Received: 19 July 2019 Revised: 27 October 2019 Accepted: 31 October 2019

DOI: 10.1002/er.4995

REVIEW PAPER

Alkane isomerization over sulfated zirconia solid acid

system

Pengzhao Wang1 | Yuanyuan Yue1 | Tinghai Wang1 | Xiaojun Bao2

1
National Engineering Research Centre of
Chemical Fertilizer Catalyst, Fuzhou
University, Fuzhou, China
2
State Key Laboratory of Photocatalysis on
Energy & Environment, Fuzhou
University, Fuzhou, China
Correspondence
Xiaojun Bao, State Key Laboratory of
Photocatalysis on Energy & Environment,
Fuzhou Univerisity, Fuzhou 350116,
China.
Email: wangpengzhao@yeah.net;
baoxj@fzu.edu.cn
Funding information
National Natural Science Foundation for
Young Scholars of China, Grant/Award
Number: 21902028
Summary
Sulfated zirconia (SZ) and its modified versions attract great interest in recent
years, because of their promising potential in n‐alkane isomerization. The
oxidative and protonation routes are active and interactional in n‐alkane
activation over SZ catalysts. The bimolecular reaction becomes dominant with
increasing the density of active sites on SZ surface and decreasing the carbon
chain of feed. Pentane and hexane are mainly isomerized by protonated
cyclopropane mechanism, while which is thermodynamically unflavored for
n‐butane isomerization. The deactivation of SZ catalysts is primarily caused
by the loss of superacidity and oxidizing ability, resulted from the structure
changes of sulfate species. Several strategies for improving the activity of SZ
are reviewed. The intrinsic structure‐reactivity relationship of SZ catalysts in
alkane isomerization is updated to illuminate the prerequisite for the highly
active catalysts and the mechanism of active sites formation. The applications
of Pt/SZ in fixed‐bed and unmodified SZ in circulating fluidizing bed in light
alkanes isomerization are compared with the conventional technologies based
on the chlorinated alumina catalysts. Finally, the future study of SZ catalysts is
outlooked from the academic investigations to the industrial applications.

KEYWORDS
activation, alkane isomerization, application prospects, catalyst modification, deactivation, structure‐
reactivity relationship, sulfated zirconia solid acid system

1 | INTRODUCTION Anion‐modified metal oxides have received an everlasting

In recent years, significant changes in gasoline properties,
especially the decreases in alkene and aromatic contents,
lead to a loss of octane number (ON). Changing the gas-
oline blending stocks becomes urgent to maintain the
ON. The environmentally friendly isomerate and alkylate
are the most promising additives for ON upgrading,
which give a renewed interest in catalytic isomerization
of n‐alkanes.1 Extensive researches have been carried
out to obtain a novel n‐alkane isomerization catalyst that
can satisfied the new requirements for both the environ-
mental legislation and the commercial practicability.
Int J Energy Res. 2020;1–25. wileyonlinelibrary.com/journal/er
interest since their birth in 1979 when Hino and Arata
found that they can isomerize n‐butane to isobutane even
at room temperature.2 In particular, the sulfated zirconia
(SZ) catalyst and its modified versions have been the most
promising candidates for being the next generation of
isomerization catalysts. The high catalytic activity, low
reaction temperature, and satisfied reaction and regener-
ation stability of SZ catalysts are all highly desirable
characteristics for their eventual industrial application
in n‐alkane isomerization.
Many efforts have been done to understand the surface
chemistry and high reactivity of SZ catalysts in the past
© 2020 John Wiley & Sons, Ltd. 1
2 WANG
few decades, because of their promising catalytic power
in many fields. In the field of academic science, a number
of studies have attempted to enhance the catalytic activity
and stability of SZ catalysts by developing new prepara-
tion methods and to elucidate the nature of active sites
by investigating the structure of SZ surface. Other impor-
tant research subjects are aimed at the commercial
application of SZ catalysts in n‐alkane isomerization,
including the promotion of SZ‐based catalysts with the
noble metals (Pt, Pd) and/or non‐noble transition metals
(Fe, Mn, Ga, Ni, La, etc). In addition, several researchers
have examined the promotion effect of hydrogen on the
reactivity of n‐alkane isomerization.
There are two review papers about the SZ catalysts and
their catalysis in the 1990s.3,4 Since then, the SZ has been
further extensively investigated, and many research
achievements of SZ in n‐alkane isomerization have been
published. The rapid development of characterization
techniques, especially the in situ optical spectroscopy
techniques, provides convenience for investigating the
catalytic mechanism of SZ‐based catalysts in alkane isom-
erization. For example, the in situ Fourier transform
infrared (FTIR) investigations conducted by several
groups unequivocally confirmed the possibility of oxida-
tive activation of n‐alkane on SZ catalysts.5-8 Addition-
ally, the advanced theoretical calculations give a new
approach to reveal the surface structure and the nature
of active sites.5,9-11 Haase and Sauer found that the most
stable configurations of sulfur species on SZ surface were
tridentate sulfate anions or tridentate SO3 complexes on
the (1 0 1) and (0 1 1) surface of tetragonal zirconia.9
The combined application of these advanced characteri-
zation techniques and theoretical calculations gives many
new slights into the structure‐activity correlation about
SZ in n‐alkane isomerization.
An overview made by Reddy and Patil in 2009 focused
on the SZ‐catalyzed organic syntheses and transforma-
tions reactions, while the n‐alkane isomerization did not
been reviewed.12 That is, there is no a special review
made on the catalysis and applications of SZ catalyst
and its modified versions in alkane isomerization. Such
a review paper is necessary because the great progress
has been made on the explanations of chemical complex-
ity of SZ catalysts and on their promising prospects in n‐
alkane isomerization. In this article, we will review the
proposed mechanisms for n‐alkane isomerization reac-
tion, deactivation, and regeneration over SZ catalysts
and show several strategies for improving the isomeriza-
tion activity. By summarizing and analyzing the prerequi-
sites for the formation of highly active isomerization SZ
catalysts, the intrinsic structure‐reactivity corrections are
presented. Then, the recent progress in the application
of SZ catalysts in n‐alkane isomerization is presented
ET AL.
and several isomerization technologies based on the SZ
catalysts are compared. Finally, several research pros-
pects are pointed out.
2 | WHY SULFATED ZIRCONIA?
The most prevalent alkane isomerization catalyst is
Pt‐promoted chlorinated alumina (Pt/Cl‐Al2O3), which
is employed in several well‐established isomerization
technologies, such as Penex (C5/C6) and Butamer (C4)
processed by UOP, BP/PSA processed by BP,
ABBLUMMUS isomerization processed by LUMMUS,
and Ipsorb processed by IFP. In the last few decades,
the Pt/Cl‐Al2O3 catalysts is extensively used because of
its high activity, isomerate selectivity, and long life. In
the course of hydroisomerization reaction, however, chlo-
rine on Pt/Cl‐Al2O3 surface lost as the form of HCl. The
fatal drawback of Pt/Cl‐Al2O3 catalyst is the requirement
for continuous addition of chloride to maintain its suffi-
cient acidity and isomerization activity. The loss of chlo-
rides brings about serious corrosion problems and
environmental pollution. An alkaline scrubber is needed
to neutralize acidic HCl in the products. In addition,
Pt/Cl‐Al2O3 catalyst requires feed and make‐up gas driers
for moisture removal to ensure long catalyst life. There-
fore, there is a great incentive to develop a new environ-
mentally friendly catalyst for n‐alkane isomerization to
boost the isomerate production.
The proposed catalyst systems for n‐alkane isomeriza-
tion include the SZ, heteropolyacids, and zeolites in the
literature. The heteropolyacid catalysts, however, suffer
from the difficulties in preparation, regeneration, and
low thermal stability. The zeolite catalyst requires a
higher reaction temperature to get a higher turnover rate
of n‐alkane, while the higher reaction temperature leads
to a low equilibrium conversion of n‐alkane and a low
selectivity to the corresponding isomerate (see Figure 1).
As a slightly exothermic reaction, the isomerization of
n‐alkanes is favored by low reaction temperature in
thermodynamics.13
Those catalysts are active within the reaction temper-
ature ranging from 100°C to 200°C are considered to be
the most applicable for C4‐C6 isomerization.14 From this
point, the zeolite catalysts are thermodynamically less
favorable in n‐alkane isomerization despite that there
are many attempts made on them. The zeolite catalysts
must be operated at a higher temperature, typically
200°C to 300°C because of their weaker acidity compared
with the Cl‐Al2O3 and SZ catalysts.15-22 In conclusion,
the SZ‐based catalysts not only have a satisfied catalytic
performance in n‐alkane isomerization compared with
the Pt/Cl‐Al2O3 catalysts but also have no problem with
WANG ET AL.
FIGURE 1 Equilibrium conversions of C4‐C6 n‐alkane to iso‐
alkanes. Reprinted with permission from Urzhuntsev et al14
[Colour figure can be viewed at wileyonlinelibrary.com]
the loss of active components. Admittedly, the SZ cata-
lyst shows high isomerization activity even without the
promotion of noble metal, despite of the lower catalytic
stability. In this article, we discuss the intrinsic
structure‐reactivity relationships of unpromoted SZ cata-
lysts firstly, and then, the roles of promotion with several
metals are reviewed.
3 | ACTIVATION OF ALKANE OVER
SULFATED ZIRCONIA
3.1 | Development history of activation
pathway
Although no a general consensus on the structure of SZ
has not been reached, it has been well accepted that
acidic Zr─OH groups and oxidizing SO42− species were
active sites in alkane isomerization reaction. Table 1 lists
several surface models of SZ proposed in literatures.
Activation of reactant molecules is the first and crucial
step in the catalytic conversion of alkanes on solid cata-
lyst surface.34 It is well reported that the carbenium
ions are essential reaction intermediates in alkane isom-
erization over SZ catalysts, the mechanism of their forma-
tion, as well as the alkane activation have not been
addressed yet. The possible ways for carbenium forma-
tion include protolysis of C─H bonds or C─C bonds by
Brønsted sites, hydride abstraction by Lewis sites, oxida-
tion of a C─H bond, and protonation of trace amounts
of olefins in the feed.35
Initially, the SZ catalyst was considered to be
superacidic.2 In the pioneering work reported by Hino
et al, the acid strength of SZ was measured to be pKa =
14.52 by Hammett indicator, which was much stronger
3
than that of the pure sulfuric acid.2 Later, Cheung et al
claimed that SZ was more acidic than USY zeolite
because it was more effective in alkane protonation.36-38
The measurements of adsorption heat of argon and
ammonia also demonstrated that the acid sites on SZ sur-
face were stronger than these on zeolites (HY, HZSM‐5,
and H‐MOR).39-42 From this rationale, it is suggested that
the carbenium ions are generated by (a) protonation of
alkanes on the superacidic Brønsted sites and subsequent
elimination of H2 or (b) hydride abstraction from satu-
rated alkanes over the Lewis superacidic sites.23
Lately, our density functional theory (DFT) calcula-
tions showed that the deprotonation energies (DPE)
values of Zr─OH on the SZ surface were depended on
their surrounding geometry and hydration degree.8 The
DPE values for terminal and bridging Zr─OH groups on
a highly dehydrated SZ surface were 1087 and 1206
kJ/mol, which is well in correspondence with the values
estimated by lglesia et al (1110‐1165 kJ/mol).43-47 The
reported DPE values of hydroxyl on zeolite surface
(1170‐1200 kJ/mol) are higher than that of bridging
Zr─OH groups, which confirms the presence of
superacidic Brønsted sites.46,48,49
The proposal of above protonation activation pathway
is derived from the superacidity of SZ catalyst. However,
several groups have questioned the superacidity of
SZ‐based catalysts because of the unreliable measurement
of Hammett acidity functions for solid.50 Generally, the
alkali is used as probe molecules to characterize acid
properties of solid catalysts. Nuclear magnetic resonance
(NMR), ultraviolet–visible (UV‐vis), and infrared (IR)
studies showed that after adsorbing base molecules, the
chemical shift of hydroxyl group on SZ was smaller than
that on the alkali molecules‐adsorbed zeolite samples,
indicating the lower acid strength of SZ catalysts com-
pared with zeolites.27,51-53 It is well accepted that the
superacidic Brønsted sites are active sites for alkane
activation over zeolites by involving a penta‐coordinated
carbonium ion as a transition state, which needs to
overcome high energy barrier.54-57 However, the zeolite‐
catalyzed alkane isomerization reaction generally
requires much higher reaction temperature compared
with the reaction on the SZ.58,59 Therefore, the proton-
ation activation of alkanes on SZ catalysts at low reaction
temperature has been challenged. At the same time,
many researchers observed that SZ catalysts showed very
low isomerization activity when removing all alkene
impurities from the raw. In contrast, the isomerization
activity significantly increases by adding a small amount
of alkene into the feed.60-64 This promoting effect of non-
specific olefins addition indicated that the alkene may be
one of the intermediates in alkane isomerization because
of its higher reactivity to form carbenium ion species than
4 WANG
TABLE 1 Sulfated zirconia surface models proposed in previous literature
Authors Surface Model
Yamaguchi24
Arata and Hino26
Bensitel et al28
Riemer et al30
White et al32
Note. Reproduced with permission from Li et al23
alkane.65 Nevertheless, SZ‐based material still exhibited
isomerization activity after removing all alkenes in the
raw,23,66-69 implying the in situ generation of olefins on
the SZ surface. At this point, the alternative oxidative
dehydrogenation (ODH) activation of alkane on SZ sur-
face was proposed and evidenced.
The ODH of butane by sulfate species produces
butene, water, and sulfur compounds with low valence.
In the excellent work of Li et al,5 they found that butene
was generated from n‐butane adsorbed on SZ catalysts at
low temperature by in situ temperature‐programmed
desorption mass spectrometry (TPD‐MS) measurements.
Thermal desorption and alkali washing of used SZ cata-
lysts evidenced the reduction of sulfated species under
the reaction conditions. They suggested that the increase
in the alkene concentration on the catalyst surface
enhanced the isomerization rate but accelerated deactiva-
tion of catalyst via formation of oligomers. Further DFT
calculations also showed that the sulfur compounds at
high valence state (mostly presented as pyrosulfate or
ET AL.
Authors Surface Model
Kustov et al25
Adeeva et al27
Clearfield et al29
Morterra et al31
Babou et al33
adsorb as SO3 species) had high oxidizing ability and
favored for the ODH of butane to butene by SZ.5 As
shown in Figure 2, the reaction of a [S2O72−, H2O, 2H+]
with a n‐butane molecule yields a [SO42−, SO2, 2H2O,
2H+] structure and a butene molecule, which is thermo-
dynamically favored (reaction energy = −10 kJ/mol).
Later, Klose et al also confirmed the formation and
adsorption of water under isomerization reaction condi-
tions by in situ IR investigations.70 Interestingly, they
found that the isomerization rate was in direct proportion
to the amount of water accumulated on the surface,6
which further confirmed the oxidative activation of
alkane by sulfate species.
Although the oxidative activation pathway can well
explain the formation of carbenium ions in alkane isomer-
ization over SZ catalyst, there are several questions still
under debate. One is that expect for the n‐alkane isomeri-
zation, the SZ also has high activity in many other types
of acid‐catalyzed reactions, such as cracking of cumene,71
esterification of long‐chain–free fatty acids,72,73 arylation
WANG ET AL.
FIGURE 2 Structure of [S2O72−, H2O,
2H ] and [SO42−, SO2, 2H2O, 2H+].
+
Reprinted with permission from Li et al5
of oleic acid with aromatics,74 dehydration of fructose,75
transesterification,76 synthesis of ethyl levulinate from
furfuryl alcohol,77 alkylation,78,79 oligomerization of
hydrocarbons,80 and so on.81-83 Most of reactants for these
reactions must be activated by protonation route on
superacid sites. Another question lies in the fast deactiva-
tion of SZ catalysts in alkane isomerization, while only a
very small amount of sulfate species are reduced. In addi-
tion, the in situ NH3‐TPD‐FTIR investigation by Katada
et al showed that the ammonia adsorbed on the SZ surface
cannot be fully desorbed even at 550°C under vacuum,84
which was higher than the temperature range for the
desorption of NH3 adsorbed on superacid sites of zeolites.85
Thus, one can conclude that the strong interaction
occurred between SZ surface and ammonia molecules.
5
To resolve above questions, we investigated the influ-
ence of the strong interaction between SZ surface and
several probe molecules with different alkalinity on the
surface chemistry and isomerization activity by in situ
FTIR.7 It was shown that the adsorption and desorption
of water were reversible on the surface of hydrated SZ
catalysts. However, the situation became complex for
the base‐adsorbed SZ samples. The adsorption of ammo-
nia resulted in that the band of S═O bonds shifted to
low frequency, concurrent with the drastic decrease of
band intensity of Zr─OH groups. While the desorption
of ammonia at 550°C cannot recovery surface properties
of SZ catalysts. The same phenomenon was also observed
in pyridine‐adsorbed SZ catalyst by Babou et al,33 indicat-
ing that an irreversible loss and/or occupation of acid
6 WANG
sites occurred during NH3 ad/desorption. Interestingly,
our latest NH3‐TPD‐MS experiments showed that the
desorption of ammonia was accomplished below 500°C
on SZ catalyst, well agreement with the desorption behav-
ior occurred on zeolites. However, the remaining strong
adsorbed NH3 was reduced to N2 by sulfate species at
500°C to 700°C (Figure 3), which was inconsistent with
the conventional assignment for the NH3‐TPD peak at
500°C to 700°C to strong acid sites.86-88 Combined with
the DPE values mentioned above, we suggested that the
oxidative and protonation activation pathways were both
effective in alkane isomerization over SZ‐based catalysts.
3.2 | Instinct relationship between
oxidizing ability and superacidity of SZ
catalyst
The oxidative and protonation activation of alkane are
attributed to the strong oxidizing ability and superacidity
respectively, and both of them are derived from the
strong interaction of sulfate species with tetragonal zirco-
nia surface. Li et al found that 40% of the sulfate species
can be readily removed from the surface by water
washing, resulting in the loss of isomerization activity of
catalyst.23 They suggested that these labile soluble sulfate
species were presented as highly covalent state and were
able to convert butane to butene via ODH route at
low temperature.67 Importantly, the strong electron‐
withdrawing effect of highly covalent S═O bonds
weakens the strength of O─H bonds in the adjacent
FIGURE 3 Desorption peaks of NH3 (m/e = 17) and N2 (m/e =
28) during temperature‐programmed desorption (TPD) process of
SZA catalyst after adsorption of NH3 at 323 K. Reprinted with
permission from Wang et al89 [Colour figure can be viewed at
wileyonlinelibrary.com]
ET AL.
Zr─OH groups and gives the superacidity of bridging
Zr─OH groups.90
The SZ surface shows strong affinity with probe mole-
cules, such as water,8 pyridine,23,33 CO,53 CO2,23 and
ammonia.7,84 Unfortunately, the adsorption of above mol-
ecules results in the decrease of isomerization activity
depending on the adsorption strength.7,91-93 From the lit-
erature, this negative effect is ascribed to the decrease in
the oxidizing ability and superacidity of SZ catalyst
because of the changes in the nature of surface properties
(Figure 4). Chiefly, it is easily understood that the adsorp-
tion of above molecules causes the superacid sites to be
poisoned since the strong adsorbed molecules cannot be
completely desorbed at reaction conditions. More impor-
tantly, the adsorption of above molecules all results in a
decrease in the covalency degree of neighboring S═O
bonds, since it is observed that the FTIR band of S═O
bonds (approximately 1390 cm−1) significantly shifted to
the low frequency.6-8,23,84,94 This indicates the decrease
in electron‐withdrawing and polarization ability of sulfate
species on O─H bonds in adjacent Zr─OH groups,
resulting in the decrease of acid strength. Namely, the
oxidizing ability and superacidity are interacted. As for
n‐butane isomerization, the oxidative and superacidic
sites are both active at the beginning of the reaction.
However, the ODH activation route produces water,
butene, and sulfite species, all of which plays detrimental
effects on the oxidizing ability and superacidity of SZ cat-
alysts. It is worth pointing out that the divergence in the
superacidity of SZ by different researchers, which was
mentioned before, can be explained by considering that
the adsorption‐induced chemical shifts of the hydroxyl
groups in NMR, UV‐vis, and IR after adsorption of above
probe molecules are unreliable for SZ because of its com-
plex surface chemistry.
4 | R E A C TI O N A N D
DEACTIVATION MECHANISM O F SZ
CATALYSTS I N n‐ A L K A N E
IS OM ERIZATION
4.1 | Reaction mechanism
It is generally accepted that the alkane isomerization fol-
lows a carbenium ion reaction mechanism. Specifically,
once an active carbenium intermediate, acting as chain
carrier, is formed, the isomerization proceeds in cycles,
including conversion of n‐alkanes to corresponding iso-
mers and generation of new intermediates.67 The chain
propagation has been the subject of many researches; in
consequence, several different reaction mechanisms have
WANG ET AL.
FIGURE 4 Schematic diagram of the relationship between ad/desorption of probe molecules and the nature of active sites on the sulfated
zirconia surface (arrows with solid line and “+” represent a positive effect, while dotted line and “–” represent a negative effect). Copied with
permission from Wang et al7
been proposed over a long period, and there is no general
consensus has been reached.95
4.1.1 | Monomolecular and/or bimolecu-
lar reaction?
The isomerization cycles are proceeded in two steps: (a)
carbon‐skeleton rearrangement of linear carbenium ions
to isomerized ones followed by (b) hydride transfer
between n‐alkane molecules and the isomerized
carbenium ions to produce the isoalkane and new
carbenium ions.68 The former step proceeds by either
monomolecular or bimolecular pathway, both of which
have been vividly discussed and supported by their own
experimental and calculation evidences in the literature.
In this review, we only focus on the new findings
reported in recent years. Difference between two
isomerization pathways lies in whether the dimeric
intermediates are formed. The monomolecular reaction
characterizes the extremely high selectivity to the corre-
sponding isomers and high energetic barrier. However,
the disproportionation products are formed from dimeric
intermediates in the bimolecular reaction, which is more
thermodynamically favored.
In the monomolecular isomerization pathway, a sec-
ondary carbenium ion is intramolecularly isomerized to
a tertiary carbenium ion that desorbs via hydride transfer
from a n‐alkane molecule.96,97 The bimolecular reaction,
however, involves an intermolecular alkylation of a sec-
ondary carbenium ion with another alkene molecule to
form a oligomeric carbenium ion, which is then skeletal
isomerized and β‐cleaved to generate an isomerized
carbenium ion and a smaller alkene molecule.58,89 It is
worth noting that the hydride transfer reaction in mono-
molecular pathway also involves two C4 moieties,
namely, tertiary carbenium ion and incoming n‐butane
molecule. Therefore, Li et al proposed that both of
7
monomolecular and bimolecular routes belong to bimo-
lecular reaction with two different pathways in a strict
sense.68
The contribution of the two reaction pathways is
strongly related to the reactants and reaction conditions.
The kinetics and isotope labeling experiments conducted
by Wulfers and Jentoft showed that the concentration of
alkenes on the catalysts bed had a strong influence on
the reaction pathways of alkane isomerization on solid
acid catalysts.58 In effect, the monomolecular reaction,
which is kinetically unfavored compared with dimeriza-
tion reaction, is dominant at low alkene concentration.
In contrary, the high alkene concentration favors nonse-
lective bimolecular pathway. Consequently, the olefin
content in the feed63 and/or the activation rate of
n‐alkane98 significantly affect the isomerization pathway.
Moreover, many researchers claimed that the skeletal
isomerization of alkanes with five or more carbon
atoms mainly occurred via a monomolecular pathway
with high isomerization selectivity over zeolite cata-
lysts.99-103 However, Essayem et al obtained only 21.6%
of isopentane selectivity on the SZ at 150°C, which
increased to 41.7% at 200°C, indicating a prevalence of
bimolecular pathway.101 The increased contribution of
monomolecular reaction with increasing temperature
was also reported by Suzuki and Okuhara,98 which can
be well explained by the thermodynamically disadvan-
tage of monomolecular pathway.
4.1.2 | Protonated cyclopropane mecha-
nism or not?
It is well reported that the monomolecular skeletal
isomerization of secondary carbenium ion proceeds via
a protonated cyclopropane mechanism according to the
minimum on the potential energy surface in n‐pentane
and n‐hexane isomerization (see Figure 5).101,102,104-106
However, as shown in Figure 5, this transition state is
8 WANG
FIGURE 5 Schematic representation of possible pathways for monomolecular isomerization of n‐butane. Copied with permission from
Boronat et al105
thermodynamically unfavorable in n‐butane isomeriza-
tion because that the primary isobutyl carbenium ion
(E) is approximately 86 kJ/mol less stable than a sec‐butyl
one (A).105 The protonated methylcyclopropane ring (D)
is directly converted to the energetically infeasible
sec‐butyl cation (A′), rather than the primary isobutyl
carbenium ion (E). This is also supported by the finding
of Luzgin et al that 1‐13C‐butane was easily scrambled
to 2‐13C‐butane using in situ 13C MAS NMR and ex
situ gas chromatography–mass spectrometry (GC‐MS)
investigations.107
Although the protonated cyclopropane pathway is
energetically unfavorable, the high selectivity to isobu-
tane in n‐butane isomerization over SZ catalysts implies
there is other alternative way for monomolecular reac-
tion.63 Two possible explanations appeared for this in
the literature. As shown in Figure 5, Boronat et al pro-
posed that the secondary n‐butyl carbenium ion (A) was
directly transformed into tertiary isobutyl cation (F)
through a primary isobutyl cation (E) transition state by
overcoming an activation energy of 86 kJ/mol, which
was well agreement with the experimental values.105
This high activation energy explained the reason for the
much lower turnover rate of n‐butane isomerization
compared with that of alkanes with five or more carbon
atoms. Another explanation proposed by Lohitharn et al
involved the concept that the bimolecular reaction
was performed with underlying characteristics of
monomolecular pathway.63 In this dual‐nature mecha-
nism (see Figure 6), the C8+ intermediates was formed
through the classical bimolecular pathway as described
before. Differently, they suggested that the isomerization
of C8+ cation occurred through the protonated cyclopro-
pane mechanism, giving rise to an isomerized C8+ pri-
mary carbenium, which was similar to the assumption
ET AL.
in the monomolecular mechanism. Subsequently, the
C8+ primary cation rapidly cracked into primary isobutyl
cation and butene through β‐scission. In short, this dual‐
nature mechanism claimed that the C8+ intermediates
were favored to generate primary isobutyl cation and
butene in energetics, rather than random cracking, giving
rise to a higher selectivity to isobutane.
4.2 | Deactivation and regeneration
mechanism
Although having high activity for n‐alkane isomerization,
the SZ catalyst suffers from fast deactivation. Many stud-
ies have focused on the deactivation mechanism of SZ in
n‐alkane isomerization, and different deactivation causes
have been reported: (a) coverage of active sites by coke
and oligomer deposition,27,66,108-111 (b) removal of surface
sulfur as H2S under reaction conditions, 112 (c) migration
of active sulfur species from the catalyst surface into the
bulk zirconia,3,113 (d) decrease in the amount and
strength of acid sites,7,114 (e) crystal transformation of
active tetragonal ZrO2 into inactive monoclinic phase,115
and (g) reduction of the high valence state sulfur to a
lower oxidation state.116-118 Our recent study has ruled
out the possibilities of the changes in textual properties
and zirconia crystallization; that is, the SZ deactivation
is caused by a chemical change in the nature of active
sites.116 It is worth pointing out that the deactivation of
SZ catalysts is not usually resulted from a single reason,
but it is a consequence of various factors depending on
the reaction conditions. For example, Song et al ascribed
the catalyst deactivation to a combination of carbon depo-
sition, loss of the Brønsted acidity, and removal of active
sulfur species.114
WANG ET AL.
FIGURE 6 The proposed dual‐nature
mechanism of n‐butane isomerization
over sulfated zirconia (SZ) catalysts.
Reproduced with permission from
Lohitharn et al63
The chain carriers are not consumed in the reaction
cycles, but the chain termination is unavoidable, espe-
cially the coke deposits from olefinic species and
carbenium ions on the acid sites. Hence, many
researchers claimed that the coke deposition primarily
causes for SZ deactivation.27,66,109-111 However, several
studies showed that only a very small amount of coke
deposits on the SZ surface,111,116,119 which was much less
than the coke formed during zeolite‐catalyzed isomeriza-
tion reaction.117 Thus, two different explanations have
been emerged. Some researchers claimed that only a
few amounts of acid sites on the SZ surface were active
for n‐alkane isomerization. Unfortunately, these sites
were readily covered by coke species,119,120 since the coke
were generally generated on the highly active sites. How-
ever, no direct evidences have been given for this. With
the verification of ODH activation route of n‐alkane, it
was proposed that the SZ deactivation was related to the
reduction of its oxidizing ability, especially when there
was no alkene contained in the feed by considering that
the reduction of sulfate species via ODH of n‐alkane
was stoichiometric, rather than catalytic.5,116
From the prospect of reaction mechanism, the deacti-
vation of SZ can be classified to two cases. One is the sup-
pression of the n‐alkane activation to form carbenium
9
intermediates, and the other is the reduction of the trans-
formation rate of sec‐carbenium to tert‐carbenium ions. It
was claimed that once the reducible sulfate species was
used up, the SZ catalysts became inactive.5 This explana-
tion was well supported by the influence of hydrogen and
oxygen on the isomerization activity. As a hydride donor,
the introduction of hydrogen inhibits the ODH activation
rate via pathways that are variants of hydride transfer.
Thus, the presence of hydrogen decreases the isomeriza-
tion activity but enhances the catalytic stability. In
contrast, the introduction of oxygen facilitates the
reoxidization of sulfite species and the production of
alkenes, resulting in an enhanced activity and an acceler-
ated deactivation.5 Further investigations by our group
suggested that the ODH of n‐butane was in reaction equi-
librium, which played a decisive role in catalytic activity.
The rate law derived from this mechanism (see Scheme 1)
indicates that the overall reaction rates are proportional
to the number of the acid sites and the reducible sites
and the partial pressure of n‐butane, while the introduc-
tion of H2 and the generation of water and sulfite species
via ODH decrease the overall conversion rate.116
n‐C4 H10 þ SO2‐
4 ⇄ k−1 n‐C4 H8 þ SO3 þ H2 O
k1 2‐
(1)
10 WANG ET AL.

SCHEME 1 Proposed reaction

mechanism of n‐butane isomerization on
sulfated zirconia–alumina (SZA) catalyst
and the derived rate law for n‐butane
isomerization. Reproduced with
permission from Wang et al116

from the surface, and the reoxidation of sulfite species to

n‐C4 H8 þ Z‐ Hþ ⇄ kk2−2 n‐C4 H9 ⋅Z (2) sulfated species.89,110,116,121 However, it was found that
the catalytic activity was almost lost when the used SZ
k3 catalysts were regenerated in nitrogen at 500°
n‐C4 H9 ⋅Z ! i‐C4 H9 ⋅Z (3)
C.116,119,122 Our further study showed that the treatment
temperature of nitrogen strongly affected the activity.
i‐C4 H9 ⋅Z þ n‐C4 H10 ⇄ kk4−4 n‐C4 H9 ⋅Z þ i‐C4 H10 (4) Specifically, the activity was restored to some extent after
treatment at 200°C to 300°C, dramatically decreased at
k5 300°C to 500°C, while interestingly, it was sharply
n‐C4 H8 þ H2 ! n‐C4 H10 (5) increased at the range of 500°C to 700°C (see Figure 7).
At 200°C to 300°C, only some of the adsorbed water
 
k 1 k2 k3 CT Pn−C4H10 SO2− desorbed from the surface, the superacidity, and oxidiz-
r¼   4


ðk−2 þ k 3 Þ k −1 SO2− ing ability were partially recovered. While at 300 to
3 ½H2 O þ k 5 P H2

Therefore, the water, hydrocarbon, and sulfite species

generated from ODH were all adsorbed on the SZ catalyst
surface, which further limited the further production of
alkenes and led to the SZ catalysts deactivation. To
explain the reason for the fast deactivation rate at the
beginning of the n‐alkane isomerization reaction, we
examined the changes of superacidity and oxidizing abil-
ity of SZ catalyst during the reaction.7 It was showed that
the desorption of water and sulfite species not only led to
the decrease in the oxidizing ability of sulfated species but
also weakened the electron‐withdrawing ability of the
sulfated species, which in turn resulted in a decrease in
acid strength of SZ catalyst. Thus, the rates of chain initi-
ation and propagation both become lower, giving rise to
the initial fast deactivation. FIGURE 7 n‐Butane isomerization activity over fresh and
The deactivated SZ catalysts can be completely regen- regenerated alumina‐promoted sulfated zirconia (SZ) catalysts in
erated in air at a high temperature, under which condi- nitrogen at different temperatures: (●) the initial and 1 hour of
tions, the superacidity and oxidizing ability of SZ reaction activity over fresh catalysts at 200°C; (■) the initial activity
catalysts, were completely recovered, involving in the after regeneration in N2. Reproduced with permission from Wang
oxidation of coke deposition to CO2, the water desorption et al116 [Colour figure can be viewed at wileyonlinelibrary.com]
WANG ET AL.
500°C, the carbon deposits were removed via a redox
reaction between sulfate and carbon deposition without
the desorption of sulfite species, resulting in the structure
destruction of active sites. Further increasing tempera-
ture, the adsorbed water, carbon species, and sulfite spe-
cies were all removed, and the remaining sulfate species
with high valence state reconstructed the superacidity
and oxidizing ability of SZ catalyst, leading to an increase
in isomerization activity, despite that it was somewhat
lower than the activity on the fresh catalyst. Hence,
one must be careful in the regeneration process to
recover the original activity.
5 | S T R A T E G I E S FO R I M P R O VI N G
n‐ALKANE ISOMERIZATION
ACTIVITY OVER SZ CATALYSTS
5.1 | Role of hydrogen in isomerization
behavior
Since the SZ catalysts are facing an inconvenient truth of
low catalytic stability in n‐alkane isomerization, two
effective strategies are proposed to slow the deactivation
rate. The first way is carrying out the isomerization reac-
tion in the presence of hydrogen. Several researchers
have observed that the presence of H2 decreased not only
the deactivation rate but also the initial turnover rate of
n‐alkane in isomerization reaction over non‐noble
metal‐modified SZ catalysts regardless of carbon chain
length of alkane.101,116,123,124 The presence of H2 facili-
tates the hydrogenation saturation of unsaturated inter-
mediates, which in turn decreases the concentration of
unsaturated species. Several works of n‐butane isomeriza-
tion under various reaction conditions with different
deactivation rates are listed in Table 2. It can be con-
cluded that the carrier gas indeed plays a key role in the
deactivation rate of SZ catalysts despite the differences
in other conditions. Namely, compared with the chemical
TABLE 2 Comparison of deactivation rate of SZ and Al‐SZ catalysts in n‐butane isomerization under different reaction conditions
Catalyst Butane Purity, % Temperature, °C
Al‐SZ >99.99 200
SZ Unknown 200
SZ 99.5 150
Al‐SZ Unknown 250
SZ 99.5 150
Determined on the assumption that the deactivation rate is first order with respect to the rate of isomerization, ie, −drisomerization/dt = kdeactivationrisomerization.
a
11
inert nitrogen and helium, the hydrogen is active species
in n‐alkane isomerization rather than only diluent gas.
Both of the experimental and calculation results sug-
gest that the molecular hydrogen generally functions as
a hydrogenation agent. The FTIR investigations by
Kondo et al proved that H2 can interact with
coordinatively unsaturated Zr4+ ions and heterolytically
dissociated on the ZrO2 surface at room tempera-
ture.126,127 Later, Manoilova et al observed an IR adsorp-
tion band at 4050 cm−1 on H2 adsorbed SZ catalyst
(Figure 8), which was assigned to the hydrogen adsorbed
on Lewis acid sites.128 In comparision with the gas‐phase
frequency of the Raman‐active stretching vibration of
H─H bond (4163 cm −1), interaction with coordinatively
unsaturated metal cations resulted in a 113 cm−1
bathochromic shift, implying the electron donation
toward acid sites wekens the H─H bond, which was well
consistent with the finding of Klose et al.129
As shown in Figure 9, Hong et al proposed a reaction
pathway for isobutene hydrogenation over SZ cluster.130
As they suggested, the dissociation of hydrogen
performed via a transition state in which a H─H bond
interacts with the Zr─O sites, forming an O─H bond and
a Zr─H bond over the SZ cluster. They also reported that
the dissociative adsorption of hydrogen can occur over
the S═O sites in the sulfate groups, however, which
requires a higher activation energy compared with that
over Zr─O sites. This is also confirmed by the latest find-
ings of Tosoni and Pacchioni that the heterolytic dissocia-
tion of H2 can occur on the (1 0 1) surface of zirconia,
which led to the formation of a hydride bound to a Zr4+
center and a proton bound to an O2− ion.131
5.2 | Role of different promoters in n‐
alkane isomerization
To improve the catalytic performance of monofunctional
acidic SZ catalysts, many studies have focused on the
metal‐promoted bifunctional catalysts.
Butane/Carrier Deactivation
Carrier Gas WHSV, h Gas in Molar Ratea, h Ref.
H2 1.19 1/1.67 0.024 Wang et al116
N2 1.55 1/9 1.2 Li and Gonzalez110
He 2.1 1/9 0.6 Yaluris et al91
H2 0.62 1/10 0.026 Yang et al125
He 2.0 1/9 1.2 Fogash et al108
12
FIGURE 8 Fourier transform infrared (FTIR) spectra of
hydrogen adsorbed on the sulfated zirconia catalyst at 77 K. The
lower line is the blank spectrum of the sample after pretreatment
for 2 hours at 673 K. For clarity, spectra are offset on the vertical
scale. Reprinted with permission from Manoilova et al128
5.2.1 | Role of alumina addition
The main role of Al is to retard the crystal phase transfor-
mation of ZrO2 from tetragonal to monoclinic
phase132,133, since only tetragonal zirconia‐based catalysts
is active in alkane isomerization reaction 53,134-136
Alumina is introduced into SZ by a co‐precipitation
method of zirconium and aluminum sources in all cases.
In addition, it is reported that the addition of alumina
increases the number of acid sites.132,137 Kim et al sug-
gested that introduction of Al increases the concentration
of intermediates on the catalyst surface.138 All these
WANG ET AL.
effects can be ascribed to the stabilized tetragonal zirco-
nia, since it was well accepted that the oxygen vacancies
on the tetragonal zirconia surface can stabilize the sulfate
species.29,139 In summary, as one of the simplest methods
to prepare a pure tetragonal ZrO2‐based catalyst, Al is a
physical structure promoter in SZ catalyst to stabilize
the tetragonal zirconia phase.
The same promotion effect is also found in Hf‐ and Ga‐
modified SZ catalysts with co‐precipitation method.135,140
Ahmed ascribed the enhancement in isomerization activ-
ity of SZ catalysts with introduction of hafnia to an
increase in sulfate density, stabilization of tetragonal
zirconia, and increases in the strength and amount of
Brønsted acid sites (Figure 10).135 Hwang and Mou found
that the activity of Ga‐promoted catalyst was higher
than that of Al‐promoted catalysts, contributed by the
improvement of redox properties on the Ga‐promoted
SZ surface.140
5.2.2 | Promotion effect of non‐noble
transition metal
From the point of commercial application, it is important
to understand whether the addition of non‐noble transi-
tion metal is effective in promoting the catalytic perfor-
mance of SZ in the n‐alkane isomerization. Many
researches have shown that the addition of non‐noble
transition metal can improve the isomerization activity
of SZ catalysts. The promoters commonly used include
iron, manganese, molybdenum, nickel, lanthanum and
so on. In general, Lange et al found that the promoting
effect of transition metals increased as following order:
Mn > Fe > Co > Ni > Zn.141
Fe and Mn promotion
Hsu et al firstly observed that the iron‐manganese doped
SZ was about three orders in magnitude more active than
FIGURE 9 Energy profile of a possible
reaction pathway for hydrogen
dissociation and isobutene hydrogenation
over the sulfated zirconia cluster.
Reprinted with permission from Hong
et al130
WANG ET AL.
FIGURE 10 The variation of the (A) initial catalytic activity, (B)
amount of Brønsted acid sites, and (C) the strength of Brønsted acid
sites as a function of HfO2 loading. The n450 and n150 represent the
amount of Brønsted acid sites determined by Py‐FTIR after pyridine
desorption at 150°C and 450°C. Reproduced with permission from
Ahmed.135 FTIR, Fourier transform infrared [Colour figure can be
viewed at wileyonlinelibrary.com]
the unmodified SZ for n‐butane isomerization, and they
ascribed this promoting effect to an enhancement of the
acid strength.142 However, the approach for detecting
the superacidity (temperature‐programmed desorption
of substituted benzenes) used by Hsu et al were proven
misleading later.27,143,144 By diffuse reflectance IR investi-
gations, Klose et al. claimed that the addition of pro-
moters (Mn and Fe) caused a slight decrease in the
strength of Lewis acid sites and had no effect on the
Brønsted acid strength for SZ,129 indicating that this pro-
motion effect must be caused by an another functionality.
Subsequent studies ascribed the promoting effect of Fe
and Mn additions to the enhancements in the formation
and stabilization of reaction intermediates (carbenium
ion and/or alkene) on the SZ surface, in spite of different
proposals for promotion mechanism. Sayari et al123
observed an induction period and found that hydrogen
had no effect on the reaction activity over Fe‐Mn/SZ cat-
alyst in n‐butane isomerization, much different with the
behavior of unmodified SZ catalyst. They attributed this
difference to the fact that the addition of Fe and Mn not
only facilitated the formation and accumulation of
hydrogen‐deficient intermediates but also enhanced their
stability on the catalyst surface.123 Morterra et al observed
that partial of Fe3+ was transformed into a reducible
form during isomerization reaction, from which they
13
concluded that the introduced Fe and Mn acted as redox
triggers in acid‐catalyzed isomerization process.145 Based
on this supposition, many researchers pointed toward a
promoted oxidative ability of SZ catalysts with the addi-
tion of Fe and Mn116,129,146,147 At this point, the role of
Fe and Mn can be easily understood by considering the
oxidative activation of n‐alkane over SZ catalysts as
discussed in Section 3.1. That is, the addition of Fe and
Mn enhanced the oxidation potential of sulfate species
and facilitated ODH activation route, instead of the
increase in the acidity.129 In addition, the X‐ray photo-
electron spectroscopy (XPS) investigations by Garcı́a
et al showed that the addition of Mn dispersed the iron
on the surface.148 In this way, more Fe3+ species were
available to act as oxidative agents in n‐alkane activation.
However, it is worth noting that although the isomeriza-
tion activity over Fe‐Mn/SZ is improved, the catalyst
deactivation is still inevitable because of the continuous
consumption of oxidizable species via stoichiometric
ODH of n‐alkane.
Ni and La promotion
Latterly, nickel and/or lanthanum have been used to
improve the reactivity of SZ catalysts for n‐butane,124,136
n‐pentane,114,149-151 and n‐hexane isomerization.118,152,153
The nickel, palladium, and platinum belong to one family,
so many attempts were made on nickel‐modified SZ to
replace the noble metal. When the impregnation method
is employed to introduce nickel on SZ surface, different
precursors result in different modification effects. Perez
et al found that the co‐impregnation of Ni (NO3)2 and
H2SO4 on the zirconium hydroxide supports increased
the n‐butane isomerization activity.124 They ascribed
this positive effect to the enhancement of bimolecular
reactions since the addition of Ni increases in the alkene
concentration on the catalyst surface.
To improve the dispersion of nickel, several
researchers employed the rare earth elements as
structural and electronic promoters for SZ cata-
lysts.114,118,136,151,152 Yu et al reported that the promotion
effects of rare‐earth oxides on n‐hexane isomerization
activity decreased as the following order: La2O3 >
Yb2O3 > Ce2O3.118 Since then, the La has been exten-
sively used as promoter for Ni‐modified SZ catalysts. Song
et al found that the Ni‐La modification on SZ by incipient
wetness impregnation way greatly improved the perfor-
mance of n‐pentane isomerization.151 They claimed that
the introduction of Ni enhances the redox performance
of catalyst and increases the number of Lewis acid sites,
while the introduction of La improves the dispersion of
Ni and facilitates the generation of new Brønsted and
Lewis sites. Specifically, the yield of isopentane increased
from 25% over unmodified SZ catalyst to 66.5% over
14
Ni‐La–modified samples (Figure 11). Actually, the addi-
tion of Ni‐La was more effective in n‐C5+ alkane isomer-
ization than that in n‐butane isomerization,136 because
that it is difficult for n‐butane to form carbenium ions
by hydride subtraction on the Lewis acid sites of SZ
catalyst at low reaction temperatures,63 while which is
feasible for n‐pentane activation.150,154 Consequently,
the enhancement in n‐pentane conversion over Ni‐La–
promoted SZ samples is resulted from the accelerated
activation of n‐pentane molecules, because of the
increase in the catalytic active Lewis acid sites resulted
from La/Ni introduction.
Cu and Ga promotion
Occelli et al found that Cu‐promoted SZ was more active
than Ag‐, Fe‐, Mn‐, and Fe‐Mn‐promoted SZ catalysts in
n‐pentane isomerization.155 They proposed that the Cu0
in the reduced catalyst can removes oxygen from t‐ZrO2
support to form oxygen‐deficient Zr atoms, which act as
Lewis acid sites during the activation process and
improves catalytic activity and/or lifetime. Ye et al sup-
ported Cu‐SZ on MCM‐41 surface and investigated its
activity in n‐hexane isomerization.156 They found that
adding 3.2 wt% CuO facilitates the formation of highly
active tetragonal zirconia, which is similar to Ga‐SZ/
MCM‐41 catalyst in n‐butane isomerization reported by
Wang et al.157 Following the same principle, Moreno
and Poncelet introduced Ga2O3 into SZ by both
FIGURE 11 Isopentane yield over parent SZA and La‐Ni–
promoted SZA catalysts prepared by incipient wetness
impregnation method. Reprinted with permission from Song
et al.151 SZA, sulfated zirconia–alumina [Colour figure can be
viewed at wileyonlinelibrary.com]
WANG ET AL.
impregnation and coprecipitation method to stabilize
the metastable tetragonal structure.158 Although exten-
sive attempts has been done, the above non‐noble
metal‐modified SZ with appropriate loading amount,
modification method, and posttreatment protocol exhibits
admirable catalytic activity of alkane isomerization, but
poor stability. Recently, Yang et al reported that the
CuGa/SZ shows the stable catalytic stability in n‐butane
isomerization for 200 hours (55% conversion of n‐butane
and 82% selectivity to isobutane), while the Ga/SZ and
Cu/SZ deactivate rapidly.159 They attributed this to the
higher ratio between Brønsted and Lewis sites, decreased
ZrO2 crystallite, stabilized tetragonal zirconia, and sur-
face sulfate of CuGa‐promoted samples. The further study
should focus on the long‐term stability of CuGa/SZ and
comparatively investigate on its catalytic properties with
the noble metal‐promoted catalysts.
5.2.3 | Promotion effect of noble metal
Compared with the non‐noble metal modification, the
addition of noble metals on SZ surface diminishes the
deactivation of SZ catalysts in n‐alkane isomerization in
the presence of hydrogen. Pt or Pd‐promoted SZ catalysts
have metal sites and acid sites. Different with activation
pathway of n‐alkane over the monofunctional acidic SZ
catalysts, n‐alkane molecules are activated by direct
dehydrogenation on the sites of Pt or Pd, forming the cor-
responding alkene. Then, the alkene molecules are
involved in isomerization cycles as chain carriers and
induce the formation of isoalkane. In this paper, we only
focus on the recent advances for several key issues about
the role of noble metal and hydrogen on n‐alkane
isomerization.
The first controversy lies in the chemical state of noble
metal on the SZ surface. Using in situ XPS and IR study
of adsorbed CO, Ebitani et al suggested that the sulfate
species on the SZ surface strongly suppressed the reduc-
ibility of platinum particles, so Pt mainly existed in the
cationic state with a very low concentration of metallic
platinum after reduction at 400°C.160 They ascribed this
inhibited reducibility to the redox metal‐support interac-
tion, which was caused by the fact that the acidic SZ sup-
port decreased the nucleation rate of platinum particles.
Further study by Paál et al showed that a bulk metal
phase of Pt presented on the surface with a coverage layer
of platinum sulfide.161 In contrast, Sayari and Dicko
argued that the platinum supported on the SZ surface
was easily reduced into metallic state during calcination
at 600°C in air, on account of a redox reaction between
Pt precursor and SO2, which was produced by the decom-
position of sulfate ions.162 Nonetheless, we think that
WANG ET AL.
there must be a fraction of Pt is in metallic state under
reaction conditions of n‐alkane isomerization, which are
responsible for the formation of alkene intermediates by
catalytic dehydrogenation. This is supported by the XPS
results reported by Manoli et al that the Pt was in a
mixture of the oxidation state and metallic form.163,164
Moreover, it was reported that the Pd0 and Pd+ coexisted
on the reduced Pd/SZ surface.14 The above different
results from different studies may be derived from the dif-
ferent storage and test conditions because the metallic
platinum is easily oxidized into its oxidation state.165
The other debate lies in the function mechanism of
noble metals in alkane isomerization. The traditional
bifunctional catalysis considers the metal sites as dehy-
drogenation function for the alkane and hydrogenation
function for the resulted isoalkene, while the SZ support
functions as acid catalyst for the skeletal isomerization
of n‐alkene. The unsaturated intermediates mainly
undergo hydrogenation to form alkane in the presence
of H2, which inhibits the coke formation and gives rise
to the steadily catalytic activity and selectivity. The above
bifunctional catalysis is challenged by the hydrogen spill-
over mechanism, since it was found that the Pt‐based zir-
conia catalysts had poor activity for hydrocarbon (de)
hydrogenation and negligible H2 and CO chemisorption
at room temperature.1,166 Earlier study by Iglesia et al
proposed that H2 can catalytically dissociate to H+ and
H− species on Pt sites of SZ. Then, the highly active
hydrogen species shorten the residence time of unsatu-
rated species and decreased their concentration via
hydride transfer reactions, which resulted in quick
desorption of isomerized intermediates before undergoing
oligomerization, so the catalytic stability was greatly
enhanced.167 Later, the hydrogen spillover model was
described by Tomishige et al in detail.97 As shown in
Figure 12, atomic hydrogen species resulted from hemo-
lytic dissociation of H2 on Pt surface spillover SZ and
form H+ and H− species by interacting with the holes
and electrons, respectively. The protons spill to the adja-
cencies of Brønsted acid sites and facilitate the generation
of sec‐butyl carbenium ions. The basic hydrides interact
with Lewis acid sites and facilitate the desorption of
tert‐butyl carbenium cations. Moreover, the spilt‐over
protons play an key role in the recovery of Brønsted acid
sites, following the same principle proposed by Ebitani
et al as below.168
Actually, we prefer the spillover mechanism over the
classical bifunctional mechanism for the following
reasons. First, Ebitani et al observed that the thermal
treatment of Pt/SZ catalyst in hydrogen atmosphere
increased the Brønsted sites and decreased the Lewis
sites, and evacuation treatment reversed these changes.168
They ascribed this to the dissociative adsorption of
15
hydrogen on Pt sites, spillover of H atoms to acid support,
and electron transfer from the H atoms to Lewis sites,
which left H+ ions on the catalyst surface. Second,
Pt/SZ catalyst shows good n‐pentane hydroisomerization
activity, while over the Pt/ZrO2 catalyst, hydrogenolysis
of n‐pentane dominates.169 Third, the reaction order with
respect to H2 in n‐heptane conversion over Pt/SZ is about
one, and it is close to zero with respect to alkane,167
which is quite different from the conventional bifunc-
tional isomerization mechanism on Pt/zeolite catalysts,
where the order with respect to H2 is negative, and with
alkane, it lies in 1 to 2 depending on the monomolecular
or bimolecular reaction.58 Last, on the bifunctional isom-
erization catalysts (Pt/Hβ), Wulfers and Jentoft proposed
that a chemical equilibrium between n‐alkane, n‐alkene,
and H2 reached inside reactor at 300°C.58 Under this cir-
cumstances, only 13 to 16 ppm of n‐alkene can be
obtained by catalytic dehydrogenation on the metal sites
even at 300°C under equilibrium conditions. At reaction
temperature for the Pt/SZ catalysts (lower than 200°C),
however, the equilibrium concentration of n‐alkene is
less than 1 ppm. It can be supposed that such low concen-
tration of n‐alkene cannot be responsible for the high
isomerization activity over Pt/SZ catalysts.
5.2.4 | Explanations for difference
between non‐noble and noble
metal‐modified SZ
Although no unambiguous interpretation has been given
yet for the origin of different promotion effects on the cat-
alytic stability between noble and non‐noble metal modi-
fied SZ catalysts, one possible cause can be concluded
from the literature. For non‐noble metal modified SZ cata-
lysts, the oxides of Ni, Mn, Fe, La, etc are difficult to be
reduced to their metallic states on the SZ surface because
of the incompatibility between their metallic state and high
valence state of sulfate species. Generally, a H2 pre‐
reduction process is required for the metal‐promoted SZ
samples to obtain highly dispersed and active metal parti-
cles.170 For Pt or Pd SZ samples, the pre‐reduction is often
carried out at temperatures from 200°C to 300°C.171-174
This temperature range is sufficient high for the reduction
of platinum oxide and palladium oxide to metallic state but
has no influence on the acid properties of SZ catalysts. By
H2 temperature‐programmed reduction (TPR) investiga-
tions, it was observed that the reduction of PtO2 and PdO
supported on the SZ catalysts proceeded within the tem-
perature range of 100°C to 250°C and 30°C to 70°C.171,175.
In further CO adsorbed FTIR investigations, Urzhuntsev
et al confirmed that Pd2+ was easily reduced to Pd0 and
Pd+ species under H2 at 150°C.14 The TPR profiles of
16
unmodified SZ samples displayed only one peak, starting
near 550°C and peaking at 670°C.136,176 This peak was
ascribed to the reduction of high valence state sulfate spe-
cies to sulfite and sulfide species, which are subsequently
removed from the surface in forms of SO2 and H2S.176
Although it was reported that the introduction of metal
components facilitated the reduction of sulfite spe-
cies,136,175-177 the Pt and Pd oxides can be reduced to their
metallic state below 300°C without a noticeable reduction
of sulfate species. For non‐noble metal‐modified SZ sam-
ples, however, the reduction of metal components must
be accompanied with the reduction of sulfate species,
which gives rise to the inability of non‐noble addition in
the improvement of isomerization stability over SZ
catalysts.
The reaction properties, type of reactor, and research
process of SZ‐based catalysts with different promoters in
WANG ET AL.
FIGURE 12 Schematic representation
of hydrogen spillover model of n‐butane
hydroisomerization on Pt/SZ catalyst. B:
Brønsted acid site, L: Lewis acid site, Hsp,
Hsp+, and Hsp−: spilt‐over hydrogen
species. Copied with permission from
Tomishige et al97
n‐butane isomerization are summarized in Table 3. From
Table 3, we can conclude that at present, the most
promising SZ‐based catalysts for commercial application
are Al‐promoted SZ in circulating fluidizing bed and
Pt (Pd)‐promoted SZ in adiabatic fixed‐bed reactor.
The future research will focus on the non‐noble
metal‐promoted SZ catalyst with high stability in
hydroisomerization of n‐alkane.
5.3 | Mesoporous material supported SZ
catalysts
One shortcoming of SZ catalysts is their relative high cost
of zirconia compared with the chlorinated alumina.
Supporting SZ particles on mesoporous materials is an
interesting alternative to maximize the specific surface
WANG ET AL. 17

TABLE 3 Comparative characteristics of SZ‐based catalysts with different promoters in n‐butane isomerization

Reaction Reaction Reactor Type and

Catalyst Conditions Performance Research Process Ref.

SZ T = 250°C At TOS of 2 min: Fixed‐bed Lei et al178

0.1 mPa Conversion = 21% Laboratory research
H2/n‐C4 = 10 Continuous deactivation
WHSV = 0.3 h
Al‐SZ T = 160°C‐200°C Conversion = 52%‐62% Circulating fluidizing bed Wang et al179
0.1‐0.15 mPa Selectivity = 72%‐82% Continuous reaction‐regeneration
H2/n‐C4 = 0 Continuous deactivation 300‐h pilot scale study
WHSV = 0.2 h
Hf‐SZ T = 250°C At TOS of 2 min: fixed‐bed Ahmed135
0.1 mPa Conversion = 19% laboratory research
N2/n‐C4 = 9 Selectivity = 81%
WHSV>3 h Continuous deactivation
Ga‐SZ T = 250°C At TOS of 16 h: Fixed‐bed Yang et al159
2.0 mPa Conversion = 20% Laboratory research
H2/n‐C4 = 3 Selectivity = 90%
WHSV = 0.4 h Continuous deactivation
NiLa‐SZ T = 200°C Conversion = 44% Fixed‐bed Wang et al136
0.1 mPa Selectivity = 89% Laboratory research
H2/n‐C4 = 0.6 Continuous deactivation
WHSV = 1.98 h
Cu‐SZ T = 250°C At TOS of 16 h: Fixed‐bed Yang et al159
2.0 mPa Conversion = 46% Laboratory research
H2/n‐C4 = 3 Selectivity = 87%
WHSV = 0.4 h Slow deactivation
CuGa‐SZ T = 250°C Conversion = 55% Fixed‐bed Yang et al159
2.0 mPa Selectivity = 82% 200‐h pilot scale study
H2/n‐C4 = 3 Stable during 200‐h pilot scale study
WHSV = 0.4 h
Pt‐SZ T = 180°C‐200°C Conversion = 50%‐55% Fixed‐bed Wang et al179
P > 1.5 mPa Selectivity = 90%‐91% Commercial application
H2/n‐C4 = 0.06‐0.1
Pd‐SZ T = 120°C‐160°C Conversion = 60%‐65% Fixed‐bed Urzhuntsev
2.3‐2.5 mPa Selectivity = 90%‐95% 90‐h pilot scale study et al14
H2/n‐C4 = 0.05‐0.15
WHSV = 2.0 h
γ‐Al2O3 supported T = 250°C At TOS of 2 min: Fixed‐bed Lei et al178
SZ 0.1 mPa Conversion = 43.3 % Laboratory research
H2/n‐C4 = 10 Continuous deactivation
WHSV = 0.3 h

area of the active phase. In general, carrier materials with
large specific surface areas, such as SiO2, γ‐Al2O3, and
MCM‐41 zeolite, are preferred in the preparation of meso-
porous material‐supported SZ catalysts.132,156,180-183 The
immobilization of SZ nanoparticles and their high disper-
sion on the carrier materials is currently of great interest
and challenge. The mesoporous material‐supported SZ
catalysts have following advantages over the bulk SZ
catalysts:
a. Enhanced reactivity for n‐alkane isomerization.
Depositing SZ particles onto mesoporous support
increases the surface area of catalysts and the num-
ber of active sites compared with conventional cata-
lysts.156,181,183,184 The interaction between sulfate
ions and zirconia particles was enhanced on the
mesoporous material supported SZ catalysts because
of the promoted formation of tetragonal zirconia. As
a result, the sulfate content, as well as the number
18
of active sites, increased.156,184,185 Consistently, Lei
et al observed that the enhancements in the strength
and density of strong acid sites on alumina‐supported
SZ catalysts gave rise to the phenomenon that the
supported catalyst was more active (2.5 times) than
the bulk SZ catalyst.178
b. Simplified catalyst preparation. Conventional SZ cat-
alyst is usually synthesized by a technologically com-
plicated procedure, including co‐precipitation, aging,
filtering, washing, drying, sulfation, and calcination
processes. While the supported SZ catalysts are usu-
ally prepared by depositing zirconium sulfate onto
the supports directly. For the conventional bulk SZ
catalysts, the calcination at high temperature, which
is indispensable for the formation of active sites for
alkane isomerization, unavoidably causes the crystal
transformation of tetragonal zirconia to monoclinic
one. For the supported SZ catalysts, however, the
tetragonal phase can be easily formed on the
surface of supports.178,184 The strong interaction
between zirconia particles and support restricts the
agglomeration and growth of ZrO2 particles; thus,
the phase transformation is suppressed.180 In addi-
tion, supporting the SZ onto the silica and alumina
surface enhances the thermal stability of the sulfate
species because of the enhanced interaction between
active components and supports.184
c. Reduced cost of catalysts. Huang et al found that the
optimal zirconium sulfate loadings were equivalent
to its apparent dispersion thresholds.184 Consequently,
the amount of zirconia component in the supported SZ
catalyst was 2 to 2.5 times lower than that in the con-
ventional catalysts.178 Thus, the supported SZ catalyst
is more cost‐effective for industrial application.
5.4 | Mesostructured SZ catalysts
Another strategy for obtaining the SZ catalyst with larger
surface area is to create more mesoporous structure in
zirconia support by surfactant‐assisted route or reflux
method. By using structure‐directing agents, such as
cetyltrimethyl ammonium bromide (CTAB),140,186 triblock
polymer surfactant (P123),187,188 and (C2H4O)nC16H34O
(Brij‐56), several researchers have successfully prepared
the mesostructured SZ catalysts with larger specific surface
area and pore volume. The resulting samples had high
reactivity of n‐alkane isomerization. Although possessing
abundant pore structures, the mesostructured SZ catalysts
with large surface area exhibited high thermal stability by
introducing Al species reported by Sun at al.187 Novelly,
in the work of Risch and Wolf,189 the precipitated slurries
WANG ET AL.
of zirconium hydroxide were stirred under reflux at 90°C
for 20 hours, which was much different with the conven-
tional aging at ambient temperature. The SZ catalysts
prepared with reflux method achieved approximately a
50% higher catalytic activity than the conventional
catalysts, resulting from the larger specific surface area
(269 m2/g) and more mesopore structures (0.400 cm3/g)
compared with the conventional catalysts (117 m2/g and
0.098 cm3/g).
6 | DETERMINATION OF
IN TRIN SIC
STRUCTUR E ‐REACTIVITY
RELATIONSHIP
6.1 | Prerequisite for the highly active
isomerization SZ catalysts
To date, it has been reached an agreement that the high
catalytic activity of SZ‐based materials for n‐alkane isom-
erization is contributed to a strong interaction between
high valence state sulfur and tetragonal zirconia supports,
resulting in the formation of necessary active sites during
calcination at high temperatures, regardless of the zirco-
nium sources, sulfation agents, and preparation methods.
Notably, the catalytic activity of SZ‐based materials
greatly improved with the increase in the fraction of
tetragonal zirconia, and the monoclinic zirconia‐based
catalysts were almost inactive for n‐alkane isomerization
(Figure 13), much different with other reactions.139,175
For instance, cyclohexane dehydrogenation175 and
Cannizzaro reaction of pyruvaldehyde to lactic acid190
FIGURE 13 Correlation among fraction of tetragonal phase
T/(T + M), (●) sulfur content, (■) concentration of Brønsted acid
site (BAS), and (▴) maximum catalytic activity for the different SO3
sulfated sulfated zirconia (SZ) samples. Copied with permission
from Li et al66
WANG ET AL.
required the monoclinic zirconia‐based catalysts, while
methanol dehydration activity was not influenced by the
crystalline form of zirconia.191
Amorphous zirconium hydroxide and crystalline zirco-
nia were often used in the preparation of zirconia‐based
catalysts.192 For n‐alkane isomerization, SZ catalyst pre-
pared by sulfating the crystalline zirconia exhibited
higher surface area, but lower acidity and reactivity com-
pared with the catalysts obtained from the amorphous
zirconia.33,139,193 This implied a strong chemical interac-
tion between sulfate species and amorphous zirconia
was formed during the calcination, which facilitated the
formation of tetragonal zirconia and highly active sites.
Indeed, the calcination protocol strongly affected the
n‐alkane isomerization activity.69,179,194-196 Chen et al
suggested that the formation of active sites involved a
two‐step surface reaction between sulfate species and
superficial hydroxyl groups of zirconium hydroxide:195
Zr ðOHÞ4n þ xH2 SO4 →Zr ðOHÞ4n−2x ðSO4 Þx þ 2xH2 O
Zr ðOHÞ4n−2x ðSO4 Þx →ZrO2n−x ðSO4 Þx þ ð2n − xÞH2 O
The first step was the formation of sulfated zirconium
hydroxide by intermolecular dehydration occurred at a
low temperature (lower than 400°C). Subsequently, an
intramolecular dehydration of sulfated zirconium hydrox-
ide occurred at a higher temperature to form an active SZ
catalyst. In this explanation, the formation of sulfated zir-
conium hydroxide strongly stabilized the tetragonal zirco-
nia and the formation of active sites by inhibiting the
sintering of zirconia particles. This explanation was also
supported by the finding of Clearfield et al that the sulfate
species favored to migrate to the surface of tetragonal zir-
conia during calcination process when the amorphous
zirconium hydroxide was used as zirconium precursor.29
By FTIR investigations, Morterra et al proposed that
the calcination step was crucial for the selective elimina-
tion of thermodynamically unstable sulfate species from
the highly energetic and crystallographic defects of tetrag-
onal zirconia, leaving the highly uncoordinated Zr4+ cen-
ters, which acted as catalytically active Lewis acid sites.196
This is somewhat inconsistent with the later finding that
it is Brønsted acidity that catalyzes n‐alkane isomeriza-
tion reaction. This inconsistence can be explained by
the latest observation by Liu et al that the interplay and
competition effects occurred between surface chemistry
and structural evolution during the thermal treatment
of sulfated amorphous zirconia.197 A portion of sulfate
species, weakly adsorbed on the zirconia surface, were
decomposed into O2 and SO2 at approximately 650°C,
while the removal of strong‐adsorbed ones required a
temperature higher than 720°C. The calcination of SZ at
19
650°C resulted in a mixture of monoclinic and tetragonal
zirconia, while it became completely tetragonal phase at
720°C, indicating that it was the strong‐bonded sulfate
species stabilized the tetragonal zirconia through a modi-
fication on the surface energetic states.197
Vera et al suggested that the anionic vacancies in zir-
conia stabilized the tetragonal zirconia in the active SZ
catalyst, which in turn directly improved the isomeriza-
tion activity through stabilizing the electrons from the
ionized intermediates.139 Grau et al claimed that the for-
mation of tetragonal zirconia strongly affected the acid
functions, but no detail explanations were given.175 Here,
we conclude that only the directly strong‐adsorbed sulfate
species on the tetragonal zirconia surface generate highly
active sites for n‐alkane isomerization, which is also sup-
ported by the fact that the n‐alkane isomerization activity
is strikingly influenced by the density of surface sulfate
species. Morterra et al highlighted that the coverage of
high valence state sulfur species determined the ratio of
Brønsted/Lewis acid sites on the surface.198 Katada et al
claimed that the monolayer loading of sulfate species on
ZrO2 surface exhibited considerably high adsorption heat
(approximately 200 kJ/mol), resulting in the superacidity.
However, the excessive loading of sulfate species with a
lower adsorption heat (approximately 150 kJ/mol) gener-
ated the weaker acid sites.173 Our study showed that the
decrease in the density of high valence state sulfur species
resulted in a drastic decrease in the isomerization activity
because of the weakened acidity and oxidizability.89
6.2 | Dependence of the activity of SZ
catalysts on the hydration degrees
An activation pretreatment at higher temperature is
required to obtain high n‐alkane isomerization activity
over strong hydrophilic SZ catalysts, because of its surface
complexity under different hydration degrees. The
temperature rather than the atmosphere during activa-
tion remarkably influences isomerization activity of
SZ.8,70,93,199 Klose et al found that more than 95% of water
adsorbed on the SZ catalyst was removed after activation
at 550°C in aerobic or inert atmosphere by in situ IR stud-
ies, corresponding with the great promotion of isomeriza-
tion activity.70 It was also reported that the activation
pretreatment facilitated the generation of highly active
sites.200
On one hand, Brønsted and Lewis acid sites can
reversibly interconvert under different dehydration
degrees. The number of Brønsted sites decreases during
the activation because of the dehydroxylation of Zr─OH,
which explains the detrimental effect of activation at high
temperature (higher than 500°C) on the isomerization
20
activity.8 Simultaneously, more unsaturated Zr4+ ions
expose on the surface and act as Lewis sites that are
active in the dissociative adsorption of water molecules,
generating Zr─OH groups with high Brønsted acid
strength. At high water coverage, however, the adsorp-
tion of water molecules, including the chemical and phys-
ical adsorbed ones, decreases the strength of acid sites,
resulting from the weakened electron‐withdrawing effect
of sulfate species. On the other hand, the DFT calcula-
tions by our group highlighted that the DPE values of
Zr─OH groups tightly depended on the hydration degree
of surface.8 Namely, with the increase of water coverage,
the DPE values of Zr─OH groups increased, implying a
weakening in the strength of Brønsted acid sites. In short,
the pretreatment affects both of the density and the
strength of catalytic Brønsted acid sites, as a result, the
activation under appropriate temperature gives the opti-
mal reactivity.
7 | A P P L I C A T IO N P R O S P E C T S O F
n‐ALKANE ISOMERIZATION OVER
SZ CATALY STS
As mentioned above, the major drawback to the applica-
tion of SZ is its rapid deactivation rate. To overcome
this, two types of technology have been developed. One
is the hydroisomerization over a Pt/Pd‐promoted SZ cata-
lyst in fixed‐bed reactor, much similar to the current pro-
cess with Pt/Cl‐Al2O3 catalysts. Adiabatic heat rise of
n‐butane isomerization is approximately 20°C, making
it possible to conduct the isomerization process in a
tubular fixed‐bed reactor.14 The technological applica-
tions based on the Pt/SZ catalysts include Isomalk pro-
cesses (Isomalk‐2 for C5/C6 and Isomalk‐3 for C4)
developed by JSC SIE Neftehim and Par‐Isom process
developed by UOP. As shown in Tables 4 and 5, the tech-
nologies based on the Pt/SZ catalysts show the compara-
ble catalytic properties in n‐alkane isomerization with the
chlorinated alumina‐based technologies. The SZ‐based
technologies benefit from the following features com-
pared with the conventional process: (a) no use of toxic
chlorine and no issues with caustic scrubbing and spent
caustic disposal; (b) sustained high activity without the
loss of sulfur; and (c) high tolerance to water, sulfur,
and nitrogen. However, the Pt/SZ catalysts show some-
what lower selectivity to isobutane in n‐butane isomeriza-
tion and liquid yield in C5/C6 isomerization than
chlorinated alumina‐based catalysts. The most likely
explanation for this lies in the heterogeneity of acid sites
on the SZ surface; that is, some of the acid sites are favor-
able for the undesired hydrogenolysis reaction.89
WANG ET AL.
The other potential application of SZ catalyst in
n‐alkane isomerization is based on the idea of achieving
continuous reaction‐regeneration cycles of unmodified
SZ catalyst in a circulating fluidizing bed (CFB) devel-
oped by our group.179 The SZ catalyst demonstrated
extremely satisfied catalytic stability in C4 isomerization
in a pilot‐scale CFB unit for 300 hours (Table 4). The con-
version of n‐butane is comparable, even slightly higher
than that obtained on the Pt‐based catalysts in the fixed‐
bed. While the selectivity to isobutane is obviously lower
than that on the Pt‐containing catalysts because of the
serious axial back mixing in the CFB and inevitable
“dimerization‐cracking” reaction occurred at the initial
of reaction. Although no sulfur is lost during the reaction,
we unexpectedly found that a very small amount of SO2
evolved in the flue gas even under an air‐regeneration cir-
cumstance. The SO2 is generated by two ways: one is that
a few of sulfite species formed during the isomerization
reaction decomposed before reoxidized to sulfate species;
the other is that a few amounts of coke deposition are oxi-
dized to CO2 by sulfate species before completely oxidized
by O2. The evolution of SO2 can be minimized to 7 ppm
in regeneration gas by regulating the gas stripping tem-
perature, increasing the space time of the feed, and
decreasing the regeneration temperature. Under such
conditions, the SZ catalysts can maintain its catalytic
activity at least for 1 year with the loss of 10.8% sulfur.179
Moreover, this CFB‐Isom process can be operated in
the absence of hydrogen and without rigorous feed
pretreatment.
8 | O U T LO O K
The research on SZ is ascendant in academic and applied
prospects in alkane isomerization. For the former, the
developments of advanced characterization techniques
and theoretical calculations greatly improve our under-
standing on the correlation between surface chemistry
and reactivity of SZ catalysts in alkane isomerization. By
in situ optical spectroscopy and DFT calculations, the role
of oxygen vacancies on the surface of tetragonal ZrO2
should be illuminated to understand the interplay
between sulfate species and zirconia support in the
future, allowing us to obtain a more definite structure‐
activity relationship model. It is worth pointing out that
the progress in the research of molecular structure of cat-
alysts is essential in developing the more efficient prepa-
ration methods and designing the more active SZ‐based
catalysts. Therefore, two aspect works should be done in
the future study: first, the reaction mechanism should
be further clarified by the application of new characteri-
zation techniques, especially the different deactivation
WANG ET AL. 21

TABLE 4 Comparative characteristics of different processes for n‐butane isomerizatio

Process Butamer Isomalk‐3 BIC CFB‐Isom

Company‐developer UOP JSC SIE Neftehim Boreskov Institute of Catalysis UPC

Catalyst Pt/Cl‐Al2O3 Pt/SO4 ‐ZrO2
2−
Pd/SO4 ‐ZrO2
2−
SO42−/ZrO2‐Al2O3
Temperature, °C 160‐220 180‐200 120‐160 160‐200
Pressure, MPa 2.5‐3.2 >1.5 2.3‐2.5 0.1‐0.15
H2/n‐alkane in mol. 0.03‐0.07 0.06‐0.10 0.05‐0.15 0
Conversion, % 50‐60 50‐55 60‐65 52‐62
Selectivity, % 98 90‐91 90‐95 72‐82
Service life, years 3‐5 2‐3 >3 >1
Limits of impurities in the raw, ppm
H2O 0.1 ≤20 ≤20 Unknown
Sulfur 0.1 2‐5 20 ‐
Fluorine 0 Unknown 300 ‐
Nitrogen 0.1‐0.5 1 ‐ ‐

Note. Reproduced with permission from Urzhuntsev et al and Wang et al.14,179

TABLE 5 Comparative characteristics of different processes for C5‐C6 alkane isomerization201

Process Penex Hysomer Par‐Isom Isomalk‐2

Company developer UOP UOP UOP JSC SIE Neftehim

Catalyst Pt/Cl‐Al2O3 Pt/HOR Pt/SO4 ‐ZrO2
2‐
Pt/SO42‐‐ZrO2
Temperature, °C 120‐130 201‐288 140‐190 120‐180
Pressure, MPa 2.94 1.08‐3.53 3.2 2.5‐2.8
H2/n‐alkane in mol. 2 1‐4 2 1.5‐2.5
Space velocity, h 1‐3 1‐3 2.5 2.5‐3.5
Octane number 85‐86 82.1 82 93
Liquid yield, vol% 99 98.4 ≥97 97‐98
Service life, years 3‐5 2‐3 2‐3 2‐3
Limits of impurities in the raw
H2O, ppm 0.1 50 ≤20 ≤20
Nitrogen, ppm 0.1 1 1 1
Sulfur, ppm 0.1‐0.5 50 1‐5 2‐5
Benzene, wt% ≤1 5 ≤10 ≤10
+
C7 , wt% <1 2‐3 ≤5 ≤5

mechanism in n‐butane and n‐C5/C6 alkane isomeriza-
tion. Second, the reactivity of SZ catalysts should be
furtherly improved by the catalyst design and the condi-
tion optimization.
The successful applications of Pt/SZ in the fixed‐bed
process and SZ in the circulating fluidizing bed process
in the light alkane isomerization suggest that the SZ cat-
alysts may replace the conventional technologies based
on the chlorinated alumina catalysts. For the fixed‐bed
technology, the high cost of noble metal and rigorous pre-
treatment of feed should be avoided or reduced by two
approaches. One is trying to reduce the loading of noble
metal by improving its dispersion on SZ surface. Actually,
the effects of intimacy and balance between metal sites
and acid sites on isomerization activity should be inten-
sively studied to reveal the synergetic effect between
them, which would bring about new opportunities for
catalysts design. The other is attempting to develop a
22
non‐noble metal‐promoted SZ catalyst with high isomer-
ization stability by overcoming the incompatibility
between metallic state of non‐noble metal and higher oxi-
dation state of sulfur in the sulfated species. For CFB
isomerization technology, the stability of active sulfate
species during regeneration process needs to be further
improved by optimizing the catalyst composition and
operating conditions. It is worth noting that several
alternatives to SZ have been well developed, such as
WOx/ZrO2192 and MoOx/ZrO2202, which are also consid-
ered as solid superacids and show similar catalytic perfor-
mance in alkane isomerization with SZ catalysts. In
conclusion, the SZ and its modified versions are much
more promising in n‐alkane isomerization and are
expected to draw great interest in the coming years.
A C K N O WL E D G E M E N T
This work was financially supported by the National Nat-
ural Science Foundation for Young Scholars of China
(21902028) and China Postdoctoral Science Foundation
(2019M662227).
ORCID
Pengzhao Wang https://orcid.org/0000-0001-6660-6097
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How to cite this article: Wang P, Yue Y, Wang
T, Bao X. Alkane isomerization over sulfated
zirconia solid acid system. Int J Energy Res.
2020;1–25. https://doi.org/10.1002/er.4995