGO) as the base feed which was spiked with various
sulfur compounds representative of those found in FCC
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
gasoline (dibutylsulfide, ethylthiophene, 2-pentylthiophene,
benzothiophene and 3-butylbenzothiophene) over an equili-
brated commercial FCC catalyst. They found that mercaptans
were highly reactive and produced H2S and olefins which
were in turn converted into alkanes through H-transfer and did
not contribute to coke formation. They paid a particular
attention to the reactivity of thiophene and alkylthiophenes
which are considered as the main sulfur impurities in gasoline.
For this purpose, they studied pure thiophene and 2-
methylthiophene and found that these two compounds which
had a rather low reactivity (thiophene especially) were mainly
converted into coke. In accordance with the work of Harding
et al. [30] who found that thiophene compounds were first
converted into tetrahydrothiophene before being cracked,
they explained the higher reactivity of 2-methylthiophene
compared to that of thiophene by supposing that its saturation
by H-transfer was easier because of the possibility of forming
a tertiary carbenium ion. This led them to the conclusion that
under FCC conditions, H-transfer was the rate-limiting step of
the decomposition of thiophene and of short chain
alkylthiophenes. This is in accordance with the observation
of Alkemade and Dougan [18] that hydrogen transfer was
particularly important for the conversion of ‘‘small’’
alkylthiophenes. The transformation of HVGO spiked with
both ethylthiophene and tetraline confirmed them in their
interpretation that H-transfer was playing a major role in the
reaction since the conversion of ethylthiophene was higher in
the presence of tetraline than in its absence. On the other hand
benzothiophene was found to have a very low reactivity when
added to HVGO. The authors found that a small portion only
was cracked. Under the same conditions 3-butylbenzothio-
phene gave methylbenzothiophene and propane through
cracking of the alkyl chain in b-position with respect to the
ring and contributed also to coke formation significantly. On
the basis of their results and assumptions, Corma et al. [15]
proposed a set of interconnected reactions for the transforma-
tion of sulfur compounds on FCC catalysts (Scheme 6).
Leflaive et al. [25] compared the reactivities of various
individual sulfur compounds diluted in nitrogen at 500 8C,
under atmospheric pressure and paid a particular attention to
Scheme 6. Interconnected reaction scheme for the formation of sulfur impurities under FCC conditions [15].
149
reaction schemes and mechanisms. In accordance with other
studies, they found that thiophene was nearly unreactive
(less than 0.2% conversion under the chosen operating
conditions). The presence of molecular hydrogen or
methylcyclohexane did not improve its reactivity which
remained very low and only traces of desulfurization
products were found. Under the same conditions 2-methyl-
and 3-methylthiophene were quite reactive but essentially
through isomerization into each other and through dis-
proportionation into equimolar amounts of thiophene and
dimethylthiophene. 2-Ethylthiophene was slightly more
reactive than the methylthiophenes; the main product was
the 3-ethylthiophene isomer, the other products were
thiophene and diethylthiophene (the disproportionation
products) ethenylthiophene (a dehydrogenation product
resulting from H-transfer), traces of di- and tetrahydrothio-
phene (also resulting from intermolecular H-transfer
between the reactant molecules) and a few mol% of C6
hydrocarbons (the desulfurization products). In fact, the
reaction scheme was rather complex due to numerous
possibilities of intermolecular reactions such as H-transfer
and disproportionation.
The hexylthiophenes gave interesting results. 2-n-Hexyl-
and 3-n-hexylthiophenes were much more reactive than 2-
ethylthiophene, at least four times after stabilization of the
catalyst (if we consider the overall conversion) and about 60
times (if we consider only desulfurization). Moreover, as
reported by Harding et al. [30], the reactivities of both
compounds in desulfurization were approximately the same.
However, as indicated above, it is probably not because the
position of the alkyl group with respect to the sulfur atom has
no influence on the reactivity, it is rather because the
isomerization of the two reactants into each other is so rapid
that it is impossible to differentiate their individual
reactivities. For each reactant, the main desulfurization
products were cracking product (C1–C6) and C10 aromatics
such as diethylbenzene. The sulfur-containing products were
the isomer, thiophene, various alkylthiophenes resulting
from the cracking of the alkyl chain in different positions,
tetrahydrothiophenes and ethylbenzothiophene which was
150 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
indeed the more abundant. This is very important in regard
of the comprehension of the origin of sulfur impurities in
FCC gasoline. Corma et al. [15] made a similar observation
with n-pentylthiophene which led to methylbenzothiophene.
It was proposed [15,25] that this compound could result
from the intramolecular Friedel–Crafts alkylation of the
long chain alkylthiophene followed by dehydrogenation
(Scheme 7). This reaction can indeed explain why, as
reported by Cheng et al. [17], the concentration of
benzothiophene in FCC gasoline has a tendency to increase
with increasing conversion. This is generally interpreted by
supposing that benzothiophene is formed by dealkylation of
high-molecular weight sulfur compounds present in the
feed. The results of Corma et al. [15] and of Leflaive et al.
[25] as well as very recent results of Lappas et al. [37]
suggest that benzothiophene and its alkylated derivatives can
also be formed during catalytic cracking by cyclization of
long chain alkylthiophenes and dehydrogenation. This can
provide an important source of benzothiophene derivatives
since long chain thiophenes can be formed in situ through
alkylation of light thiophene compounds by olefins produced
by cracking of hydrocarbons during the FCC process.
Scheme 7. Transformation of n-hexylthiophene through cyclization in the presence of a FCC catalyst.
However, the chain has to be at least five carbon atoms
long in order to provide a stable carbenium ion for cyclization
(Scheme 7). With butylthiophene a primary carbenium
ion would be involved, which would make the reaction
very slow.
Tetrahydrothiophene was found very reactive, about 50
times more reactive in desulfurization than thiophene under
standard conditions after stabilization of the catalyst. This is
in accordance with the results reported by Harding et al.
[30]. As generally reported [14,15,38], it gave dehydro-
genation products (thiophene, about 55 mol% and dihy-
drothiophene, 5 mol% at 10% conversion); desulfurized
products (but-1-ene, but-2-enes, but-1,3-diene, n- and iso-
butanes, 30%); cracking products (C1–C3 hydrocarbons,
mainly propene, 11%); traces (3%) of various products, such
as alkylthiophenes, benzothiophene, benzene, toluene and
xylenes. Dehydrogenation was clearly a primary reaction.
No effect of hydrogen when used as the carrier gas instead of
nitrogen, nor of added Ni or V to a fresh catalyst was
observed on the selectivity of the reaction. Therefore it was
concluded that the reaction was exclusively acid-catalyzed.
Concerning the desulfurization reaction, it seemed that but-
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
1,3-diene was the only product formed initially. Taking into
account thermodynamics and in particular the fact that under
the conditions of FCC, tetrahydrothiophene can dehydro-
genate into thiophene, it is clear that if tetrahydrothiophene
can be formed, for instance by condensation of H2S with
olefins or diolefins and cyclization (the reverse process of its
decomposition), thiophene compounds which were not
originally present in the FCC feed can appear in FCC
gasoline.
3.2.3. Recombination of H2S with olefins and diolefins
Corma et al. [15] studied the effect of the addition of both
1-nonene and ethylthiophene to a HVGO. They did observe
a positive effect of 1-nonene on the cracking conversion of
the gas oil but surprisingly, they did not observe any direct
interaction between 1-nonene and ethylthiophene and very
little effect on the sulfur level. Leflaive et al. [25] studied the
transformation of hex-1-ene and of dienes (penta-1,3-diene
and hexa-1,5-diene) in the presence of H2S over an
equilibrated FCC catalyst. As could be expected, hex-1-
ene was very reactive (100% conversion initially) and led
principally to its alkene isomers and to cracking products
(90%), but also to alkylthiophenes (about 10%) and to traces
of hexanethiols. Under similar conditions which were
defined as standard, penta-1,3-diene led to 3% conversion
(not considering the isomers). The products were hydro-
carbons (75%), methylthiophene (24%) and pentanethiols
(about 1%). Hexa-1,5-diene gave slightly different results.
The main products were also hydrocarbons (98%), propene
principally, and traces of alkylthiophenes and tetrahy-
drothiophene derivatives; hexanethiols were not detected.
Tetrahydrothiophene and thiophene derivatives were sup-
posed to be formed through the acid-catalyzed addition of
H2S to the alkene or diene followed by cyclization as shown
in Scheme 8 in the case of hex-1-ene.
Scheme 8. Formation of 2,5-dimethylthiophene through the addition of H2S to hex-1-ene (the scheme shows only the carbenium ions involved in the
cyclization) [25].
151
3.2.4. Reaction scheme
Except for benzothiophene which can be formed directly
from heavier benzothiophene derivatives and also for some
of the alkylthiophenes which can be formed from long chain
alkylthiophenes if present in the feed, the other sulfur
compounds found in FCC gasoline result from a more
complex process of formation. This process includes the
recombination of compounds issuing both from the
decomposition of the sulfur compounds present in the feed
(H2S in particular) and from the cracking of the
hydrocarbons (such as olefins and diolefins). Therefore it
is clear that the two main options presented in Scheme 2 are
plausible. However as proposed by Corma et al. [15], quite a
number of other reactions must be taken into consideration
(e.g. alkylation reactions) in order to give a more complete
representation of the fate of sulfur under FCC conditions.
According to the results obtained by Corma et al. [15], if
long chain alkylbenzothiophenes are present in the feed,
they can easily transform either through dealkylation or
cracking of the side chain into benzothiophene and short
chain alkylbenzothiophenes which will end up in the
gasoline range. As indicated by the authors, these
compounds can also undergo alkylation into heavier
compounds and eventually into coke. Moreover, if long
chain alkylthiophenes are present in the feed (which
however is seldom the case [23]), they can transform both
into benzothiophene derivatives through cyclization and
dehydrogenation and into thiophene and short chain
alkylthiophenes through dealkylation or cracking of the
side chain [15,25].
On the other hand, most of the sulfur compounds present
in FCC gasoline are formed indirectly from the compounds
present in the feed. For instance, long chain alkylthiophenes
can result from the alkylation of preexisting thiophene or
thiophene derivatives [12,15,25] formed in a first step and
152 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
they can lead in turn to the compounds mentioned in the
foregoing discussion (Scheme 2c). The other important
possible route is the addition of H2S to olefins or diolefins
resulting from the cracking of hydrocarbons [14,15,25]. The
intermediate thiol compound could cyclize into tetrahy-
drothiophenic compounds which would dehydrogenate
readily into thiophenic compounds [38]. By considering
the mechanism of this process, the reaction is expected
to be particularly easy in the case of diolefins. However,
this reaction is reversible and it was also reported
[12,15,18,25,30] that, under FCC conditions, thiophene
transformed into tetrahydrothiophene which decomposed
very rapidly into H2S and olefins.
Nevertheless, short alkyl chain thiophenes (methyl- and
ethylthiophenes) undergo mainly isomerization and dis-
proportionation reactions and thiophene is quite unreactive.
No significant desulfurization was observed with these
compounds which can therefore be considered as fairly
stable under FCC conditions [18,25].
All the reactions which were observed are typical acid-
catalyzed reactions (formation of thiols, cyclization,
hydrogen transfer, isomerization, disproportionation, crack-
ing), and consequently can be expected to occur readily in a
FCC unit.
The relative contributions of the possible pathways very
likely depend on the composition of the feed, but also on the
reaction conditions, in particular on the contact time.
Considering the possible mechanisms of formation of the
sulfur impurities, it can be concluded that their concentra-
tions depend both on thermodynamics (intermediates
resulting from the addition of H2S to olefins or diolefins)
and on kinetics (products resulting from consecutive steps).
4. The HDS of FCC gasoline
As early as in the mid-1950s, in a study aiming at
improving the lead susceptibility of cracked gasoline
fractions by sulfur reduction, Casagrande et al. [39] pointed
out that it was possible to adjust the operating conditions of a
process using a nickel-tungsten sulfide catalyst so as to
perform efficient hydrodesulfurization while maintaining a
good octane rating in the fraction. This was made possible
by taking advantage of the acidic properties of the catalyst in
order to promote skeletal isomerization of the olefins and
hence compensate their saturation. However, Meerbott and
Hinds [40] found that under the conditions required for
substantial skeletal isomerization to take place, extensive
saturation of olefins resulted. This enlightens the necessity
of finding means to limit olefin hydrogenation, which is of
course even more crucial in the present context (where lead
additives are totally prohibited and the content in aromatics
as well as the use of oxygen additives are limited) than in the
fifties. Meerbott and Hinds [40] reported also qualitative
evidence that normal olefins saturate faster than branched
olefins, which as we will see could be of some importance
regarding the hydrodesulfurization versus hydrogenation
selectivity.
4.1. Studies regarding reaction mechanisms and catalytic
centers involved in the hydrogenation of olefins and HDS
of thiophene and related compounds
Given the importance of the subject in relation with
petroleum refining, numerous studies of the next decades
were dealing with the HDS of thiophene and related
compounds with the objective of understanding the reaction
mechanism mainly through the identification of the reaction
products and intermediates [41–46]. On the other hand,
because thiophene was found to afford butadiene and/or
butenes as primary products [41,42,44–46], a number of
authors addressed more specifically the question of whether
the sites active in HDS were the same as those active in
hydrogenation or not [41,47–56]. As mentioned already, this
issue has gained a renewal of interest in recent years with the
need of deep desulfurization coupled to the necessity of
saving a maximum of octane rating in the fractions
composing commercial gasoline.
4.1.1. The HDS of thiophene and related compounds:
reaction products and mechanism
Kolboe [43] compared the rates of desulfurization of
thiophene, tetrahydrothiophene and n-butanethiol over
various catalysts including alumina-supported cobalt–
molybdenum. He found that the reactivities of thiophene
and tetrahydrothiophene were similar while that of n-
butanethiol was much higher (15–40 times). He found also
that thiophene and tetrahydrothiophene gave qualitatively
similar (although not equal) product distributions. Never-
theless he concluded that both reactants did not give the
same primary desulfurization products, in other words
that tetrahydrothiophene was not an intermediate in the
desulfurization of thiophene. Thiophene and tetrahydrothio-
phene were supposed to give adsorbed diacetylene and
butadiene respectively and in each case the reaction was
supposed to involve two C–S bond cleavages through a b-
elimination process. Accordingly, this meant that no
hydrogenation of thiophene was required prior to its
desulfurization. The author explained that the primary
adsorbed diacetylene was not likely to appear among the
gaseous products because it is known to be strongly
adsorbed. The role of hydrogen was then to clean the surface
from the acetylenic residue.
However, certain studies regarding the HDS of thiophene
over molybdenum sulfide catalysts concluded that butadiene
was the sole primary product [41,45] but it was also shown
that this product was so reactive under the conditions of most
of the experiments that it could not be detected [41,42]. In
fact, several authors found that both butadiene and butenes
were primary products [44,46] assuming parallel reaction
pathways. It seems actually that the most likely reaction
scheme and mechanism is the one proposed by Kwart et al.
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Scheme 9. Mechanism of C–S bond cleavage in dihydrogenated thiophene
over sulfided CoMo/Al2O3 and related catalysts [44].
[44]. The authors proposed a mechanism in which thiophene
is first partially hydrogenated, which makes the first C–S
bond cleavage possible through b-elimination (Scheme 9).
The intermediate could then add a second molecule of
hydrogen before the second C–S bond cleavage occurred
through the same mechanism as the first one so that
butadiene could be formed. However, it was also proposed
[44] that once the first C–S bond would be opened, the
double bond the most remote from the C–S bond in the
butadienyle sulfide intermediate (Scheme 9) could be
reduced before the vinylic sulfide double bond. The result
would be the desorption of but-1-ene instead of butadiene.
Consequently it is not surprising that butenes appeared as
primary products in most cases and were found to transform
eventually into butane [41,42,44,46,51–53]. Another pro-
posal made by Sauer et al. [57] on the basis of a kinetic study
carried out with model catalysts was the formation of
butadiene with 2,5-dihydrothiophene as intermediate. One
could also suppose that thiophene is first totally hydro-
genated into tetrahydrothiophene which then can undergo
twice a C–S bond cleavage step to produce butadiene as
proposed by Hargreaves and Ross [53] or to produce either
butadiene or butene as can be deduced from the work of
Moser et al. [46] who suggested surface butene thiolates as
intermediates. Without entering into details which are
beyond the scope of this review, we may add that the
elimination is also in accordance with 35S [58–60] and
deuterium tracer experiments [45,61] of the hydrodesulfur-
ization of thiophene showing that the S-atom of the
produced H2S comes from the catalyst rather than from
the organic substrate while part of the hydrogen atoms at
least comes from the latter and not exclusively from the
hydrogen of the gas phase. A detailed description of the
various steps of the overall hydrodesulfurization process
accounting for these observations was reported recently
[62].
The debate about one-point versus two-point or multi-
point mechanisms [43,44,49,50] is in a way difficult matter.
Actually, it is clear that if at least partial hydrogenation of
the substrate is required prior to C–S bond cleavage, which
seems very likely, then it is sensible to assume a multipoint
adsorption. However, this is not necessarily so for C–S bond
153
cleavage itself although a concerted elimination process
means in principle two-points adsorption in the transition
state as shown by Kwart et al. [44].
What precedes (in particular the fact that the HDS of
thiophene requires most probably its preliminary total or
partial hydrogenation) could obviously lead to predict the
actual difficulties encountered today to deeply desulfurize
FCC gasoline without saturation of the olefins. Nevertheless
as we will see in the next section, the hope was placed in part
on the fact that one could reasonably envisage that the two
reactions occurred on distinct centers.
4.1.2. Reaction of thiophene and hydrogenation
of olefins: kinetics and poisoning studies
Several authors [41,49–51,55,56] studied the effect of
coreactants (H2S, organic sulfur compounds) and poisons
(ammonia, pyridine, etc.) on the HDS of thiophene and
related compounds (alkylthiophenes, tetrahydrothiophene)
and on the hydrogenation of olefins.
Most of them [41,49,51,55,56] found that the two
reactions had not the same sensitivity to the coreactants or
poisons and concluded that they occurred on distinct centers.
For instance, by using pyridine as poison, Desikan and
Amberg [41] concluded that the sites involved in each of the
two reactions differed in acid strength, the strongest being
responsible for olefin hydrogenation. Another typical
investigation was reported by Satterfield and Roberts [49]
who made a kinetic study of thiophene hydrodesulfurization
and of the hydrogenation of the butene intermediate. Their
Langmuir–Hinshelwood kinetic modeling of both reactions
and particularly of the inhibiting effect of H2S on these
reactions led them to conclude that butene was not
hydrogenated on the desulfurization sites. They acknowl-
edge however that it is often difficult to draw definite
conclusions regarding reaction mechanisms from kinetic
equations. Nevertheless, numerous other kinetic studies [63–
66] were in favor of the existence of two types of active sites,
one for hydrogenolysis and one for hydrogenation.
In fact several studies [51–53] concluded that if the sites
involved in hydrogenation and desulfurization are different,
there must be some connection or relationship between the
two. For instance, Lee and Butt [51] who also studied the
kinetics of the HDS of thiophene and hydrogenation of
butene do conclude from their rate correlations that the
catalytic centers for the two reactions are different but that
they have similar sensitivities to pyridine. On the other hand
in their study on Mo and CoMo-on-alumina catalysts,
Hargreaves and Ross [53] proposed that hydrogenation and
desulfurization occurred on distinct but interrelated centers.
Both were found to be promoted by Co although the former
were less affected than the latter.
Other authors even come to the conclusion that both
reactions occur on the same centers [50,54]. Lipsch and
Schuit [50] found in particular that pyridine had the same
effect on butene and thiophene adsorption, which they
considered as an indication that both adsorb on the same
154 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
sites. However, their CoMo catalysts were activated by
reduction with hydrogen and they found that sulfidation did
not improve the activity, which limits the significance of the
results with respect to practical hydrodesulfurization condi-
tions. Moreover, this is in complete disagreement with the
work of Okamoto et al. [54] who found that the activity of their
Mo-on-alumina catalyst in the transformation of thiophene
depended exclusively on the sulfidation degree of molybde-
num. Nevertheless, Okamoto et al. found that the relative
activity for the hydrogenation of butenes with respect to
desulfurization was constant, which led them also to conclude
that both reactions occurred on the same centers [54].
However, as we will see in a subsequent section, more
recently Hatanaka and coworkers found that the olefins
inhibited the HDS of the sulfur impurities contained in FCC
gasoline [11]. A similar observation was made previously by
Meerbott and Hinds [40] although these authors mentioned
that this was true only under certain conditions. To account
for this phenomenon and for the fact that H2S had not the
same effect on the hydrogenation of normal and iso-olefins,
Hatanaka et al. [19,67,68] suggested the existence of three
categories of active centers. One category of centers was
supposed to be active in HDS and to adsorb n- and iso-
olefins, the second category of centers was supposed to be
active in n-olefin hydrogenation and the third to be active in
iso-olefin hydrogenation.
Obviously, the question of the number and nature of the
catalytic centers involved in hydrogenation and hydro-
desulfurization is not yet definitely settled. It can also be
considered that the surface is not stable in the presence of the
reactants [69] and that the interconversion of sites can occur
depending on gas phase composition [65,70–72]. For
instance, the interconversion of hydrogenation and hydro-
genolysis centers was supposed to take place through
reaction with H2S and/or with spillover hydrogen [71,72 and
references therein] (see Section 4.2.2), the consequence of
which is that the distribution of these sites depend very much
on the H2/H2S molar ratio. This hypothesis made it possible
to account for the activity of sulfide catalysts in olefin
hydrogenation and in hydrodesulfurization [70–72].
4.1.3. Hydrogenation of olefins over sulfides
As we have seen, there is in the literature a large number
of studies on the hydrogenation of butenes either in
combination with the HDS of thiophene or separately.
However, there is only a very limited number of studies
dealing with the hydrogenation of olefins of different
structure over sulfide catalysts. In their study on the
isomerization of olefins Meerbott and Hinds [40] noticed
however that n-olefins seemed to saturate faster than
branched olefins, which is in agreement with what is found
on metals [73]. Uchytil et al. [74] studied the hydrogenation
of a series of olefins with various structures over a Co-on-
alumina catalyst. However the samples were reduced and not
sulfided, which again reduces the interest of the study in the
context of hydrodesulfurization. Nevertheless they found
some differences in the sequence of reactivities as compared
to transition metals. In particular they did not find the same
decrease in reaction rates with increasing number and size of
substituents on the double bond, which they assumed was
due to the fact that on their catalyst, the rate-limiting step of
the reaction was the addition of the second hydrogen atom
instead of the first one on transition metals.
4.2. The HDS of real feeds and of model FCC gasoline
factors influencing the HDS/HYDO selectivity
The studies undertaken on the desulfurization of gasoline
in the present context of drastic limitation of sulfur emissions
aim at understanding (or identifying) the factors which govern
the selectivity in desulfurization with respect to the
hydrogenation of olefins (HDS/HYDO) in order to improve
this selectivity. For this purpose, certain groups have used real
feeds or spiked gasoline [7,11,19] while others have used
model or synthetic gasoline [19,67,68,75–77].
4.2.1. Designing a test reaction to evaluate catalysts for
the HDS of FCC gasoline
4.2.1.1. Measuring the ‘‘HDS/olefin hydrogenation’’ (HDS/
HYDO) selectivity. Several methods can be used to measure
the HDS/HYDO selectivity of hydrotreating catalysts. In
numerous studies using thiophene as reactant the butane
concentration among the desulfurization products was
considered as representative of the hydrogenation activity
of the catalyst and compared to its HDS activity was used to
estimate its selectivity. However, since we are dealing with
consecutive reactions it is difficult to obtain precise
quantitative values with this method. Another possibility
consists in measuring in separate experiments the activity of
the catalyst in the hydrogenation of one given olefin on the
one hand and in the HDS of a sulfur compound such as
thiophene or benzothiophene on the other. This, of course,
is not at all representative of actual situations in refining
and in particular does not account for possible competi-
tion phenomena between olefins and sulfur compounds. In
principle, the most reliable method is to measure
simultaneously both activities by using mixtures of chosen
sulfur compounds and olefins (a synthetic gasoline) or to
measure the HDS and hydrogenation activities by using a
real FCC gasoline feed. The former is certainly the most
precise although it is not necessarily representative of what
would be obtained with real feedstocks, the latter is of course
the most representative of real practical conditions but is not
always precise and the results not always extendable to
all feedstocks. Another possibility could be the kinetic
modeling [71,72] of the hydrodesulfurization of FCC
gasoline using the lumping technique or the more recent
approach based on structural contributions [78–80].
4.2.1.2. Components of a ‘‘synthetic gasoline’’. The com-
ponents of a model or synthetic FCC gasoline were chosen
so as to represent at best the compounds present in real feeds
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172 155

Scheme 10. Main products of transformation of alkenes on hydrotreating catalysts.

(see Section 2). As we have seen, FCC gasoline contains products as described in Scheme 11, compounds like 2-
mainly thiophene and alkylated thiophenes as well as small methylthiophene can undergo reactions such as methyl
amounts of benzothiophene as sulfur compounds. In migration and disproportionation (Scheme 12). However,
addition to saturated hydrocarbons and aromatics it contains these reactions are seldom observed with conventional
also olefins mostly branched and internal rather than normal hydrotreating catalysts.
and methylenic or terminal olefins [11,19]. Therefore certain
authors when using only one representative compound of 4.2.1.5. Side reactions. We must also consider the possi-
each category have chosen for instance methylthiophene and bility of reactions between model olefins or olefins issuing
one branched olefin in solution in n-heptane [75–77]. Others from desulfurization and H2S to produce thiols (recombina-
have used several different olefins (for instance, iso-octene, tion or recombinant mercaptans). In fact, as early as in 1975,
oct-1-ene, cyclohexene) and several thiophene derivatives Satchell and Crynes [81] pointed out that the deep
[19,67,68]. desulfurization of cracked (olefinic) naphtha could be
limited by both the olefin and hydrogen sulfide partial
4.2.1.3. Selection and reactivity of the olefin. Depending pressures in the HDS reactor. Olefins, hydrogen sulfide and
on the reaction conditions, on the nature of the hydrotreating hydrogen could react according to Scheme 13.
catalyst as well as on their own structure, olefins may
undergo various reactions. However, the catalysts which we
have to consider in this review are either weakly or non-
acidic. Consequently, olefins are expected to undergo only
isomerization and hydrogenation reactions. For instance, a
terminal olefin such as oct-1-ene is expected to undergo
principally double bond migration and hydrogenation into
n-octane (Scheme 10a). Similarly di-iso-butylene or iso-
octene (2,4,4-trimethylpent-2-ene) and 2,3-dimethylbut-2-
ene give essentially double bond migration and hydrogena-
tion into iso-octane and 2,3-dimethylbutane, respectively
(Scheme 10b), while cyclohexene gives almost exclusively
cyclohexane. Given the nature of the olefins present in FCC Scheme 11. Possible pathways for the transformation of 2-methylthiophene
gasoline, an olefin with a branched skeleton and internal over sulfided CoMo catalysts.
double bond which can give rise to a rather limited number
of isomers such as 2,3-dimethylbut-2-ene seems to be quite
appropriate as a model molecule.

4.2.1.4. Selection and reactivity of the sulfur compoun-

d. Alkylthiophenes can be considered as representative of
the major sulfur impurities of FCC gasoline. In addition to
desulfurization and consecutive reactions of the primary Scheme 12. Isomerization and disproportionation of 2-methylthiophene.
156 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Scheme 13. Reactions between olefins, hydrogen sulfide and hydrogen
(adapted from Ref. [81]).
Considering that the recombination of H2S with olefins is
at the thermodynamic equilibrium (recombination being
much faster than hydrogenation), the following relationship
between thiol, hydrogen sulfide and olefin partial pressures,
Pthiol ¼ ½Polefins ½PH2 S ðk1 =k2 Þ;
should apply at a given temperature. This means that the
amount of thiols should be proportional to the partial
pressures of H2S and of olefins. In fact, for high desulfur-
ization levels (i.e. when hydrogen sulfide partial pressure is
practically constant), the amount of thiols should be propor-
tional to the amount of the olefins in the treated gasoline.
This was indeed observed. Obviously in the specific case of
the selective HDS of FCC gasoline, where a maximum of the
olefins should be preserved from hydrogenation, this phe-
nomenon can be of great importance.
4.2.2. Effect of the promoter
The promotion or synergy effect of Co or Ni on the
activity in HDS of Mo or W sulfide catalysts has been known
for many years and various theories or hypotheses were
proposed to explain it [82–84 and references therein].
Mainly two of them have been the subject of a large debate
in the literature: (i) the remote control theory [84,85] in
which it is supposed that the phase made of the sulfided
promoter is necessary to produce spillover hydrogen which
then migrates to the MoS2 or WS2 phase where it can react
with the organic substrate or create new catalytic centers; (ii)
the model based on the so-called mixed CoMoS or NiMoS
phases discovered by Topsøe and coworkers [83 and
references therein, 86–90]. A combination of the two
models was also proposed to explain the gain in activity
obtained by mixing for instance Co9S8 with a NiMoS sample
[91]. The mixed phase model was interpreted as an
illustration of the Sabatier principle by supposing that the
promoter donates electrons to the main constituent and leads
to a weakening of the metal–sulfur bond down to the
optimum required for the HDS activity [92 and references
therein, 93]. This interpretation was recently updated on the
basis of ab initio calculations using the density functional
theory and a new metal–sulfur bond energy model was
proposed [94]. However, the promoter has also an effect on
many other reactions catalyzed by sulfides [71,95 and
references therein, 96–99] including the hydrogenation of
olefins [71,95 and references therein, 99]. It was also shown
that the synergetic maximum (corresponding generally to a
promoter/(promoter + Mo (or W)) atomic ratio of about 0.3)
could depend on reaction conditions [100]. Then, the
question arises of whether the promoter could have an effect
on the HDS/HYDO selectivity for FCC gasoline or not.
Indeed, one could wonder if, as certain results in the
literature seemed to indicate, the optimum in synergy for
HDS and olefin hydrogenation could occur for different
concentrations in promoter [71,99], or if the effect could be
different in magnitude for the two reactions [101].
Hatanaka et al. [68] studied the effect of Co in CoMo-on-
alumina catalysts on the main reactions involved in the
hydrotreating of FCC gasoline: the HDS of thiophenic
compounds and the hydrogenation and isomerization of
olefins. For this purpose, they used mixtures made of
thiophene and an olefin (di-iso-butylene or oct-1-ene)
dissolved in toluene. As expected they found that Co had a
promoting effect on the HDS of thiophene but surprisingly
they found also that it had an inhibiting effect, although
moderate, on the hydrogenation of iso-olefins and a
pronounced inhibiting effect on the hydrogenation of n-
olefins. This was for them a confirmation of the existence of
three different categories of centers as mentioned above (see
Section 4.1.2).
In their study on the selective hydrodesulfurization of
FCC naphtha, Miller et al. [7] examined various factors
including the effect of Co on the properties of MoS2
catalysts. As we will see below, they found that the only
factor which led to lower olefin saturation, in other words to
an improved HDS/hydrogenation selectivity was the
promotion by Co. At sulfur concentrations in the gasoline
greater than about 300 ppm at least, the olefin concentration
(hence the RON) decreased much less than the sulfur
concentration (Fig. 1), which was not the case with the
unpromoted catalysts. Below about 100 ppm however olefin
saturation occurred significantly.
Recently, Choi et al. [75] reported results on the effect of
Co and Sn introduced by surface organometallic chemistry
(SOMC) on the activity and selectivity of molybdenum-
based catalysts in the transformation of a model FCC
gasoline containing 3-methylthiophene and 2,3-dimethyl-
but-2-ene. They found that Co enhanced HDS more than
olefin hydrogenation. Their catalyst modified by SOMC was
nearly as active as a conventional commercial CoMo
catalyst but was not more selective. On the other hand tin
introduced by the same method had an effect which was
opposite to the desired effect: it inhibited the HDS activity
more than the hydrogenation activity.
Apart from the inhibiting effect of Co on the
hydrogenation of olefins reported by Hatanaka et al. [68]
the results are in general agreement with recent and
more ancient studies which indicate that the promoter
enhances the rate of C–S bond cleavage steps more than
the rate of hydrogenation steps. This was found with
compounds representative of diesel fuel sulfur impurities
such as dibenzothiophene or 4,6-dimethyldibenzothiophene
[62,98,102,103] as well as with thiophene [52,53,88,
101,104,105,106 and references therein]. Actually, if one
excepts the work of Hagenbach et al. [107] in which the
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Fig. 1. Relationship between sulfur concentration (ppm sulfur remaining in
the gasoline) and olefin concentration (a) or RON (b). (x) FCC naphtha feed;
(*) CoMo/alumina; (*) CoMo/2% K-alumina (data from Ref. [7]).
authors found similar effects on the HDS of thiophene and
on the hydrogenation of olefins, most of the studies which
are relevant to the issue of selective HDS of FCC gasoline
have indeed shown that the promoter had a more significant
effect on HDS than on hydrogenation [52,53,88,101,104,
105,106 and references therein]. In fact, the catalysts used
by Hagenbach et al. [107] were obtained by sulfiding a blend
of the cobalt and molybdenum oxides and although the
authors considered that the promoting effects they measured
were significant (30–40% enhancement in activity), these
effects were much weaker than those reported in other
studies made with commercial catalysts [104] or with
catalysts where at least both sulfide precursors were
deposited on the same support [52,53,104,105,106 and
references therein].
By studying the HDS of thiophene and the hydrogenation
of but-1-ene separately, Hargreaves and Ross [52,53] found
that their most active promoted catalyst was about 10 times
more active in the HDS of thiophene than the unpromoted
catalyst whereas it was only three times more active in the
hydrogenation of but-1-ene. This added to kinetic con-
siderations led them to conclude that C–S bond cleavage and
hydrogenation occurred on distinct although interrelated
centers, the hydrogenation centers being less affected by the
promoter.
Several other groups who studied simultaneously the
HDS of thiophene and the consecutive hydrogenation of the
157
primary butenes [88,101,104,105,106 and references
therein] found also that HDS was enhanced to a greater
extent by the promoters than hydrogenation but they did not
come exactly to the same conclusion as Hargreaves and Ross
[52,53]. For instance, Massoth and Chung [104] found that
the promotion by cobalt of the secondary hydrogenation of
butenes was appreciably lower than that of the HDS
reaction. However, they pointed out that since hydrogena-
tion is consecutive to desulfurization it is rather difficult to
appreciate the extent of the promotion of the former. They
noticed in particular that at the same thiophene conversion
the hydrogenation selectivities of all the promoted catalysts
were quite similar. They concluded accordingly that the
same sites were involved in both reactions.
Moreover it seems, according to the results reported by
Candia et al. [101], that the promoting effect of nickel on the
hydrogenation of olefins is more significant than the effect of
cobalt while the difference is not so pronounced in the HDS
of thiophene. This is in accordance with results reported
recently showing that cobalt had nearly no effect and nickel
had clearly a promoting effect on the hydrogenation of
cyclopentene (Fig. 2) [108] while both had similar effects on
the HDS of dibenzothiophene [98]. This may explain why
cobalt-promoted catalysts are more efficient than nickel-
promoted catalysts in the selective HDS of FCC gasoline.
4.2.3. Effect of the nature of the support and of various
additives
It has been known since many years that the nature of the
support can have a critical effect on the catalytic properties
of sulfides [109,110]. The subject was updated very recently
in a series of review articles [111] which pointed out that the
effect of the support can be very complex as it can affect in
an interconnected manner the dispersion as well as the
geometric and electronic properties of the active component
[112]. In this article we shall focus on the studies related to
the HDS of FCC gasoline.
In this respect, it was shown that acidic supports such as
zeolites can promote the hydrogenation activity of metals
[113,114] as well as of sulfides [115–117]. The enhancement
Fig. 2. Hydrogenation of cyclopentene over sulfided NiMo/alumina and
CoMo/alumina catalysts (150 8C, atmospheric pressure). Effect of the
promoter/(promoter + molybdenum) atomic ratio (Pr/(Pr + Mo)) on the
activity. Open symbols: commercial catalysts [108].
158 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172

of the activity was attributed, in part at least, to electronic

transfer phenomena from the metal or sulfide to acceptor
sites in the zeolite lattice. Such transfers would favor the
adsorption of the substrate and therefore the hydrogenation
activity of the metal or sulfide [116]. However, this kind of
effect could also be interpreted in terms of a modification of
the intrinsic hydrogenation properties of the material.
Evidence for the electronic transfer was found in FT-IR
of adsorbed CO which showed that the absorption bands
were shifted towards high frequencies indicating an electron
deficiency of the catalytic centers [116]. Conversely it can be
expected that increasing the basicity of the support should
decrease the hydrogenation activity. This is indeed what was Fig. 3. Effect of SiO2 content in the support on the HDS/hydrogenation
observed with Pt-zeolites [118,119] in the case of benzene selectivity of CoMo/SiO2–Al2O3 catalysts (data from Ref. [123]).
hydrogenation and with molybdenum sulfide in the case of
1-methylnaphthalene hydrogenation [120]. Moreover, it was HDS/hydrogenation selectivity increased (Fig. 3). This was
also expected that basic supports could keep deactivation by particularly clear when taking into consideration pure SiO2.
coke deposition to a low level [121,122]. Several attempts Otherwise (when pure SiO2 was not taken into considera-
were made either by changing the nature of the support or by tion), the effect was not very significant and, as indicated
modifying the hydrotreating catalysts or their alumina above, it was actually the opposite of what would be
support with various additives. Actually, we will see that expected from changing the acidity. Incidentally, the authors
there are some discrepancies regarding the effect of the concluded that the change in HDS/hydrogenation selectivity
acid–base properties of the support or catalyst on the provided support to the existence of different catalytic
hydrogenation activity. centers for HDS and hydrogenation.
Okamoto and coworkers [125,126] examined also the
4.2.3.1. Effect of the nature of the support. A number of effect of the nature of the support (Al2O3, TiO2, ZrO2 and
studies have dealt with the effect of the support on the HDS SiO2) on the activity in the HDS of thiophene and in the
and hydrogenation activities of hydrotreating catalysts hydrogenation of butadiene of supported Mo sulfide and of
although they did not address the question of the HDS of supported CoMo sulfide model catalysts. The CoMo
FCC gasoline specifically [123–126]. catalysts were prepared by chemical vapor deposition
For instance, Muralidhar et al. [123] studied separately (CVD) of Co(CO)3NO on the supported Mo sulfide. They
the HDS of thiophene and the hydrogenation of hex-1-ene as found that the Co species deposited in this way were located
well as the hydrocracking of 2,4,4-trimethylpentene over at the edges of the MoS2 particles. Significant support effects
various supported CoMo catalysts. They compared CoMo were found with the unpromoted catalysts (Fig. 4). In HDS,
supported on different types of alumina to CoMo supported the SiO2-supported MoS2 catalyst was the most active and
on SiO2–Al2O3, SiO2–MgO and TiO2. They found that the the Al2O3-supported MoS2 catalyst was the least active
CoMo–Al2O3 catalysts were more active than the others, while in the hydrogenation of butadiene the ZrO2-supported
both in HDS and in hydrogenation, which they attributed to a MoS2 catalyst was by far the most active and the SiO2-
better dispersion of the Mo phase on Al2O3. However, the supported MoS2 catalyst the least active. The interpretation
Al2O3-supported catalysts were less active in hydrocracking,
which is an indication that they were less acidic than the
other catalysts. They found also that increasing the SiO2
content in SiO2–Al2O3 decreased both the HDS and
hydrogenation activities but increased the hydrocracking
activity. Since it is known that increasing the SiO2 content in
SiO2–Al2O3 increases its acidity [127] the effect on
hydrocracking was indeed expected. However, the results
regarding the hydrogenation of hex-1-ene are not in line with
the expectation that increasing the acidity of the support
should increase the hydrogenation activity (and vice versa).
A possible explanation of the results of Muralidhar et al.
[123] could be an increase in deactivation by coking due to
the increase in acidity. Nevertheless according to the results Fig. 4. Effect of the nature of the support on the activities of MoS2 catalysts
in thiophene HDS (open bars) and in butadiene hydrogenation (black bars).
of the authors, the hydrogenation activity decreased more The turnover frequencies were calculated on the basis of the number of sites
than the HDS activity as the SiO2 content increased, determined by NO adsorption (data from Ref. [125]; hydrogenation activity
particularly in the case of the CoMo catalysts, so that the of the MoS2/ZrO2 catalyst was divided by 10).
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
of the authors was that the HDS/hydrogenation selectivity of
these unpromoted catalysts was in agreement with the rim-
edge theory of Daage and Chianelli [128] since a more
significant stacking of the layers in the MoS2 crystallites was
observed with SiO2. However, the authors did not exclude
the possibility of geometric or electronic effects. The same
effects were not found with the Co promoted catalysts. The
promotion effect itself depended on the support and in fact
when the CoMoS phase was formed the specific activity of
the Co species at the edge sites of MoS2 particles became
equalized. Consequently, the thiophene HDS activity was
proportional to the amount of Co whatever the support,
except for SiO2, which the authors interpreted by supposing
that the interactions between the CoMoS phase and the
support were weaker than those between the MoS2 edge sites
and the support for the unpromoted catalysts. Therefore,
they concluded that no real support effect existed for the
reaction regarding at least the Al2O3, TiO2 and ZrO2
supports. The higher activity of the SiO2-supported catalyst
was attributed to the formation in this specific case of the
CoMoS(II) phase [89] which would not exist on the other
supports. On the other hand the Al2O3-supported catalyst
showed the best activity in the hydrogenation of butadiene
while the catalysts supported on TiO2, ZrO2 and SiO2
showed the same activity. Obviously HDS and hydrogena-
tion were affected differently by the support. From the
results obtained in both HDS and hydrogenation one could
conclude that the best catalyst regarding the HDS/
hydrogenation selectivity and therefore the best catalyst
for the HDS of FCC gasoline would be CoMo/SiO2.
Another recent study by Flego et al. [124] aimed at
improving the activity of CoMo catalysts in view of the deep
desulfurization of fuels and more particularly of gasoline.
They prepared CoMo catalysts with various supports
containing metal (Zr, Ga, Si, and B) oxides having different
acid–base properties and measured their activity in the HDS
of thiophene. They estimated also the hydrogenation activity
of the catalysts from the butane selectivity in the HDS
products. Both HDS and hydrogenation activities increased
with increasing acid site density although again, the HDS
activity increased more than the hydrogenation activity, the
latter passing through a maximum (Fig. 5). The consequence
was that the support had only a very small effect on the HDS/
hydrogenation selectivity. The authors interpreted the
relative decrease in hydrogenation activity of the samples
containing boron oxide by supposing that the olefins were
too strongly adsorbed on the acid sites to migrate to the
sulfide phase.
Among the various supports which were used in this
context, MgO and other materials containing MgO or other
basic compounds received particular attention. Several
patents recommended the use of MgO-supported catalysts
for the selective HDS of FCC gasoline [129–134] and a
series of recent academic studies on MgO and hydrotalcite-
derived oxides as supports addressed also this issue more
specifically [121,135–140].
159
Fig. 5. Relationship between the number of acid sites (measured by NH3
adsorption) and the HDS and hydrogenation activities of sulfided CoMo
catalysts (data from Ref. [124]).
Klimova et al. [135] used Mg–Al mixed oxides
(x = MgO/(MgO + Al2O3) = 0–1) prepared by the sol–gel
method as supports for Mo and NiMo catalysts. They used
thiophene HDS as the test reaction and estimated the
hydrogenation activity through the production of butane
among the HDS products. The results indicated that even
with the incorporation of small amounts of magnesia to
alumina the hydrogenation function of the unpromoted Mo
catalyst was substantially reduced while the thiophene
conversion was much less affected (Fig. 6a). The gain in
HDS/hydrogenation selectivity resulting from the addition
of magnesia was attributed to the fact that the size of the
MoS2 crystallites increased with increasing magnesia
content as compared to their size on pure alumina. This
interpretation implies that hydrogenation takes place at
corner sites, the addition of magnesia leading to an increased
proportion of edge versus corner sites. However, with the Ni-
promoted catalysts with a Ni/(Ni + Mo) ratio of 0.3 there
was a continuous and substantial drop in HDS activity with
increasing magnesia loading which paralleled the decrease
in hydrogenation activity (Fig. 6b). Consequently, there was
no substantial gain in HDS/hydrogenation selectivity with
these catalysts. The decrease in activity with increasing
magnesia content was attributed by the authors to the
formation of magnesium molybdate and of a NiO–MgO
solid solution which impeded the incorporation of Ni at the
edges of the MoS2 particles and therefore the promotion
effect. The consequence was that it was necessary to use Ni/
(Ni + Mo) atomic ratios up to 0.6 to recover the promotion
effect of Ni.
In recent contributions, Zdrazil and coworker [121,140]
reported detailed studies on the preparation and catalytic
properties of MgO-supported catalysts. As pointed out
previously [135,141] the main difficulty with MgO supports
is to avoid their deterioration by contact with water during
the introduction of the active phase precursor. Actually, a
key point is the tendency of MgO to hydrate into Mg(OH)2
and to form solid solutions with CoO and NiO in the
presence of water, which makes the preparation of
Co(Ni)Mo catalysts with this support quite delicate. For
160 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172

Table 3
Effect of hydrotalcite (HT) and of potassium on the HDS and hydrogenation
activities of CoMo catalysts [136]
Support Additive HDS (%) HYD (%) Selectivity RON
factor
Al2O3a – 97.8 98.7 0.88 –
Al2O3a K 87.8 70.9 1.70 –
HT/Al2O3 (4/1, w/w)a 51.8 17.8 3.72 –
HTa 50.3 15.9 4.03 –
HTa K 46.9 11.5 5.18 –
Al2O3b 99.0 80.6 2.8 9.5
HTb 69.1 7.0 16.2 1.8
a
HDS of model compounds.
b
HDS of FCC gasoline.

350 8C. They attributed the high synergistic effect they

Fig. 6. Effect of the molar fraction of MgO (x) in Al2O3 supports on the
HDS and hydrogenation activities of non-promoted MoS2 catalysts (a) and
NiMo catalysts (b) (350 8C, atmospheric pressure; data from Ref. [135]).
this reason Zdrazil and coworker developed a non-aqueous
method for the deposition of MoO3 on MgO [142–144].
More recently [121,140] they reported results on the
introduction of Co(Ni) promoters on a MoO3/MgO starting
material. However, they did not address explicitly the
question of the HDS/hydrogenation selectivity but were
essentially interested in improving and preserving the
dispersion of the MoO3 precursor and in limiting the coking
process which occurs during HDS with other supports. They
found that the texture of the starting MoO3/MgO was indeed
maintained during its impregnation with methanol solutions
of Co or Ni nitrates and that the Co(Ni)Mo catalysts
prepared in this manner were 1.5–2.3 times more active than
their commercial Al2O3-supported counterparts in the HDS
of benzothiophene [140]. They also pointed out that with this
kind of support, the activity of the catalysts and in particular
the promotion effect of Co(Ni) on MoS2 depended on the
calcination temperature very much. According to them this
may explain for instance why they observed a much higher
promotion effect than Klimova et al. [135]. Their catalysts
were calcined at 350 8C for less than one hour while those of
Klimova et al. were calcined at 500 8C for 24 h. The
conclusion of Klicpera and Zdrazil [140] was that for a good
promotion to occur two conditions must be fulfilled: (i) the
Co(Ni) promoter must be deposited by a method (non-
aqueous) such that the dissolution of Mo species as
MgMoO4 and the hydration of MgO be avoided and (ii)
the promoted material should not be calcined above 300–
observed to the basicity of the support which according to
them favors high dispersion and therefore increases the ratio
of surface edge planes/basal planes and hence the number of
potential sites for promotion.
Zhao and coworkers [136–139] reported a series of
studies on CoMo catalysts with oxides from hydrotalcite and
related materials as supports for the selective HDS of FCC
gasoline. They used model reactions (the HDS of thiophene
and the hydrogenation of hex-1-ene) as well as the HDS of
FCC gasoline. They found [136] that the catalysts with
mixed hydrotalcite–alumina supports containing a high
concentration of hydrotalcite or the catalysts with pure
hydrotalcite as support had a better HDS/hydrogenation
selectivity both for model compounds and for FCC gasoline
(Table 3). The consequence was that the loss in octane
number was much less significant with hydrotalcite than
with alumina as support. However, under the same
conditions, the HDS conversion was much lower with
hydrotalcite than with alumina as support. Nevertheless, a
very recent study [139] confirmed that CoMo catalysts with
supports containing hydrotalcite were more efficient than a
traditional CoMo/Al2O3 catalyst for the selective HDS of
FCC gasoline. The CoMo/Al2O3 catalyst was the most
active in HDS but also in the hydrogenation of olefins while
the CoMo catalyst with a mixed Zn–Al oxide support was
the least active for both reactions but was, by far, the
most efficient regarding the HDS/hydrogenation selectivity
(Fig. 7).
The same group [138] compared also a traditional
CoMo/Al2O3 catalyst to a CoMo deposited on MgO–Al2O3
oxide obtained from hydrotalcite and to a CoMo catalyst
with MgO dispersed on Al2O3 as support. The supported
MgO solid base was obtained by the so-called monolayer
dispersion method which consisted in mixing Mg(NO3)2-
6H2O with Al2O3 at a concentration (about 12 wt.%) such as
a monolayer was obtained. The authors showed that the
catalyst obtained by this method exhibited the best HDS/
hydrogenation selectivity in the HDS of FCC gasoline
(Fig. 8).
They reported [137] also that the addition of HZSM-5 to
the alumina support of a CoMo catalyst increased slightly
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Fig. 7. Hydrodesulfurization of FCC gasoline. HDS (open bars) and
hydrogenation (hatched bars) activities (% conversion) of alumina- and
hydrotalcite (HT)-supported catalysts (data from Ref. [139]).
Fig. 8. Hydrodesulfurization of FCC gasoline. HDS (open bars) and olefin
hydrogenation (hatched bars) activities of sulfided CoMo catalysts. Cat-1:
commercial CoMo/Al2O3 catalyst; Cat-2: CoMo supported on MgO–Al2O3
obtained from hydrotalcite; Cat-3: CoMo supported on MgO–Al2O3
obtained by the so-called monolayer dispersion method (data from Ref.
[138]).
the RON (because of increasing hydroisomerization of the
paraffins) but decreased the HDS conversion of the gasoline.
However up to now, Zhao and coworkers [136–139] did
not propose any general explanation regarding the effect
of the nature of the support on the selectivity of their
hydrotreating catalysts.
A complementary approach in line with the idea that less
acidic catalysts should be less active in hydrogenation was
to modify either the support or the catalyst with various
additives such as alkali metals, alkaline earth elements,
carbon or nitrogen poisons.
4.2.3.2. Alkali metals and alkaline earth elements. The use
of such additives was recommended in several patents [145–
149]. In particular, Hatanaka et al. [148,149] showed that the
presence of potassium (either predeposited on the support
or introduced at the same time as the Co and Mo active
components) in a HDS catalyst inhibited coke deposition
and therefore improved the HDS stability of the catalyst over
a large period of time. They claimed also that it could
minimize octane loss [149].
161
However, several authors [7,123] who studied also the
effect of alkali metals and alkaline earth elements on the
properties of hydrotreating catalysts did not find any
improvement regarding the HDS/hydrogenation selectivity.
For instance, Miller et al. [7] found no effect at all of the
addition of cesium and potassium to MoS2 and of potassium
to CoMo catalysts regarding both their activities and their
HDS/hydrogenation selectivity or octane loss in a range of
sulfur contents between zero and 800 ppm (Fig. 1).
Muralidhar et al. [123] found that sodium and potassium in
particular decreased both the HDS and hydrogenation
activities of CoMo catalysts markedly but that the latter was
less affected than the former. This of course is not the effect
which would be desirable in the case of FCC gasoline.
On the opposite, Zhao et al. [136,137] obtained a
beneficial effect of alkali metals. By using their synthetic
gasoline made of thiophene and hex-1-ene in cyclohexane,
they found that potassium could indeed improve the HDS/
hydrogenation selectivity of CoMo catalysts with both
Al2O3 and hydrotalcite as supports (Table 3) [136]. A similar
effect although rather limited was obtained with barium in
the HDS of FCC gasoline [137]. Mey et al. [77,150,151]
observed also a positive effect of potassium on the HDS/
hydrogenation selectivity of a commercial CoMo catalyst
but this was at a relatively low HDS conversion. By using
also a model FCC gasoline (2-methylthiophene and 2,3-
dimethylbut-2-ene in solution in orthoxylene and n-heptane)
they were able to measure the HDS and the olefin
hydrogenation activities at the same time but through two
distinct reactions (see Section 4.2.1). The authors found that
potassium inhibited HDS (Fig. 9a) less than olefin
hydrogenation (Fig. 9b), the result was an improvement
of HDS/hydrogenation selectivity (Fig. 9c). They found also
that the isomerization of 2,3-dimethylbut-2-ene into of 2,3-
dimethylbut-1-ene was slower with the catalyst containing
potassium (Fig. 9d).
As can be seen from the foregoing, there are noticeable
differences among the results which were reported. The
reasons for such discrepancies are not clear yet. We may
notice however that Muralidhar et al. [123] measured the
HDS and hydrogenation activities separately while Zhao et
al. [136] and Mey et al. [77,150,151] made competitive
experiments. Moreover, the results may also depend on the
conversion which is not always known precisely. Actually, it
is sensible to expect that when approaching 100% HDS
conversion it becomes more and more difficult, even with
selective catalysts, to avoid olefin hydrogenation since the
inhibition of the latter by sulfur compounds which is quite
significant at low HDS conversion [76] is disappearing.
Nevertheless, several proposals were made to account
for the beneficial effect of alkali metals and alkaline earth
elements. As we shall see, some of them are hard to
conciliate. Hatanaka et al. [148,149] supposed that
potassium inhibited coke deposition through olefin poly-
merization and therefore improved the HDS stability of the
catalyst. However, they observed also that octane loss was
162 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172

Fig. 9. Transformation of a model FCC gasoline (T = 200 8C, P = 20 bar). Formation of the HDS products from 2-methylthiophene vs. residence time (a);
formation of the hydrogenation products (HYDO) from 2,3-dimethylbut-2-ene vs. residence time (b); HDS/HYDO selectivity vs. HDS yield (c); formation of
2,3-dimethylbut-1-ene from 2,3-dimethylbut-2-ene vs. HDS yield (d). Effect of the presence of potassium [150,151].

limited presumably because olefin hydrogenation was
also inhibited. Consequently, it must be assumed that both
reactions occur on discrete centers otherwise olefin
hydrogenation should be equally stabilized. However, the
catalysts were not compared exactly under the same con-
ditions, which makes the conclusions questionable. More-
over, as we will see in the next section coke predeposition
was also found to improve the HDS/hydrogenation
selectivity [19,67]. Therefore we can wonder how both
coke deposition and its inhibition could produce the same
effect.
In line with the interpretation of support effects it can
also be supposed that alkali metals and alkaline earth
elements would induce electronic effects which would
limit hydrogenation in the same manner as basic supports
[118–120]. According to Mey et al. [150,151] such
electronic effects existed with their potassium-containing
catalyst as shown by FT-IR spectroscopy of adsorbed CO
and could explain in part at least the decrease in
hydrogenation activity they observed. However, the fact
that HDS is supposed to involve hydrogenation steps prior
to C–S bond cleavage makes this explanation question-
able unless we suppose again, as several authors did
[19,41,49,51,53,68], that the reactions occur on different
catalytic centers and that potassium inhibits those involved
in olefin hydrogenation mainly. One may notice that this
constitutes an easy way out.
Another possible explanation proposed by Mey et al.
[77,150,151] is that the decrease in olefin hydrogenation
activity of the potassium-containing catalyst compared to
the non-modified catalyst would be the consequence of the
inhibition of double bond isomerization due to the
neutralization by the alkali metal of the acid sites of the
support. Actually, with the unmodified catalyst, it was found
that the isomerization of 2,3-dimethylbut-2-ene into 2,3-
dimethylbut-1-ene was very fast [76] and that the latter (a
terminal olefin) hydrogenated much faster than the former
(an olefin with a tetrasubstituted double bond) [77,151]. This
may also explain at least in part the effect of potassium on
the HDS/hydrogenation selectivity. With the unmodified
catalyst, the isomerization was very fast so that 2,3-
dimethylbut-1-ene could be regenerated in concentrations
close to the equilibrium as soon as it was consumed through
hydrogenation, which was apparently no longer the case
with the catalyst containing potassium. This explanation
may also account for the effect of potassium reported by
Hatanaka et al. [149] since catalytically cracked gasoline
contains mostly internal olefins ( 75 vol.%) which are less
reactive than 1-olefins. It may account for the effect of
coking they reported as well (see next section) [19,67].
They found that coking limited iso-olefin (di-iso-butylene)
hydrogenation more than terminal olefin (oct-1-ene)
hydrogenation, which they attributed to the deactivation
by coking of catalytic centers which would hydrogenate iso-
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Fig. 10. Effect of coke deposition on the activities of a commercial CoMo/
Al2O3 catalyst in the HDS of thiophene (*) and in the hydrogenation of
cyclohexene (*) (data from Ref. [155]).
olefins specifically. An alternative explanation would be that
coking deactivates the acid sites which are the most efficient
in isomerizing iso-olefins into terminal olefins.
4.2.3.3. Carbon predeposition—deactivated or spent cata-
lysts. Deactivated hydrotreating catalysts [152] or spent
resid upgrading catalysts [153] were claimed to achieve
extensive and selective HDS of FCC naphtha, that is HDS
with minimum octane loss. Of course, the reason for the
improvement of the selectivity of these catalysts as
compared to the selectivity of regular (fresh) hydrotreating
catalysts is not clear because, in addition to coke, the
deactivated or spent catalysts can contain other deposits such
as metals (Fe, Ni, V, etc.) as well as other contaminants, for
instance heavy sulfur- or nitrogen-containing compounds.
Arteaga et al. reported a study on the deactivation and
regeneration of an industrial CoMo/Al2O3 catalyst
[154,155]. The catalyst ageing was obtained by coke
deposition from either buta-1,3-diene or methylcyclopen-
tane. The HDS and hydrogenation activities were measured
by using a mixture containing thiophene and cyclohexene
dissolved in cyclohexane. They found that coke deposition
inhibited both HDS and olefin hydrogenation (Fig. 10).
However, the HDS/hydrogenation selectivity was apparently
little affected by coke deposition [154].
More recently, Hatanaka et al. [19,67] studied the effect
of coke deposition on the HDS of catalytically cracked
gasoline. The authors examined the HDS of FCC gasoline on
a presulfided CoMo catalyst aged with a straight run naphtha
[19]. They found that the HDS/hydrogenation selectivity
changed with time-on-stream: the HDS activity decreased
gradually from the beginning while the olefin hydrogenation
activity decreased drastically during the first 30 h on stream
and stabilized afterwards (Fig. 11). According to them, this
confirms their previous assumption [68] that HDS on the one
hand and part at least of olefin hydrogenation on the other
occur on different catalytic centers (see Sections 4.1.2
and 4.2.2). However, it should be mentioned that HDS
conversion started from 100% (Fig. 11) so that initial
163
Fig. 11. Hydrodesulfurization of FCC gasoline over a CoMo/Al2O3 catalyst
aged with straight run naphtha (300 8C, 0.4 MPa). Effect of time-on-
stream on the HDS (*) and hydrogenation (*) activities (data from
Ref. [19]).
deactivation in HDS, if any was made undetectable under the
conditions of the experiment. Their interpretation was that
coke formation resulting from olefin oligomerization deac-
tivated the olefin hydrogenation sites selectively. Moreover,
the authors observed that part of the adsorbed oligomers
could be washed out from the catalyst by toluene while the
rest was irreversibly deposited on it. This added to the fact
that they observed two periods of deactivation regarding
olefin hydrogenation (fast at the beginning then slow and
steady) led them to conclude in accordance with their
previous proposal [68] that there were two different active
sites for olefin hydrogenation, one which is easily deac-
tivated through olefin oligomerization and the other hardly.
As indicated in the previous section another possible
explanation is that the catalytic centers (presumably on the
support) active in olefin isomerization are rapidly deacti-
vated through coke deposition so that after a short period on
stream the isomerization of internal olefins into terminal
olefins becomes very slow and, from then on, the fraction
of olefins which can be the most rapidly hydrogenated
corresponds only to the terminal olefins originally present in
the feed. Consequently, since internal olefins are much less
reactive than terminal olefins, the extent of hydrogenation
becomes less significant.
Whatever the explanation, the effect of coke deposition
on the HDS/hydrogenation selectivity was patently obvious
from the results of Hatanaka and coworkers and it gave them
the idea that it could be possible to selectively predeactivate
the hydrogenation sites by a coking pretreatment. In the
continuation of their study, they compared fresh catalysts to
the same catalysts which underwent various pretreatments:
simple ageing with straight run naphtha after sulfiding;
sulfiding and ageing followed by coking with a mixture of
cyclohexene and 1-methylnaphthalene. They found [19,67]
that at equal HDS conversions of a FCC gasoline, the olefin
conversion was much lower with the catalyst on which coke
had been deposited than with the fresh sulfided and aged
catalyst (Fig. 12). In other words the precoked catalyst had a
better HDS/hydrogenation selectivity than the fresh sulfided
164 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Fig. 12. Hydrodesulfurization of FCC gasoline over CoMo/Al2O3 catalysts
(300 8C, 0.4 MPa). Effect of various treatments on HDS and olefin hydro-
genation (data from Ref. [19]): (*) sulfided and aged fresh catalyst; (*)
sulfided, aged and coked fresh catalyst; (&) coked, sulfided and aged fresh
catalyst; (^) sulfided spent catalyst; (&) regenerated, sulfided and aged
spent catalyst.
and aged catalyst. They found also, in accordance with the
Texaco patents [152,153], that a refinery spent catalyst
containing 8.8 wt.% coke had a good HDS/hydrogenation
selectivity and noticed that the effect disappeared when the
spent catalyst was regenerated. On the other hand, coking
before sulfiding had no effect on the selectivity. Again they
concluded on the basis of the assumption of three different
catalytic centers (for thiophene HDS (type 1), for n-olefin
hydrogenation (type 2) and for iso-olefin hydrogenation
(type 3)) that the coking pretreatment deactivated type 3
centers selectively, which again can be questioned. Actually,
their main argument was that their FCC gasoline contained
mostly iso-olefins. However, as indicated above it is clear
that under the HDS conditions internal olefins (n-olefins as
well as iso-olefins) can isomerize into terminal olefins,
especially on fresh catalysts. Moreover, one can wonder
whether it is really sensible to call for three different types of
sites. In fact the authors acknowledge that the way that coke
could affect the three categories of sites is unclear. To
ascertain their interpretation they used again three different
catalysts (sulfided, sulfided and aged, sulfided aged and
coked) in the transformation of model reaction mixtures
made of thiophene and di-iso-butylene on the one hand, and
of thiophene and oct-1-ene on the other [19]. The results
confirmed that the hydrogenation of iso-olefins (here di-iso-
butylene) was markedly decreased by coking with respect to
the HDS of thiophene (Fig. 13) while (surprisingly) oct-1-
ene hydrogenation was less inhibited than thiophene HDS
(Fig. 14). Again, this can perfectly be interpreted in terms of
isomerization of the olefins and of its inhibition. Actually,
the isomerization of the olefins (and consequently its
inhibition) is expected to have opposite effects on the
hydrogenation depending on whether we are starting from
an internal or a terminal olefin: in the former case the
isomerization should increase the reactivity since terminal
olefins are more reactive than internal olefins (and
conversely its inhibition should decrease it) while, for the
same reason, in the latter case, the isomerization should
Fig. 13. Effect of various catalyst pretreatments on the HDS of thiophene in
the presence of di-iso-butylene (CoMo/Al2O3; 175 8C; 1.3 MPa; data from
Ref. [19]): (*) sulfided catalyst; (*) sulfided and aged catalyst; (&)
sulfided, aged and coked catalyst.
decrease the reactivity (and its inhibition increase it). This
was actually what was observed in the work of Hatanaka et
al. [19].
4.2.3.4. Nitrogen. In a recent patent, Hatanaka et al. [156]
reported that the modification with a basic organic nitrogen
compound of a presulfided CoMo or NiMo hydrotreating
catalyst led to an increase of its HDS/hydrogenation
selectivity. Starting from the observation made in a previous
study that H2S poisoned HDS and the hydrogenation of n-
olefins but activated the hydrogenation of isoolefins which
are found in large amounts in FCC gasoline [67,68], they
thought that a basic poison should have the reverse effect.
Actually, they found that after treating the presulfided
catalyst with a basic compound such as pyridine for instance
at 150 8C, then returning to a nitrogen-free feedstock, the
catalyst could recover nearly 100% of its original HDS
activity but 50% only of its olefin hydrogenation activity.
Hence, the HDS/hydrogenation selectivity of the catalyst
was increased significantly and the decrease in octane
number prevented to a large extent. The effect of the
nitrogen compound was confirmed by studying the HDS of
both synthetic gasolines containing thiophene, benzothio-
Fig. 14. Effect of various catalyst pretreatments on the HDS of thiophene in
the presence of oct-1-ene (CoMo/Al2O3; 175 8C; 1.3 MPa; data from Ref.
[19]): (*) sulfided catalyst; (*) sulfided and aged catalyst; (&) sulfided,
aged and coked catalyst.
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
phene and olefins and FCC gasoline in the presence of a
presulfided CoMo/Al2O3 catalyst treated with pyridine at
150 8C [157]. It was found that after partial desorption of the
latter at 300 8C, the HDS of thiophene was little affected and
that of benzothiophene was slightly inhibited while, on the
other hand, olefin hydrogenation and thiol formation were
strongly inhibited, which means that the HDS/hydrogena-
tion selectivity of the catalyst was improved.
4.3. Existing desulfurization processes and
technologies—practical aspects
Several recent review articles were dedicated to new
technologies and processes for deep desulfurization of motor
fuels [2,4,5,158,159]. In this section we will focus on the
desulfurization of FCC gasoline and more specifically on the
selective catalytic processes. Other processes regarding the
purification of FCC gasoline will be reviewed briefly.
As pointed out by Rhodes [160], hydrotreating FCC
gasoline through a conventional process would lead to a
significant octane loss. Because of this, existing catalytic
processes for the desulfurization of FCC gasoline are the
result of two different strategies: selective HDS preserving
octane number (Prime G+1, SCANfining1 and catalytic
distillation (CDHydro/CDHDS1)) and deep desulfurization
associated to octane recovery through alkane isomerization
(Oct-Gain and Isal). However, up to now, the selective HDS
processes are by far the ones which are the most generally
selected by the refiners.
4.3.1. Selective HDS processes
FCC gasoline can be separated into three main fractions
(light, medium and heavy cracked naphtha) through splitting
or distillation [158]. The light fraction (LCN) contains a
large part of the olefins with mercaptans as sulfur impurities
which can be withdrawn through caustic treatment. The
medium or intermediate fraction (MCN or ICN) has a low
octane rating and contains essentially thiophene and light
alkylthiophenes as sulfur impurities. The HCN fraction
contains a relatively low concentration of olefins but most
of the sulfur impurities including benzothiophene and
alkylbenzothiophenes [158 and references therein].
Several processes (Prime G+1, SCANfining1, CDHydro/
CDHDS1) combine this possibility of fractionating the
gasoline with catalytic HDS in order to optimize the overall
HDS/hydrogenation selectivity and to minimize octane loss.
Moreover, as we will see, selective HDS processes generally
include a selective hydrogenation unit ahead of the HDS
section in order to ensure the required duration under
operation of the HDS catalyst (typically 3–5 years). The
main purpose of this unit is to selectively hydrogenate the
diolefins contained in the FCC gasoline so as to prevent the
deactivation of the catalyst. As mentioned previously
(Section 4.2.1.5), the difficulty to reach high levels of
sulfur removal in the hydrotreated gasoline is partly due to
the possible recombination of H2S with olefins to form
165
Fig. 15. The Prime G+1 process (IFP-AXENS).
mercaptans. Under the mild conditions of the process
(relatively low temperature and medium pressure), this
reaction which is thermodynamically controlled can afford
relatively high concentrations of these ‘‘recombination
mercaptans’’ and can therefore constitute a serious obstacle
to achieve the goal of ultra-low content of sulfur imposed by
the regulation (10–15 wt ppm S) for the near future.
4.3.1.1. The ‘‘Prime G+1’’ process (Axens-IFP). The
Prime G+1 process [161–163] is licensed worldwide and
today more than 80 units are under design, construction or
operation. Typically, the full Prime G+1 process scheme
comprises a selective hydrogenation unit (SHU), a splitter
(which separates the light from medium and heavy naphtha)
and a selective HDS unit for the treatment of the medium and
heavy cracked naphtha (Fig. 15).
Three main reactions are taking place in the SHU (Prime
G+1 first step): (i) the selective hydrogenation of the
diolefins (typically the diolefin content in the full range FCC
naphtha goes from 0.5 to 2 wt.%); (ii) the double bond
isomerization of the olefins; (iii) the conversion of light
mercaptans and light sulfides into heavier sulfur compounds.
The first reaction ensures the protection of the catalyst used
in the selective HDS unit from deactivation. The specific
tailoring of the catalyst (HR845) and the choice of
appropriate process conditions allow the total hydrogenation
of the diolefins with a very limited amount of olefin
saturation. The double bond isomerization reaction trans-
forms the olefins present in the FCC naphtha into their
thermodynamic equilibrium at the temperature of the SHU
reactor. In fact, this reduces the amount of terminal olefins
and produces higher octane olefins (internal olefins have a
better RON than terminal olefins [164]). As we have seen,
this could also contribute to the limitation of olefin
saturation in the HDS reactor since terminal olefins are
more reactive in hydrogenation than internal olefins. The
conversion of light mercaptans and light sulfides to heavier
sulfur compounds through reaction with olefinic compounds
makes it possible to transfer them to the medium and heavy
fractions which will be hydrotreated in the HDS unit.
166 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Fig. 16. Selectivity of the Prime G+1 process compared to conventional
hydrotreating. Olefin saturation vs. extent of HDS.
The combination of the splitter with the SHU (Prime
G+1 first step) leads to the production of a mercaptan-free,
low-sulfur LCN fraction (C5, 65 8C) which does not need to
be hydroprocessed. Hence, the most valuable and reactive
olefins in the feed (typically C5-olefins) are preserved from
hydrogenation and recombination reactions. It has to be
mentioned that the end point of the LCN stream (65 8C) is
imposed by the presence of thiophene in the feed. Actually,
a great challenge of the fractionating step is to avoid
the distilling of thiophene into the light fraction. This is
because thiophenic sulfur cannot be easily removed by the
conventional or related extractive processes and can
therefore contribute significantly to the presence of sulfur
in the gasoline pool if it is left in the light fraction. Another
advantage of the presence of the splitter is that it makes it
possible to reduce the size of the HDS unit by decreasing the
volume of the gasoline to be treated.
The Prime G+1 second unit (selective HDS) achieves the
deep HDS of the MCN and HCN fractions with (i) a minimum
of olefin saturation (and no aromatic loss) leading to a
maximum octane retention (Fig. 16), (ii) a minimized amount
of recombination mercaptans (production of a ‘‘sweet’’
naphtha) and (iii) no cracking reactions, which means nearly
100% liquid yield (no increase in light product formation and
consequently no Reid vapor pressure increase). All this can be
achieved thanks to a dual catalyst reactor system operated
under optimal conditions. The first HDS catalyst (HR806) was
tailored so as to have a minimum hydrogenation activity
towards olefins while having still sufficient hydrodesulfuriza-
tion activity to convert the most refractory sulfur compounds
encountered in cracked naphtha. The polishing catalyst
(HR841) exhibits almost no olefin hydrogenation activity at
all, but is able to reduce the amount of recombination
mercaptans and to complete the desulfurization of the final
product in order to meet the legal requirements. Moreover,
hydrogen consumption of the overall process is also limited as
is the case with all selective processes.
The first two commercial units were started in September
2001 in Germany. They produced a 10 ppm sulfur gasoline
with a very limited octane loss (1–1.5 points only).
Recently Axens-IFP and BP formed an alliance which
enables Axens to offer the OATS1 (olefin alkylation of
Fig. 17. The Prime G+1/OATS1 integration [166].
thiophenic sulfur, see Section 4.3.3) process from BP in
conjunction with the Prime G+1 process [165,166].
Similarly to the SHU of Prime G+1, the OATS1 process
converts the light sulfur species (sulfides, mercaptans) into
heavier sulfur compounds, but in addition it transforms also
most of the thiophene into alkylthiophenes through its
reaction with light olefins. Therefore, the end-point of the
stream coming out of this unit can be as high as 100 8C.
Actually, when integrated in the Prime G+1 process [166],
the OATS1 unit is fed with the MCN (65–120 8C) coming
from the splitter next to the SHU (Fig. 17). This MCN
fraction contains olefins, thiophene and methylthiophenes.
The OATS1 unit makes it possible to switch these
thiophenic compounds to the HCN fraction which goes to
the Prime G+1 selective HDS unit. The resulting benefit of
the Prime G+1/OATS1 association is (i) the production of
ultra-low sulfur, mercaptan free LCN (C5, 65 8C) with no
octane loss thank to the Prime G+1 first step, (ii) the
production of ultra-low sulfur MCN (65–100 8C) with no
octane loss thanks to the OATS1 reactor and (iii) the
production of ultra-low sulfur HCN (100 8C+) with minimal
octane loss and a minimized amount of mercaptans, thanks
to the Prime G+1 second step
4.3.1.2. The ‘‘SCANfining1’’ process (ExxonMobil). This
process was invented by Exxon Research and Engineering
and Akzo Nobel who developed jointly a selective HDS
catalyst called RT-225 for this purpose [2 and references
therein, 167]. At the end of 2003, 32 refineries had selected
the SCANfining1 process [168]. The process is based both
on the development of a selective HDS catalyst and on the
optimization of process conditions [167]. Fig. 18 shows that
with such a selective catalyst when used in SCANfining1,
the extent of olefin saturation is much lower than with a
regular HDS catalyst used in a conventional HDS process
(20% instead of 80%) and therefore the octane loss is also
minimized. The process (Fig. 19) has some similarities with
the Axens Prime G+1 process.
The naphtha feed is first pretreated with hydrogen in a
saturator designed for the conversion of the diolefins which
can cause fouling in the heat exchangers as well as in the
HDS reactor. The effluent of the pretreating section is heated
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172 167

Fig. 18. Selectivity of the SCANfining process (A) compared to conventional hydrotreating (B) [2].

Fig. 19. Schematic diagram of the SCANfining process (ExxonMobil) [158].

and passes through the HDS reactor (containing a CoMo
catalyst (RT225)) where it is desulfurized with a minimum
of olefin saturation. The desulfurized naphtha is then cooled
and fractionated. As for the Axens Prime G+1 process,
fractionation is essential and the design of the splitter as well
as the choice of the cut points are particularly critical [169].
Because of the very low sulfur content objectives it is
necessary to remove the sulfur from the LCN which contains
the valuable C5–C6 hydrocarbons. This can be done with
caustic extraction for example, without affecting the olefins.
However, as for the Prime G+1 process, it is very important
to prevent thiophene from distilling into the light fraction.
Other options of this process are also available [169].
SCANfining1 can be associated with Sweeten Plus1 pre-
treating which involves the oxidation of the mercaptans to
higher boiling point disulfides using a conventional caustic
sweetener. The high-boiling point disulfides are known to be
stable enough to be separated from the LCN fraction and
sent to the HDS reactor together with the intermediate and
heavy cracked naphtha. The post-treatment of the effluent
with the EXOMER1 process (extraction of mercaptans, see
Section 4.3.3) is also possible.
The authors [2] claim that the SCANfining1 selective
catalyst developed by ExxonMobil and Akzo Nobel could
still be improved by poisoning selectively hydrogenation (or
rim) sites according to the concept proposed by Daage et al.
[128,170]
4.3.1.3. Catalytic distillation (CDTech). Catalytic distilla-
tion (CD) combines separation of FCC gasoline in several
fractions through distillation and catalytic HDS in a same
elaborate process using in its simplest fitting up a single
reactor or vessel, in fact a distillation column packed with a
desulfurization catalyst [5,158 and references therein]. As
we have seen, the concentration of olefins as well as the
concentration and nature of the organic sulfur compounds in
the gasoline depend very much on the boiling range of the
latter. The olefins concentrate in the low-boiling fraction
while most of the sulfur compounds are found in the high-
boiling fraction. Moreover, the differences in nature of the
sulfur compounds require different levels of severity in order
to achieve complete or nearly complete elimination of these
compounds. Catalytic distillation makes it possible to treat
separately various fractions of FCC gasoline under the most
168 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
Fig. 20. Schematic diagram of the CDHDS process (CDTech) [5].
appropriate conditions for each of them in a single operation
and allows at the same time to preserve to a large extent
olefins from saturation. In fact, the severity of the
desulfurization conditions is controlled by the boiling
temperature range of the fraction itself. The lighter fractions
containing the olefins and the most reactive sulfur
compounds will be in contact with the desulfurization
catalyst at a relatively low temperature at the top of the
column. The heavier fractions containing more refractory
sulfur impurities will undergo desulfurization at higher
temperatures at the bottom of the column (Fig. 20).
The process can be made even more efficient by using
two columns instead of one (Fig. 21). In this design, two
distillation columns (CDHydro1 for the light fractions and
CDHDS1 for the heavy fractions) are packed with
desulfurization catalysts. CDHydro1 can be used separately
to produce various hydrogenated fractions while in
combination with CDHDS1 it is used to produce low
sulfur gasoline with a minimum octane loss. In this case the
mercaptans and part of the diolefins contained in the lighter
fraction combine together to give heavy sulfur compounds
Fig. 21. Combined CDHydro and CDHDS technologies (CDTech) [158].
while the rest of the diolefins is hydrogenated into olefins.
The bottoms (medium plus heavy fractions) enter the
CDHDS1 section where they undergo desulfurization under
such conditions that a maximum sulfur removal is achieved
and a minimum of saturation of the olefins is occurring
thanks to the fact that the latter concentrate at the top of the
column where the temperature is lower.
4.3.2. HDS processes with octane recovery or
compensation
4.3.2.1. Oct-Gain1 (ExxonMobil) and ISAL1 (UOP-IN-
TEVEP) processes. These processes do not resort to
selective HDS. They associate conventional deep HDS to
subsequent octane recovery through isomerization of the
paraffins and alkylation essentially. These two processes are
quite similar but use different catalysts and operating
conditions [158 and references therein]. Both use a fixed bed
reactor with a first catalyst bed over which the organic sulfur
compounds of the feed are converted into H2S and
hydrocarbons and the olefins almost completely hydro-
genated. The second bed containing a different catalyst leads
to octane recovery through cracking, isomerization and
alkylation of the paraffins, which compensates a significant
olefin saturation [171,172]. The ISAL1 process uses a
CoMo–P/Al2O3 associated to a Ga–Cr/HZSM-5 zeolite
[5,158 and references therein, 173]. Anyhow the second
catalyst, if not a pure acidic catalyst and especially when
containing precious metals must be designed to be sulfur
tolerant [174,175]. One of the drawbacks of these processes
can be some yield loss in gasoline due to cracking into light
products. This however could be improved with new
catalysts used in the ISAL1 process [172]. Another
disadvantage with respect to selective processes is the
hydrogen consumption needed for the quasi total olefin
saturation.
 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
4.3.2.2. Prearomatizing and HDS (Phillips Petroleum
Co.). Another option is to prearomatize the gasoline before
regular HDS [176]. Although olefin saturation is almost
complete, octane is boosted because of the increase in
aromatic concentration. However, the present and future
regulations limiting aromatic concentration in gasoline
make this process much less attractive than Oct-Gain1 or
ISAL1 [5].
4.3.3. Other processes
Numerous other processes (mainly non-catalytic) can be
considered in order to achieve deep desulfurization of FCC
gasoline (for details, see for instance, [5,158]). Existing or
promising technologies involve selective or reactive
adsorption as well as alkylation of sulfur compounds.
Selective oxidation or extraction seem up to now less
appropriate for FCC gasoline and will not be considered
here.
S-Zorb1, a process from Phillips Petroleum Co. [177]
uses a solid sorbent (a metal that reacts with sulfur to give a
sulfide) which is continuously withdrawn from a fluid (or
bubbling) bed reactor. The sorbent is able to extract the
sulfur from the organic molecule and to release the
hydrocarbon part of it in the medium. The process operates
in gas phase to avoid retention of the oil in the porosity.
Hydrogen is needed to limit coking as well as to help the
extraction of the sulfur from the organic molecules and its
capture by the sorbent. The sulfided sorbent is sent to a
regenerator where the sulfur is burnt. The sorbent is then
reduced before recycling. As shown by Tawara et al. [178–
180], zinc oxide associated to nickel oxide can play such a
role of sorbent through a mechanism proposed by Babich
and Moulijn [5]. Actually, the sorbent consists in silica (20–
60 wt.%), alumina (5–15 wt.%), zinc oxide (15–60 wt.%)
and nickel and/or cobalt (a few wt.%). Hydrogen
consumption is as low as 4.4–13 l/l of gasoline, the pressure
is between 7 and 21 bar, the temperature between 340 and
415 8C and the LHSV between 4 and 10 h1. This process is
really innovating as the chemistry it involves is inventive
compared with conventional HDS processes. It really limits
the octane number loss but is very costly regarding inves-
tments, operating costs and SOx treatment after regenera-
tion. This added to some apprehension of the refining
industry to use non-fixed bed technologies explains probably
why a very few units have been built up to now.
The IRVAD1 process developed by Black and Veatch
Pritchard [181] which uses a promoted alumina-based
sorbent and the TReND1 process, another reactive
adsorption process by the Research Triangle Institute
[182] are similar in their principle to S-Zorb1 but are still
at the pilot or exploratory stage. Other selective adsorption
processes such as SARS (selective adsorption for removing
sulfur) from Pennsylvania State University [158 and
references therein] remain at the laboratory scale.
GT-DeSulf1 (GTC) separates the organosulfur com-
pounds and aromatics by extractive distillation. This process
169
is apparently not very attractive regarding selectivity and
efficiency and the choice of the solvent seems to be really
critical [5].
OATS1 (olefin alkylation of thiophenic sulfur) from BP
[183,184] is an acid-catalyzed process which makes it
possible to shift the sulfur compounds from light to heavier
fractions of the gasoline by increasing their molecular
weight. This can be obtained by alkylation of thiophene with
the olefins present in the gasoline. As we have seen, this
process can be advantageously associated with other
processes such as Prime G+1 for instance. Other processes
are also proposed in view of the separation of sulfur
compounds from the gasoline such as S-Brane1 (Grace)
which uses a polymer membrane [185] and Exomer1
(Merichem, ExxonMobil) involving caustic extraction
[186]. Processes aiming at the extraction of sulfur by using
ionic liquids [187,188] or by photochemical oxidation [189]
are also considered.
5. Conclusion
There are several possibilities regarding the origin of
sulfur impurities in FCC gasoline.
If long chain alkylthiophenes are present in the feed, they
can easily transform into thiophenic compounds during the
FCC process as shown in the case of n-hexylthiophene for
instance. However, long chain alkylthiophenes can also
result from the alkylation of thiophene by olefins issuing
from the cracking of the paraffins and lead to short chain
alkylthiophenes (methylthiophenes in particular) through
cracking of the side chains. The thiophenic compounds
present in FCC gasoline can also result from a series of
consecutive reactions including the addition of H2S to the
olefins or diolefins present in the reactor, cyclization into
tetrahydrothiophene derivatives, dehydrogenation of the
latter through H-transfer.
Part of the benzothiophene compounds present in the
high boiling fraction of the gasoline can result from the
transformation of heavier substituted benzothiophene
derivatives present in the feed. However, they can also
result from the cyclization of long chain (containing at least
five carbon atoms) alkylthiophenes.
Thiols and sulfides result mainly from the addition of H2S
to olefins. They can also be the result of the partial
decomposition of other sulfur impurities.
Numerous studies are in favor of distinct centers for HDS
and olefin hydrogenation. This encouraged numerous groups
to modify conventional catalysts or to design new catalysts
in view of favoring HDS with respect to the hydrogenation of
olefins.
The selectivity of hydrotreating catalysts used in the HDS
of FCC gasoline can be estimated at best by using model
synthetic gasoline or real FCC gasoline. It is clear that the
presence of a promoter (Co in particular) favors the HDS/
olefin hydrogenation selectivity of the catalyst. In general it
170 S. Brunet et al. / Applied Catalysis A: General 278 (2005) 143–172
was found that the promoter enhanced HDS or C–S bond
cleavage more than hydrogenation steps.
The nature of the support has also an influence on the
selectivity. Basic supports such as magnesium oxide and
hydrotalcite in particular lead to improved HDS/olefin
hydrogenation selectivity. Another approach was to modify
conventional catalysts with alkali metals or alkaline earth
elements. It was indeed found that these elements can
definitely improve the selectivity although there exist some
discrepancies among the results. In some instances no effect
at all was detected. These discrepancies can be attributed
mainly to differences in HDS conversion. It is clear that
when approaching 100% HDS conversion, the experimental
or process conditions have to be adjusted carefully otherwise
the effect of any modifier on the HDS/olefin hydrogenation
selectivity is bound to disappear.
Preadsorbed basic poisons such as pyridine or carbon
predeposits were also found to improve the selectivity.
Various interpretations can be put forward such as
electronic effects due to a decrease in acidity of the support
which would decrease the hydrogenation activity of the
catalyst or selective poisoning of the hydrogenation centers.
Another explanation could be the neutralization or poison-
ing of the sites (presumably on the support) which can
catalyze the isomerization of the internal olefins into more
reactive terminal olefins.
Among the catalytic desulfurization processes, selective
HDS processes like SCANfining1 and Prime G+1 seem to
be very efficient and are already in practice world-wide.
Indeed, both of these processes which are based on
conventional catalytic fixed-bed technology and need low
cost investments, are by far the most attractive for the
industry. Catalytic distillation seems also promising. Other
possibilities are to restore octane after conventional HDS
(with processes such as Oct-Gain1 or ISAL1) or to anti-
cipate octane loss by prearomatizing the feed.
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