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Zeolites as catalysts in oil refining

Cite this: DOI: 10.1039/c3cs60394f
Ana Primo*a and Hermenegildo Garcia*ab

Received 1st November 2013
DOI: 10.1039/c3cs60394f
www.rsc.org/csr
Oil is nowadays the main energy source and this prevalent position most probably will continue in the next
decades. This situation is largely due to the degree of maturity that has been achieved in oil refining and
petrochemistry as a consequence of the large effort in research and innovation. The remarkable efficiency of
oil refining is largely based on the use of zeolites as catalysts. The use of zeolites as catalysts in refining and
petrochemistry has been considered as one of the major accomplishments in the chemistry of the XXth
century. In this tutorial review, the introductory part describes the main features of zeolites in connection with
their use as solid acids. The main body of the review describes important refining processes in which zeolites
are used including light naphtha isomerization, olefin alkylation, reforming, cracking and hydrocracking. The
final section contains our view on future developments in the field such as the increase in the quality of the
transportation fuels and the coprocessing of increasing percentage of biofuels together with oil streams.
This review is intended to provide the rudiments of zeolite science applied to refining catalysis.

Key learning points

 Role of zeolites in the most important oil refining processes.
 Nature of Brönsted and acid sites in zeolites.
 Relationship between structure and composition of zeolites and catalytic activity.
 Bifunctional acid and hydrogenation catalysts based on zeolites.
 Major general trends in oil refining.

Introduction and large surface area supports for developing environmentally

Modern societies require extensive consumption of energy that
nowadays is predominantly based on the combustion of fossil fuels
provided by refining.1–3 From the point of view of Sustainability and
Environment protection, currently there is much interest in repla-
cing as a primary energy resource fossil fuels by alternative renew-
able energy sources.4 However, considering the degree of maturity
and efficiency in the use of oil and the difficulty in developing on a
massive scale other energy sources, it is very likely that the
prevalence of refining and petrochemistry will continue in the next
decades, particularly considering the new oil fields found and
modern extraction technologies that recover more exhaustively
hydrocarbons from bituminous sand and unconventional
sources.5,6 The current efficiency of refining and petrochemistry is
largely based on the use of highly active, selective and durable
catalysts,7,8 zeolites being the paradigmatic example of solid acids
a
Instituto de Tecnologı́a Quı́mica CSIC-UPV, Univ. Politecnica de Valencia,
Av. De los naranjos s/n, 46022 Valencia, Spain. E-mail: aprimoar@itq.upv.es,
hgarcia@qim.upv.es
b
Center of Excellence for Advanced Materials Research, King Abdulaziz University,
Jeddah, Saudi Arabia
benign processes.8 This outstanding level of development in refin-
ing and petrochemistry has been achieved over the years by a
combination of intensive research and innovation.
The purpose of this tutorial review is to summarize the prevalence
in refining of catalytic processes based on the use of zeolites. We will
start with a brief description of the composition, structure and
properties of zeolites with a focus on their application as solid
catalysts. The main part of this review will be the description of some
catalytic processes, such as paraffin isomerization, isobutene–butene
alkylation, reforming, cracking and hydrocracking, currently per-
formed in the refining industry to produce massive amounts of fuels
and lesser quantities of chemicals. In the final part, we will provide
our view on future developments in the field, particularly, the quest
for even more efficient zeolites and co-processing of biofuels.
Zeolites: composition, structure and
synthesis
Zeolites can be defined as crystalline, porous aluminosilicates
in which the primary building blocks are TO4 tetrahedra having
a Si4+ or Al3+ cation (T atoms) at the center and four oxygen

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Fig. 1 Classification of zeolites and porous solids depending on the
dimensions of the voids.
atoms at the corners.9 Each corner is shared by two TO4 units
forming a tridimensional framework defining cavities, chan-
nels and empty spaces generally denoted as ‘‘micropores’’. This
porosity defined by the rigid crystal lattice is open to the
exterior of the solid crystallite allowing the mass transfer from
the exterior to the interior of the zeolite particle and the
intracrystalline diffusion of molecules smaller than the micro-
pore dimensions. Zeolites can be classified depending on the
pore size as small, medium and large pore size zeolites when
the openings of the micropores are constituted by rings of
eight, ten or twelve oxygen atoms (Fig. 1).10
The key parameter that controls many properties of the
zeolites having a large influence on their catalytic activity is
their aluminum content. Depending on the zeolite family, this
aluminum content can vary from one Al atom per Si atom
(zeolite X) to the case of all-silica zeolite (silicalite) in which the
amount of aluminum in the composition should be zero.
Scheme 1 summarizes the chemical composition of a zeolite
and the properties that derive from it.
Due to the different charge of Al3+ and Si4+, the TO4 tetra-
hedra can have a net negative charge (AlO4) or can be neutral
(SiO4). The consequence of the presence of Al3+ in framework
positions is the appearance of an equivalent number of nega-
tive charges in the framework that require the presence of
Ana Primo obtained her PhD from
the Institute of Chemical
Technology (ITQ) in Valencia,
Spain, under the guidance of
Avelino Corma and Hermenegildo
Garcı́a. She was a postdoctoral
researcher in the Institut Charles
Gerhardt of Montpellier (France,
2007–2009). She is currently an
associate researcher at the ITQ,
where she works on the synthesis
of heterogeneous catalysts based
Ana Primo on metal nanoparticles supported
on porous polysaccharides, gra-
phenes and metal oxides for their application in biomass and
photochemistry. She has co-authored 28 publications.
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Scheme 1 Chemical composition of zeolites and possibilities for its
control. Key parameters are the nature of charge-balancing cations and
the Si/Al ratio.
charge-balancing cations to ensure the electroneutrality of the
solid. These charge-balancing cations are occupying the micro-
pore space and because they are not grafted into the framework
and are bonded to the lattice by Coulombic forces, they can be
totally or partially exchanged by different cations. In fact, one of
the main applications of zeolites is in detergent formulations as
water softener to remove Ca2+ ions from hard waters by ion
exchange with Na+.11–15 These compensating cations are intro-
duced primarily during the synthesis of the zeolites and can be
either inorganic, typically alkali metal ions, or organic such as
quaternary ammonium ions. Quaternary ammonium ions are
very common in the composition of synthetic zeolites because
this type of organic cations act in the synthesis of zeolites as
structure directing compounds.16
Since zeolites are crystalline solids with a defined unit cell,
the position of the charge compensating cations in the frame-
work can be fixed. Neutron diffraction has shown that alkali
metal ions in faujasites occupy three defined positions, corre-
sponding to hexagonal prism faces (site I, 16 cations per unit
cell), sodalite cages (site II, 32 cations per unit cell) and in the
large cavity (site III, variable number). In other zeolites, such as
bidirectional pentasil, the cations are preferentially located at
Hermenegildo Garcı́a (Herme) has
been a full Professor and member
of the Institute of Chemical
Technology at the Technical
University of Valencia since 1996.
He has co-authored over 500
papers, has supervised over 38
PhDs and holds 14 international
patents. His main current interests
are green chemistry and catalysis
as well as the use of zeolites, metal
organic frameworks and meso-
Hermenegildo Garcia porous materials in supra-
molecular photochemistry, photo-
catalysis and nanotechnology.
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the channel crossings. It is assumed that for divalent cations,
some of the positions will be vacant and that their location is
determined by maximization of the Coulombic forces, reducing
the distances between the positive and negative centers.
One type of zeolites that has attracted considerable attention
in recent years that holds promise as catalyst or support for
heavy oil fraction processing is the so-called delaminated
zeolites. The first example of this type of delaminated zeolites
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is the material known as ITQ-2.17 The preparation of this
material is based on the knowledge of the crystallization of
zeolites and in the particular case of ITQ-2 on the synthesis
of MCM-22.18 This MCM-22 zeolite is obtained by calcination of
the pre-MCM-22 solid resulting from the hydrothermal crystal-
lization of the mother aluminosilicate gel using hexamethylene
imine as a structure directing agent. It happens that the pre-
MCM-22 solid obtained in the hydrothermal crystallization is a
layered material that during calcination undergoes sintering of
the layers forming a 3D framework characteristic of MCM-22
(Scheme 2). If the pre-MCM-22 solid is submitted to ion
exchange using cetyl trimethyl ammonium surfactant, then
those template molecules located at the interlayer space can
be exchanged by bulkier quaternary ammonium ions. This ion
exchange results in an expansion of the interlayer distance
reducing Coulombic interactions between the layers that can be
subsequently disordered by sonication. If, after this swelling
and disordering, the material is submitted to calcination, then
the resulting aluminosilicate is not the expected well-
crystallized MCM-22 but a new material that consists of zeolitic
layers without stacking in the Z direction. The layers have a
zeolitic nature being constituted by hexagonal prisms joining
the upper and lower twelve-membered ring cups. The rims of
these cups contain terminal OH groups and are open to the
exterior.
The layered morphology of ITQ-2, characterized by dis-
ordered zeolitic layers, is responsible for a large external sur-
face area up to 700 m2 g 1 and a very limited microporosity.
This surface area value is much higher than the normal BET
area of zeolites that ranges from 100 to 400 m2 g 1 and
indicates that part of the framework that is not accessible after
Scheme 2 Preparation of delaminated ITQ-2 from pre-MCM-22.
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formation of the MCM-22 framework is accessible after dela-
mination. Thus, for ITQ-2, layers with zeolitic structure having
sites totally accessible to reagents without intracrystalline dif-
fusion limitations are obtained.
Acidity in zeolites
One particular case that is of considerable importance for the
use of zeolites as catalysts in refining is the case in which the
charge compensating cation is formally a proton. In this case,
zeolites are called ‘‘solid acids’’ and due to the microporosity
these internal protons can act as Brönsted centers in hetero-
geneous catalysis.19 Although Si4+ and Al3+ ions have very
similar ionic radius and fit nicely in the center of TO4 tetra-
hedra, the presence of Al3+ introduces a relative lattice instabil-
ity due to the somewhat larger ionic radius of Al3+ with respect
to Si4+, the charge unbalance and low coordination number
around Al3+. Thus, there is a tendency of Al3+ to migrate outside
the lattice forming octahedrally coordinated Al species that are
generally denoted as extra framework aluminium (EFAL). EFAL
species are more probable when the Al3+ content of the zeolite
is high and also when the zeolite is submitted to physical or
chemical stress as, for instance, in thermal treatments espe-
cially in the presence of steam or other chemicals. According to
27
Al NMR spectroscopic data, EFAL is constituted mainly by
octahedral Al3+, appearing at about 0 ppm, and this species is
believed to be responsible for contributing to Lewis acidity in
zeolites. Initial proposals suggested that Lewis acid sites in
zeolites could be correlated with tricoordinated Al species
similarly to what was accepted for conventional BX3 or AlX3
halides as Lewis acids. However, spectroscopic techniques fail
to detect this type of tricoordinated aluminum atoms even for
those zeolite samples in which the presence of Lewis acidity
was confirmed. In fact, by using pyridine as a probe molecule to
monitor the titration of acid sites by IR spectroscopy, it has
been demonstrated that zeolites can exhibit Brönsted and Lewis
acid sites.20 The Brönsted acid sites are ascribed to bridging
OH groups between Al and Si tetrahedra [RAl–(OH)–SiR],
while the Lewis acid sites have been associated to the presence
of EFAL.
There are several polyaluminum species that can be pre-
pared in solution by well established synthetic procedures. In
particular, the so-called Al13 is a cluster of 13 Al ions connected
by hydroxyl and oxo bridges that can be prepared by controlled
hydrolysis of hydrated AlCl3. By analogy, EFAL are also con-
sidered as being constituted by clusters of a few Al atoms. The
number of Al atoms increases with the age of the zeolites and
the strength of steaming or reaction conditions. Since EFAL is
detached from the zeolite framework and several polyaluminum
species are soluble in water in a certain pH range, it should be
possible to remove completely or in part EFAL from zeolites. In
general, EFAL species with low Al content are more soluble than
when the number of Al is high.
The protonic forms of zeolites as solid acids differ from
conventional molecular acids since they have a distribution of
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Scheme 3 Brönsted acid strength of OH groups as a function of the
composition of the second coordination sphere and, therefore, the Si/Al
ratio of the zeolite. This acid strength is deduced from the positive charge
density on the H (qH) estimated by theoretical calculations.
sites with different acid strength. Experimentally, the strength
distribution of the acid sites for a particular zeolite can be
determined by thermoprogrammed desorption techniques
using ammonia as a probe.20,21 It is observed that a certain
percentage of the total adsorbed ammonia can be removed by
heating at temperatures around 150 1C (ammonia absorbed on
weak acid sites), while much higher temperatures, about 300 1C
or more, are necessary to desorb ammonia from strong
acid sites.22 Theoretically, the acid strength of a particular
RSi–(OH)–AlR site depends on the electronegativity of the
cations, Si4+ or Al3+, present in the second coordination sphere
around the bridging OH group.23 Thus, as it can be seen in
Scheme 3, the strongest acid sites are those in which the second
coordination sphere around acidic OH contains six Si4+ atoms
and the strength decreases gradually as the number of Al3+
atoms in the second coordination sphere increases. DFT calcu-
lations have shown that the distance between two neighbor Al
atoms should also influence the acid strength and that in the
case of the faujasite structure Al atoms tend to be in the
sodalite cages and can be easily located in diagonal positions
of the four membered ring.
The consequence of this relationship between Al3+ content
and the strength of the zeolite is that, as it is experimentally
observed, zeolites having high Al3+ content exhibit a high
density of low strength acid sites, while on the other hand
dealuminated zeolites have a low density of acid sites, but of
higher acid strength. In addition, high Al3+ content makes the
zeolites very prone to develop EFAL, generating Lewis acid sites.
The Brönsted acidity of a zeolite is also influenced by the
presence of Lewis acidity. This synergy between EFAL and
Brönsted acid sites resulting in an increase of the acid strength
is similar to that found in liquid acids in which the combi-
nation of Brnsted and Lewis acids can render superacids with
remarkably enhanced strength (Scheme 4).
Besides the composition, the acidity of the zeolites also
depends on their structure. It has been found that for similar
chemical composition, the strength of acid sites in medium
pore size zeolites is higher than that found in large pore size
zeolites.24,25 It has been proposed that this apparent increase in
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Scheme 4 Synergy between Lewis acid sites (AlO+) and Brönsted OH site
leading to an increase in acid strength.
acidity in medium pore size zeolites such as ZSM-5 derives from
the so-called ‘‘confinement effect’’.20,26,27 This ‘‘confinement
effect’’ should be observed, according to theoretical calcula-
tions, when the dimensions of the zeolite pores are commen-
surate with those of the base molecule adsorbed in the internal
space.28 In this case, confinement leads to an increase in the
energy of the HOMO and LUMO orbitals, meaning that the lone
electron pair of the base is being activated in a restricted space.
According to this concept, acidity of a given site does not
depend only on the local environment and composition of the
center but also on the long range ordering and dimensions
of the cavities. Also, the acidity of a site would be different
depending on the molecular size of the probe, being of max-
imum strength when the size of the molecule fits closely within
the interior of the cavities. In general terms, this confinement
effect, particularly applied to the case of acid catalyst for
refining, leads to the conclusion that medium pore size zeolites
are those exhibiting the strongest acidic sites. This is a con-
sequence of the confinement and the matching of the pore
dimension and the size of hydrocarbons found in oil fractions.
Acidity is an extremely important property in catalysis by
zeolites for refining since many of the processes29–32 are proteo-
lytic C–C bond cleavages or involve the generation of carbo-
cations. As we will see later, the most widely accepted mechanism
for hydrocarbon cracking involves protonation of single C–C or
C–H bonds of alkanes and the generation of carbocations that
subsequently undergo b-scission forming a smaller carbocation
and an alkene. One point that has been controversial and of wide
interest is to determine whether or not the acid sites of zeolites
can be considered as superacidic and what is the maximum acid
strength that can be achieved in zeolites. By means of solid-state
13
C NMR spectroscopy, searching for the detection of carbo-
cations generated upon absorption of probe molecules inside
zeolites, Haw and co-workers have determined that the maximum
strength of an acid site that roughly corresponds to the average
acidity of highly dealuminated ZSM-5 is equivalent to 70% of
sulfuric acid in water.33 However, all these measurements have
been carried out at room temperature and, since catalytic cracking
is typically carried out at temperatures of 200 1C or above, the
strength under these conditions has to be sufficiently high to
protonate single C–C and C–H bonds, characteristic of superacidic
behavior at room temperature.34
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Besides acidity, another important catalytic activity of high
relevance in refining is hydrogenation/dehydrogenation. Acid
zeolites are not hydrogenation catalysts and this functionality
has to be implemented in these solids by adding metals,
particularly Pt, Pd or Ni. In this case, the zeolite acts as a support
providing a large surface area to deposit highly dispersed metal
nanoparticles. In this way, bifunctional, acidic and hydrogenat-
ing, catalysts based on impregnation or deposition of a metal on
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a protonic zeolite can be developed. These bifunctional zeolites
are important in the isomerization of linear alkanes and hydro-
cracking of heavy oil fractions as it will be discussed below.
Diffusion and kinetics
One of the main problems in porous solids in which the reaction
takes place predominantly inside the pores is intracrystalline
diffusion. The pores defined by the framework are open to the
external surface allowing the mass transfer from the exterior
toward the interior of the particle, provided that the size of the
molecule is smaller than the dimensions of the pores. As
commented above, zeolites are microporous materials (pore size
o 2 nm), the prefix ‘‘micro’’ meaning that the pores are smaller
than materials with ‘‘meso’’ (from 2 to 10 nm) or ‘‘macro’’ (larger
than 10 nm) pores. As it can be seen in Fig. 1, zeolites can be
classified according to the pore size. In ‘‘small pore’’ zeolites,
having apertures defined by 8 oxygen atoms, only small gas
molecules can access the interior. In the case of ‘‘medium pore’’
zeolites (10-membered ring apertures) such as ZSM-5, benzene,
toluene and para substituted aromatics can enter through the
pores. The range of molecules that can diffuse in ‘‘large pore’’
zeolites having 12 membered rings is much larger, since the
dimensions of these pores are typically around 0.7 nm. Besides
pore dimension, the geometry of the pore system is crucial to
determine the intracrystalline diffusion coefficient of molecules.
Diffusion in monodirectional zeolites having parallel channels,
like mordenite, is generally more difficult than in bi- and
tridirectional zeolites. In the case of monodirectional pores,
molecules diffusing in the channel have to move one after the
other following the same direction and can be easily blocked by a
single molecule. In contrast, diffusion in open tridirectional
zeolites, like faujasites X and Y, is easier, since the cavities can
be accessed through four independent windows. Furthermore,
monodirectional zeolites are prone to become deactivated by a
small percentage of poisons blocking the entrance of the chan-
nels, while bi- and tridirectional zeolites can tolerate a larger
percentage of poisons before undergoing deactivation.
Concerning reactivity, the pore size can be responsible for the
control of the product distribution. The term ‘‘shape selectivity’’
has been coined to denote those cases using zeolites or other
microporous solids as catalysts in which the reason why a product
is predominantly formed is exclusively the molecular shape and
dimensions.7 This is the case of xylene isomerization, toluene
disproportionation or alkylation in ZSM-5 as solid acid, processes
that are carried out on a very large scale in petrochemistry. In this
case, the thermodynamic mixture at equilibrium should contain
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Scheme 5 Pictorial illustration of shape selectivity in ZSM-5 for the
formation of p-xylene in toluene disproportionation.
o- and p-xylenes, with lesser amounts of the meta isomer. How-
ever, when carrying out the reaction inside the medium pore
zeolite ZSM-5 in which the pore dimension only allows diffusion
of p-xylene, m- or p-xylene formed in the crossings of the channel
system cannot diffuse out of the crystals and become entrapped
until they rearrange to the p-xylene that is the only one that can go
out of the pores (Scheme 5).
Intracrystalline diffusion of linear alkanes decreases with the
chain length. Considering the pore size of large pore zeolites
employed in oil refining, there are some heavier fractions whose
diffusion inside the zeolite crystallites is slow. This is one of the
reasons why there is a frequent need to increase porosity in
zeolites. This can be achieved by controlled damage of the crystal
structure and post-synthetic creation of larger pores by acid, base
or steam treatments of the zeolite. Citric and phosphoric acids
and sodium hydroxide at appropriate concentrations are com-
mon reagents for this purpose. Ultrastable USY zeolites are
generally obtained by steaming under optimal temperatures
and times from as-synthesised Y zeolite samples. Steaming leads
to partial framework dealumination and to the creation of larger
pores not present in well crystallized samples. As a consequence
of steaming, diffusion in USY is favored and, in addition, deal-
umination results in a more robust and stable framework that is
less prone to undergo further changes.
The above discussion highlights the crucial influence that
pore dimension and porosity of zeolites have on the kinetics of
the reactions taking place inside the confined reaction cavity
defined by zeolite internal voids and how it can determine the
cracking severity and reaction product distribution.
Gasoline pool
In the initial times of the automotive industry the light naphtha
fraction of the crude oil refining was used directly as gasoline
(‘‘light straight run’’ gasoline). As the power of car engines
increased, higher quality gasoline was needed to stand the
pressure and temperature of the compression cycle in the
engine cylinders. The quality of the gasoline is quantitatively
measured by the octane number, the higher the octane number,
the higher the ability of the gasoline to stand high pressure and
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Scheme 6 Streams contributing to the gasoline pool.
temperature. In this scale the performance of n-heptane and 2,4,4-
trimethylpentane has been arbitrarily assigned 0 and 100. In
general, the octane number of a pure hydrocarbon increases with
the degree of branching, presence of cycles or for aromatic com-
pounds. As the demand for gasoline increased as well as the need
for octane numbers higher than those characteristic of light straight
run gasoline (about 70), it was necessary to blend various streams of
the refinery in a pool to meet the requirements of gasoline
production and quality. Scheme 6 presents the composition of
a representative gasoline pool indicating the origin of the
individual components.
Linear paraffin isomerization
One of the components of the gasoline pool is the naphtha
fraction denoted as light straight run gasoline, generally after
submitting this stream to isomerization to increase its octane
number. Light straight run naphtha is constituted, mainly, by
linear alkanes accompanied by a small percentage of aromatics,
and has typically an octane number about 74 or below, insuffi-
cient to be added directly to the gasoline pool. This light
straight run naphtha should be, therefore, submitted to iso-
merization, a process that is based on the use of acid zeolites as
catalysts. The octane number of linear alkanes decreases as the
number of carbons increases, and therefore, these long-chain
linear compounds present in this fraction (mainly C7 and C8)
should be preferentially isomerized in the process.
Isomerization of linear alkanes is a process controlled
thermodynamically and the composition of the equilibrium
depends on the temperature. Thus, at a given temperature the
equilibrium distribution among isomers limits the extent in
which linear paraffins are converted into branched isomers.
The general tendency is that isomerization is disfavored as the
temperature increases in the range from 0 to 600 1C. Therefore,
from the thermodynamic point of view, it is convenient to work
at the lowest possible temperature. Thus, the role of the catalyst
is to increase the reaction rate allowing the reaction to reach
equilibrium at the lowest possible temperature.
Isomerization of linear alkanes requires acidity combined
with dehydrogenation/hydrogenation capability. For this reason,
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a typical catalyst for linear paraffin isomerization is a bifunc-
tional zeolite or an acid metal oxide both containing noble
metals. Commercial linear paraffin isomerization reactions that
are based on zeolites are the HYSOMER from Shell/UOP and the
Cepsa HYSOPAR technology.35 In these two commercial pro-
cesses, acid zeolites, and particularly mordenite, are the pre-
ferred solid acids. Mordenite is a monodirectional zeolite whose
structure is defined by twelve membered ring channels of about
0.7 nm diameter. In order to increase the acidity of mordenite,
the as-synthesized zeolite is submitted to dealumination to reach
the optimal Si/Al ratio. Framework dealumination leads to the
formation of EFAL and heavy oligomers of this EFAL cannot be
removed by washing. The EFAL presence modifies the overall
acidity of the zeolite (total acid site population and strength
distribution), influencing the catalytic activity of the mordenite
for linear alkane isomerization, altering the proportion of iso-
alkanes. In this context, highly dealuminated mordenites, with
the Si/Al ratio around 16, obtained by a combination of steaming
and acid washing, are more efficient for light straight run
naphtha isomerization than alternative dealumination treat-
ments based exclusively on acid washings or steam treatment.
Also, it has been found that there is an optimal FAL/EFAL ratio in
the range from 2 to 4 to obtain a maximum isomerization
proportion for Pt-mordenite.
In the technology for linear straight run alkane isomerization,
conventional zeolites undergo poisoning and deactivation due to
the presence of sulfur in the stream. The main advantage of the
HYSOPAR process based on Pt supported on dealuminated zeolite
is the higher sulfur tolerance of the catalyst as it is shown in Fig. 2.
In fact, the two main current tendencies in the design of catalysts
for light straight run paraffin isomerization are to develop catalysts
efficient at lower reaction temperatures from 100 to 200 1C and
tolerant to sulfur and water. In a certain sense, the ideal catalyst
should combine the high activity at low temperatures of chlori-
nated alumina with the good stability found for zeolites.
It has been proposed that Pt supported on sulfated zirconia
could be an alternative to zeolites for light straight run paraffin
isomerization. Sulfated zirconia has been considered as a super-
acid solid and can perform isomerization of linear alkanes at
temperatures between 150 and 200 1C, which is an interval
remarkably lower than that employed in zeolites that operate in
the range from 240 to 280 1C. Unfortunately, Pt supported on
sulfated zirconia has a low stability in the presence of sulfur
Fig. 2 Influence of sulfur content on the catalytic activity of modified
mordenite (HYSOPAR) (a) for n-pentane isomerization compared to
chlorinated alumina (b).
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and water. Even addition of Nb to the Pt supported on zirconia to
increase catalyst resistance towards sulfur or water is not sufficient
to maintain the stability of this material and, for this reason,
zeolites still continue to be the preferred catalysts for this process.
Another current tendency in the refinery is to operate the light
straight run isomerization with a stream in which components
coming from reformate, particularly benzene, are present. Since the
percentage of benzene allowed in the reformate is decreasing due to
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environmental concerns, there is a surplus of benzene which should
be introduced into the gasoline pool after adequate hydrogenation.
In particular, one option is co-processing light straight run and
benzene, in such a way that the isomerization of linear alkanes
takes place simultaneously with benzene hydrogenation and iso-
merization. A convenient catalyst for co-processing linear alkanes
and benzene has Pt nanoparticles supported on nanocrystalline
Beta (ncBeta) zeolite.36 The comparative activity data of the conver-
sion of n-alkanes into the corresponding isoalkanes in the presence
of benzene have shown that the Pt-ncBeta is more stable and
efficient than Pt-mordenite. In addition, Pt-ncBeta is able to perform
hydrogenation of benzene to a mixture of cyclohexane and methyl-
cyclopentane with complete conversion under the conditions where
isomerization of linear alkanes takes place. Also, Pt-ncBeta is more
tolerant to sulfur than catalysts based on zirconia.
Isobutane–butene alkylation
About 12% of the blend in the gasoline pool may come from
butene alkylation. The acid catalyzed mechanism for isobu-
tane–butene alkylation is shown in Scheme 7. This stream has a
Scheme 7 Simplified mechanism for isobutane–butene alkylation and
competing unwanted processes. t-C4+: tert-butyl cation; 2-C4Q: isobutene;
TMP: trimethylpentanes; sec-C4+: sec-butyl cation; DMH: dimethylhexanes;
HT: hydride transfer.
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high octane number, ideally 100, and is much valued since it
does not contribute to the gasoline sulfur content, because
isobutane and butene are free of this element.
Classical alkylation processes are based on the use of homo-
geneous liquid acids and particularly HF and H2SO4.37,38 From
the catalytic point of view, the two main relevant properties of the
liquid acids are their decay and isobutane solubility in the acid
phase. Isobutane solubility is much higher in HF than in H2SO4.
This allows reaching a higher concentration of isoalkane favoring
hydrogen transfer steps to carbenium ions, reducing the carbo-
cation lifetime and minimizing secondary reactions. These
advantages exhibited by HF allow shorter contact times and
operation at higher temperatures where the reaction rate is
higher. In contrast, although the acid strength of H2SO4 is much
higher, this acid presents also high viscosity and density unfavor-
able for the mixing with hydrocarbons, complicating significantly
reactor design to ensure sufficient contact between the two
phases. An additional problem with the use of H2SO4 is that
the amount of acid lost in the products is much higher, requiring
larger catalyst make up. Make up and regeneration are about 30%
of the total operation cost in the case of H2SO4, while they
represent only 5% for HF. The main problem of HF is, however,
its large negative environmental impact that requires strict safety
measures due to the high risk of accidental leakages and the fact
that HF aerosol can stand as highly corrosive, persistent clouds
over long periods of time. For this reason, there is no clear
advantage in the use of HF vs. H2SO4 as alkylation catalyst.
One alternative to the use of liquid acids is the use of solid
acids. Amorphous silica–alumina has been used as solid
catalyst, but zeolites have the advantage of a higher activity,
higher durability and lower deactivation. The activity of zeolites
depends on the Si/Al ratio and on the crystal structure. Table 1
presents a typical product distribution of isobutane alkylation
depending on the zeolite used as catalyst.
It appears that the use of large pore zeolites favors the
formation of preferred trimethylpentanes and that stronger acidity
leads to 2,2,4-trimethylpentane that is the standard isoalkane with
an octane number of 100. Of large pore zeolites, zeolite Beta is the
one that exhibits higher stability against deactivation. Large pore
acid zeolites are preferred to minimize the loss of activity along the
time on stream. Besides deactivation, it appears that the presence
of some coke causing a partial decrease of the catalytic activity also
affects the product distribution, reducing the percentage of C5–C7
with respect to C8–C9+, while dimerization of butenes may become
the predominant process vs. isobutane alkylation.
In isobutane alkylation, as in most of the refining processes
using microporous solids, catalyst reactivation is the key issue.
Catalyst regeneration requires, on the one hand, adequate
Table 1 Activity and selectivity of some acid zeolites as alkylation catalysts
Zeolite USY Beta Mordenite ZSM-5 MCM-22
2-Butene conv. (%) 100 97 94 100 95
C8 (wt%) 40.9 50.6 70.2 83.5 33.0
Trimethylpentanes 74.1 76.9 76.9 20.9 36.9
2,2,4-Trimethylpentane 37.7 52.4 57.2 27.3 4.1
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engineering of the process using moving bed reactors to allow
continuous regeneration and, on the other hand, also requires
durable formulations. Thus, the presence on the catalyst of
some noble or transition metals is advisable since these metals
allow in the regeneration step the use of hydrogen to perform
gasification and hydrocracking of coke which is the poison that
deactivates the catalyst by neutralizing the acid sites and by
pore blocking. With hydrogen and noble metals, the coke is
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completely removed in the zeolite regeneration.
Several commercial isobutane alkylation technologies like
the Lurgi Eurofuel, Exsact and Alkyclean processes are using
solid catalysts,39 some of them based on acid zeolites as the
active component. In the Alkyclean technology, noble metal-
containing zeolites, probably Y or b zeolites, are used in multi-
ple fixed bed reactors in a swing configuration, allowing
continuous operation through reactors with active catalysts
while the others are in the regeneration cycle.
Fluid catalytic cracking (FCC)
FCC provides a surplus of high octane number gasoline by
converting vacuum distillates, particularly vacuum gasoil, into
gasoline. From the chemical point of view, several molecular
transformations are concurrently taking place during FCC,
including shortening of linear long alkanes, isomerization of
linear into branched alkanes and dehydrogenation of cyclic
olefins into aromatic naphthenes (Scheme 8).
Scheme 8 Elementary processes taking place in FCC.
Scheme 9 Elementary steps assumed to take place in catalytic cracking on zeolites.
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The elementary steps taking place in alkane cracking in
zeolites are complex but require strong Brönsted acid sites
leading to proteolytic cracking and carbonium ion generation,
as well as strong Lewis acids forming carbenium anions by
hydride abstraction. Subsequently, most of the chemistry
derives from the behavior of the carbenium anions including
rearrangements, hydride abstraction, b-scission and olefin
formation (Scheme 9).
Typically, the FCC catalyst contains an active component
(10 to 50 wt%) dispersed on a solid matrix (between 50 and 90%
of the total) providing physical and mechanical resistance and
embedding the active component, and some additives that
increase the tolerance of the catalyst against deactivation by
poisoning (Scheme 10). The active phase is generally a large
pore zeolite and most commonly dealuminated zeolite Y con-
taining rare earths. In general, an increase in the percentage of
rare earths leads in an increase in feed conversion accompa-
nied by an undesirable decrease in the octane number of the
resulting gasoline. Also, framework dealumination results in an
increase in the activity of the zeolite, particularly considering
that zeolite Y has high Al content. Steam treatment is a
convenient procedure to reduce framework Al, producing a
USY zeolite with high structural stability. Besides dealumina-
tion, this treatment with steam also increases mesoporosity of
the crystallites due to the partial damage of the zeolite particles
leading to the creation of mesopores above 6 nm, highly
beneficial for the activity and stability of the zeolite by favoring
intracrystalline diffusion of substrates and products reducing
poisoning derived from long contact times of substrates and
products with the acid sites. Besides composition (Si/Al ratio)
and post-synthetic treatments (steaming) the crystal size of the
Y zeolite is also a key parameter controlling activity and
selectivity, which in general increase as the average crystal size
decreases. Scheme 11 summarizes the parameters that control
the activity of zeolites as cracking catalysts.
As commented earlier, strong Lewis acid sites are conveni-
ent to promote hydrocarbon cracking. Therefore, the presence
of EFAL may be convenient in USY catalyst. EFALs can be
classified between those with a few Al atoms that can be
dissolved by acids and those oligo- and polymeric EFALs
formed by condensation of low-weight EFALs that cannot be
dissolved in acids remaining entrapped on the zeolite pores.
There is a strong influence of the EFAL type on the Lewis
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Scheme 10 Components present in general formulations of a FCC
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catalyst.
Scheme 11 Main parameters that influence the catalytic activity of zeo-
lites in FCC formulations.
acidity, with low-weight EFALs being stronger Lewis acids and
with a higher tendency to interact with Brönsted acid sites.40
Besides as active components in catalysis, other zeolites can
also form part of the FCC catalysts as additives, for instance, to
increase the octane number of the resulting FCC gasoline. Thus,
the presence of HZSM-5 in the FCC catalyst formulation favors
the selective cracking of linear olefins with molecular weights
in the range of the gasoline fraction. This preferential conversion
of linear olefins into smaller olefins, mainly propylene, by HZSM-5
leads indirectly to an increase in the octane number of the
gasoline by removing linear alkenes from the liquid fraction.
The medium pore size of HZSM-5 only allows diffusion of linear
hydrocarbons but not branched alkanes. On the other hand,
propylene from FCC can be a desirable byproduct as feedstock
in bulk chemical industry and operation and unit design can
be adjusted to increase the severity of the cracking, to yield pro-
pylene of up to 20% of the initial feed weight.
One problem of FCC catalysts is the tolerance to the
presence of metals and particularly Ni and V. These and other
metals can be present in high molecular weight organic
Scheme 12 Desulfuration based on catalytic oxidation of sulfur compounds present in heavy gasoil fractions.
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compounds present in the FCC feed. Deposition of Ni on the
catalyst favors the generation of coke on the catalyst due to its
dehydrogenating capability. To minimize the influence of Ni,
FCC catalysts contain additives, such as Sb that acts as a poison
of Ni by forming Ni–Sb alloys, inactive to promote dehydro-
genation. Also, the effect of Ni can be neutralized by alumina
present abundantly in the catalyst matrix by forming Ni alumi-
nates that have much lower dehydrogenation activity. V also
has some activity for hydrogen evolution and coke formation
during the FCC process. However, the main problem caused by
V is the formation of strong acids during regeneration of FCC
catalyst that produce deterioration of the zeolite crystal struc-
ture reducing its service life. To minimize this effect of V, the
use of more robust zeolites, generally those having low Na and
Al content, as well as the presence of vanadium trapping
compounds in the additives, generally basic solids such as
CaO, Al2O3 or MgO, is recommended.
The fraction of additives of FCC catalysts may also contain
some components to effect NOx decomposition. Nitrogen is
present in the FCC feed and about 50% of the N in the FCC feed
becomes deposited on the catalyst as coke. During FCC catalyst
regeneration by combustion of coke, part of the nitrogen
evolves as N2, but the other part forms NOx that have to be
decomposed to avoid their emission to the atmosphere.
Another problem of the FCC stream is that this fraction
contributes to a large extent to the total sulfur content present
in gasoline and diesel. About 90% of the total sulfur content of
the gasoline is due to the FCC contribution, coming mainly
from the heaviest fractions. Typical sulfur-containing com-
pounds in FCC gasoline are mercaptans, dialkylsulfides, thio-
phenes, alkylthiophenes and benzothiophene, while heavier
aromatic sulfur components particularly dibenzothiophene
and its alkyl derivatives are present in diesel. Legal regulations
are constantly reducing the sulfur content of fuels and achieve-
ment of such low S contents currently requires the combination
of several technologies. The overall strategy to control the sulfur
content in fuels includes the selection of crude oil and ade-
quate fractionation of FCC gasoline to reduce the sulfur in the
feed, but also post-treatment of FCC gasoline and diesel.
Among FCC desulfuration post-treatments, one of the emerging
technologies is the selective liquid-phase oxidation of thio-
phene and aromatic S compounds under mild conditions,
using tert-butyl hydroperoxide or H2O2 as the oxidizing reagent.
In this way, the sulfur atom becomes oxidized to sulfoxide or
sulfone, increasing considerably water solubility and boiling
point of the sulfur compounds, allowing their easier separation
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from the fuel (Scheme 12). This catalytic oxidative desulfura-
tion could lead to fuels with sulfur content below 10 ppm that
will be the legal specification in the very near future in many
Western countries. One promising catalyst for oxidative desul-
furation is Beta zeolite containing Ti atoms.
Other alternative strategy to reduce the sulfur content con-
sists in the olefin alkylation of thiophenic compounds. This
process, combined with adequate pretreatments, can reduce
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the fuel sulfur content to less than 10 ppm, consuming only a
small amount of hydrogen and without reducing the octane
number of gasoline. The process consists in increasing the
boiling point of sulfur compounds above 200 1C by increasing
the molecular weight of sulfur compounds by alkylation with
olefins. Since over 90% of the total sulfur compounds present
in FCC gasoline and gasoil are aromatics, they can undergo
Friedel–Crafts alkylation with olefins. The alkylated sulfur
compounds are heavier and easier to separate from the FCC
stream. Later, these alkylated aromatic sulfur compounds can
be combined with the diesel stream submitted to hydrotreat-
ment and partially recovered increasing desulfuration
efficiency.
Reforming
One of the most important processes in refining is the reform-
ing of the heavy naphtha fraction into mixtures in which
aromatic compounds and particularly benzene, toluene and
xylenes are the predominant compounds. Chemically, the
reforming corresponds to the chemical transformation of satu-
rated acyclic and cyclic hydrocarbons into aromatic compounds
by dehydrogenation without reducing substantially the number
of carbons of the products with respect to the substrates.
Scheme 13 presents the elementary transformations that take
place in reforming. These transformations include cyclization
of acyclic compounds, isomerization of cyclic compounds into
cyclohexene and dehydrogenation and aromatization.
The main purpose of reforming is to obtain aromatics
because these compounds exhibit octane numbers over 100
and following their addition into the gasoline pool they lead to
a notable increase in the octane number of the resulting blend.
A minor percentage of reformate is used by the chemical
industry to obtain pure benzene, toluene and xylenes and from
them bulk chemicals, monomers and commodities, but this
Scheme 13 Elementary reactions occurring simultaneously in the
reforming of naphtha.
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Scheme 14 Co-processing of benzene in naphtha isomerization.
use represents around 10% of the total reforming capacity. Two
processes related to the industrial use of reformate are toluene
disproportionation and xylene isomerization.
The composition of gasoline and transportation fuels have
been evolving to comply with legal regulations, and one com-
mon trend in developed countries, together with providing
gasoline with high octane number and the use of the three
way catalysts to avoid the presence of unburned hydrocarbons
in the flue emissions, has been to limit and reduce the
percentage of benzene in gasoline. Among all the aromatic
compounds, benzene is the most toxic one and has a well
proven carcinogenic effect. Thus, the tendency in the refinery
has been to reduce the percentage of benzene in reformate by
adjusting the operation conditions and also to separate ben-
zene from reformate to reprocess this chemical mainly with
linear alkenes in the isomerization process. Scheme 14 illus-
trates the use of reformate and the connection between refor-
mate and linear isomerization of alkanes.
Since according to the chemical transformation dehydro-
genation with hydrogen evolution is the major individual
process taking place in the reforming, acidity is not a require-
ment for the catalyst, which, in contrast, should have noble
metals with high hydrogenation/dehydrogenation activity as
the main active component. Thus, most of the commercial
reforming catalysts are based on Pt supported on large surface
area solids such as non-acidic zeolites or metal oxides.
Hydrocracking
One constant feature in refining is the need to convert effi-
ciently less-valuable, heavier fractions into mixtures of hydro-
carbons of lesser number of carbons for their consumption as
transportation fuels. For the conversion of heavier into lighter
fractions, one of the processes that is performed on a large
scale is the hydrocracking of heavy gasoil, vacuum gasoil and
gasoil from coke into lighter compounds. To carry out this
process hydrogen is required to minimize the formation of coke
and carbonaceous residues on the catalyst and for this reason is
termed ‘‘hydrocracking’’.
Several elementary chemical transformations are taking
place in the hydrocracking process, similar to those that have
been already commented for the cracking. These classes of
individual reactions include shortening of the chain length of
the paraffins in the feed, isomerization of the linear into
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Scheme 15 Elementary steps occurring simultaneously during hydrocracking.
branched alkanes, ring closure and hydrogenation/dehydro-
genation of the C–C bond (Scheme 15).
There are two main general types of hydrocracking processes
although each of them can be subjected to modifications
depending on the needs of each refinery. One of these types is
the single-stage hydrocracking in which the fractionating unit is
located after the hydrocracker (Scheme 16). In this type, it can be
more than one hydrocracker in series and it could be also
recycling or not of the unconverted feed. In the other case, the
process is known as once-through, single-stage hydrocracking.
The two-stage hydrocracking is characterized by having the
main fractionating unit located between two hydrocrackers
(Scheme 16). Generally the first reactor is used to perform
hydrotreatment of the feed to eliminate sulfur, nitrogen, oxygen
and metals that could be present in the heavy gasoil fractions.
In this first reactor, it could also be a light hydrocracking of the
alkanes with formation of a certain percentage of lighter
alkanes. Hydrocracking producing effective shortening of the
Scheme 16 Diagram of a single-stage (top) and a two-stage (bottom)
hydrocracking process.
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average number of chain carbons takes place predominantly in
the second hydrocracker.
Hydrocracking requires bifunctional catalysts able to pro-
mote hydrogenation of olefins and cracking of alkanes. At the
metal sites of the catalyst dehydrogenation of the n-paraffin
gives rise to the formation of n-olefins that subsequently are
protonated by the acid sites to form secondary carbenium ions
that undergo spontaneous rearrangement to more stable
tertiary carbenium ions. These tertiary carbenium ions can
form cracked products through b-scission at the carbocation
center or can give rise to an isoolefin that upon hydrogenation
will form finally isomerized alkanes.
Conventional catalysts for hydrocracking contain a metal
that has as the main function the capability to perform hydro-
genation/dehydrogenation of unsaturated/saturated hydro-
carbons. This metal component can be noble metals such as
Pt, Pd or their alloys or can be even metal sulfides such as
combinations of Ni, Mo, Ni–W and Co–Mo. The hydrogenating
capability is the highest for Pt and noble metals and is lower for
metal sulfides that require higher percentages and higher tem-
peratures in order to exhibit the desired activity, but are less
prone to deactivation by sulfur. The order of hydrogenating
performance of sulfides is Ni/W 4 Ni/Mo 4 Co/Mo. This
metallic component is supported on an acid solid such as
amorphous silica–alumina or preferably zeolites such as morde-
nite, zeolite Y and Beta. The acid strength of zeolites is higher
than that of amorphous silica–alumina and, for this reason,
zeolites require lower temperature to act as hydrocracking
catalysts, typically, between 300 and 330 1C. In contrast, amor-
phous silica–aluminas operate at temperatures between 340 and
390 1C. In addition, zeolites also exhibit a lower tendency to
deactivate which can be measured, for instance, by keeping
constant the operation temperature required to perform 50%
conversion of the feed. Generally, amorphous silica–aluminas
undergo a quick deactivation at short time on stream leaving a
residual acidity that then decreases in activity more gradually for
longer times on stream.
Concerning the performance of zeolites in hydrocracking, it
has been found that high acid strength leads to an increase in
the percentage of naphtha formation in hydrocracking at the
expense of middle distillates. Increasing the catalyst zeolite
content and using strong acid zeolites increases feed conver-
sion and naphtha selectivity.
One problem of zeolites as catalysts is the impeded diffusion
of large molecules through the internal pores. It has been
found that the catalytic activity of Ni-containing Y zeolite
decreases drastically along the alkane chain length, a para-
meter that correlates with the boiling point of the gasoil. In
contrast, amorphous silica–aluminas lacking porosity exhibit
higher activity as the boiling point of the feed increases. This
increase of feed conversion with the average chain length of the
paraffin is a reflection of the intrinsic higher reactivity of long
alkanes towards cracking and should also be observed for zeolites if
intracrystalline diffusion was not opposing to this effect.
In order to increase the activity of zeolites for high boiling
point gasoil fractions, it is necessary to increase accessibility of
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the reactants to the acid sites. One way to enhance the popula-
tion of accessible sites is to increase the zeolite external surface
area. This increase of the external area can be achieved by
reducing the average particle size of the zeolite crystallites from
the micro to the nanometer length. As commented in the
paraffin isomerization, ncBeta can be obtained by varying the
synthesis conditions of these zeolites, reducing crystallization
time and increasing the concentration gel of the zeolite precur-
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sors in the synthesis. This decrease in the particle size of ncBeta
is beneficial for its catalytic activity in hydrocracking with respect
to conventional USY zeolite of micrometric particle size or with
respect to less acidic amorphous silica–alumina. In addition,
ncBeta zeolite shows higher product selectivity than USY zeolite
for middle distillates at the expense of lower weight percentage
of undesirable gaseous alkanes. These gases are undesirable
byproducts in hydrocracking, where the aim is to convert
vacuum gasoil and heavy fractions into liquid fuels for transpor-
tation, and the evolved gases have low commercial value.
A new type of zeolite that shows considerable promise in
hydrocracking due to the accessibility of its acid sites is
delaminated zeolites. The advantages of delaminated zeolites,
and specifically ITQ-2, as catalysts for hydrocracking of vacuum
gasoil derive from the accessibility of their active sites that are
located on the layers and not embedded in the microporous
system. Thus, comparison of the vacuum gasoil conversion in
the range of temperatures from 340 to 460 1C shows that Ni
supported on ITQ-2 performs better than Ni–USY and much
better than Ni supported acid alumina, while exhibiting lower
selectivity than USY for undesirable gas formation.
One example of how the dimensions and geometry of the
pore system can control the product distribution that has
considerable implications in refining is the cracking of heavy
gas oil to gasoline with minimum amounts of gases using a
bidirectional zeolite ITQ-36 zeolite.41 In this case, there are two
intersecting channels with different dimensions. Gas oil mole-
cules can diffuse through the larger channels accessing the acid
sites, but not through the smaller channels. In the acid sites,
gas oil molecules undergo cracking forming smaller molecules
in the range of the gasoline fraction that diffuse away preferentially
Scheme 17 Molecular traffic of gas oil through the 18 membered ring
channels reaching acid sites and diffusion of gasoline through the smaller
channels.
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Fig. 3 Relative performance of MCM-41 containing Ni–Mo for hydro-
cracking of vacuum gasoil; (E) MCM-41, (’) USY, (m) amorphous silica–
alumina.
through the smaller channels without undergoing undesirable
consecutive cracking. Scheme 17 illustrates the process.
An alternative to the use of microporous zeolites for hydro-
cracking of long-chain, high-boiling point hydrocarbons is the use
of acidic mesoporous aluminosilicates. The synthesis in the 80s of
MCM-41 and related mesoporous silicas by Mobil researchers
constituted a breakthrough in materials science, since these
porous materials overcome the pore size limitation found for
conventional large pore zeolites below 1 nm and constitute a
logical expansion of porous aluminosilicates into the mesopore
range.42 Since one of the main problems for cracking of long
chain hydrocarbons is the small diffusion coefficient for micro-
porous zeolites, this problem could be alleviated by using meso-
porous acid solids. Thus, not surprisingly, a catalyst constituted
by Ni–Mo supported on MCM-41 performs better than analogous
Ni–Mo/USY and Ni–Mo/amorphous silica–aluminas, while also
leading to a reaction mixture where the percentage of the gaseous
fraction is lower (Fig. 3). Typically, gaseous hydrocarbons are
formed by consecutive cracking processes and the probability
that more than one cracking occurs in a substrate increases along
the residence time of substrates and primary products inside the
micropores of the catalyst. This contact time is related to low
diffusion coefficients. In other words, if the time spent by a
hydrocarbon inside the micropores of a zeolite increases, then
the probability to reduce the size of this hydrocarbon to C1–C4
products by consecutive cracking increases.
In spite of the promises initially held by acidic MCM-41 and
related mesoporous catalysts, none of these materials have
become yet commercial catalysts due to their very poor structural
stability, especially to steam regeneration. During cracking and
hydrocracking operation, the catalytic activity of fresh materials
mostly disappears in a few seconds, and for this reason, con-
tinuous addition of fresh catalyst in the reactor and continuous
reactivation of used catalyst is necessary. Thus, during the
service life of a solid catalyst, many cycles of catalyst deactiva-
tion/regeneration have to be performed. Unfortunately, while the
initial activity of mesoporous MCM-41 materials is very high, due
to their large pore size, their structural stability is so low that it is
notoriously insufficient for meeting the high durability required
in the hydrocracking units. Other mesoporous acid alumino-
silicates either with structural ordering (SBA-15, FSM) or with
worm-like mesopores having increased stability have been synthe-
sized or tested, but their performance is yet far from application.
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In order to increase the quality of gasoil for diesel engines,
measured by the cetane number, it is necessary to increase the
initial cetane number of each of the individual gasoil effluents to
the required range between 50 and 70. In general terms, a low
cetane number of a gasoil fraction can be associated to a high
percentage of aromatics in the composition. In particular, the
percentage of aromatics in the light cycle oil stream can be as high
as 60–70%. Therefore, one of the chemical processes that should
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take place during hydrocracking is the conversion of aromatics into
linear alkanes, i.e., the selective opening of naphthenic rings.43–49
Some catalysts have been developed to produce the selective
opening of naphthene rings into linear acyclic hydrocarbons.
Most of them contain noble metals and particularly Ir sup-
ported on large surface area solids. Ir as an active component of
the catalyst has the advantage of a high selectivity for the
naphthene ring opening with a very low tendency to promote
cracking.50 However, Ir has several drawbacks that have to be
solved independently, the two major ones being the low toler-
ance to the presence of sulfur in the feed and the low ability to
promote hydrogenation of aromatics. This last problem can be
solved by performing the conversion of C10+ aromatics into
linear saturated hydrocarbons in two separate stages consisting
in aromatic hydrogenation followed by Ir catalyzed ring opening.
In the context of developing highly efficient catalysts for
selective naphthene ring opening, it has been found that the
presence of acid zeolites can boost the activity of Ir metal. The
reason for this synergy between Ir-catalyzed ring opening and
acid zeolites derives from the ability of acid sites to promote
cycloisomerization of six membered rings into cyclopentyl
rings. This isomerization arises from the fact that cyclopentenyl
ions are among the most stable carbenium ions and acid
zeolites promote the formation of carbenium anions from
saturated hydrocarbons that evolve through spontaneous alkyl
and hydride rearrangements toward the thermodynamically
more stable carbocations. Thus, decaline having two fused C6
rings undergoes in the presence of Ir/Al2O3 ring opening at
275 1C under 3540 kPa with only 4% conversion, while under
the same conditions, perhydroindane having fused C6 and C5
rings and bicyclo(3,3,0)octane having two fused C5 rings are
converted with 68 and 81% conversion, respectively. The combi-
nation of Pt/USY together with Ir/Al2O3 to effect the ring opening
of naphthene exhibits a synergy with respect to the activity of the
separate components, since it can be envisioned that the zeolite
is able to isomerize methyl cyclohexane to a mixture containing
dimethylcyclopentanes and subsequently the Ir/Al2O3 promotes
the opening of the cyclopentane to the acyclic alkane.
In this selective naphthene ring opening process, the struc-
ture of the zeolite host also plays a role. Thus, comparison of
the catalytic activity of Pt supported on three large pore zeolites
including USY, Beta and ITQ-21 at constant selectivity towards
C10 of 85% has shown that ITQ-21 (zeolite with a 3D pore
network containing 1.18 nm-wide cavities, each of which is
accessible through six circular 0.74 nm-wide windows) is the one
that exhibits the best performance reaching a yield of tetralin ring
opening products of about 20%, in comparison with the 17 or 14%
yield that can be achieved for Beta and USY, respectively.
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A further improvement would be to prepare a catalyst in
which Pt promoting aromatic hydrogenation and Ir catalyzing
selective ring opening are supported on the same acid zeolite.
Thus, it has been reported that decalin undergoes transforma-
tion to acyclic decanes with high cetane numbers in high yields
using Pt and Ir supported on Y zeolite. This acid Y zeolite is
obtained by partial proton exchange with alkali metal ions.
Conclusions and future prospects
Modern societies are based on the massive consumption of
fossil fuels to obtain energy for heating, transportation, and
electricity production. Since the reserves of crude oil and
natural gas are still very high, it is clear that the present
situation, in which about 80% of the total energy consumption
in 2013 derives from fossil fuels according to the data issued by
the International Energy Agency (Energy Outlook 2013), will
still continue for the next decades. In the transformation of
the fossil fuels and refining processes, zeolites play a key role
as catalysts. In the present tutorial, we have shown that for
key processes, like paraffin isomerization, isobutane–butene
alkylation, cracking, hydrocracking and reforming, the current
commercial catalysts contain zeolites as the key components
responsible for the catalytic activity, overall selectivity and
stability. Considering the degree of maturity and the enormous
investment in research that has been made in refining, it can
be expected that the future advances in the formulation of
catalysts will be relatively minor and mostly driven by more
stringent legal regulations on the quality of transportation
fuels. Desulfuration and hydrodesulfuration have to be com-
plemented by new catalytic processes to reduce even further the
sulfur content of fuels below the legal limits. Also in trans-
portation fuels, the continued tendency is to reduce the
presence of aromatics, particularly benzene, and alkenes in
their composition. This will require probably some adjust-
ments in the operation conditions of the reactors and minor
modifications in the catalyst formulation to improve the final
product distribution and also new processes to convert these
unwanted unsaturated compounds into suitable mixtures.
Perhaps the major changes, also forced by governmental
regulations, could be the need to combine classical refining
processes with biofuel conversion. In this way, the feed of
certain processes could contain some streams coming from
second or third generation of biodiesel or fractions from
biomass pyrolysis and conversion. Since the quality of the fuel
provided by refineries is very high fulfilling the market require-
ments, the idea is to blend this high quality fuel from refining
with some relatively minor proportion (5–10%) of streams
coming from renewable resources. In the long term, this
tendency of combining fossil and renewable fuels can increase
the proportion of the stream coming from renewables adjusting
their percentage to the target set by economical and political
grounds. Certainly, co-processing of fossil and renewable fuels
would require changes in the nature of the catalyst that
gradually would be evolving in parallel with the composition
Chem. Soc. Rev.

Tutorial Review
of the streams. It can be anticipated that zeolites with higher
pores and hierarchical structure combining micro and meso-
pores will play an increasing role considering the size of
biomass derived molecules.
Acknowledgements
Published on 27 March 2014. Downloaded by University of Southern California on 07/04/2014 07:33:10.
Financial support by the Spanish Ministry of Science and Com-
petitiveness (Severo Ochoa and CTQ2012-32315) and Generalidad
Valenciana (Prometeo 12/013) is gratefully acknowledged.
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