Fuel xxx (xxxx) xxx

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Review article

Effect of metal–acid balance and textual modifications on

hydroisomerization catalysts for n-alkanes with different chain length: A
mini-review
Chenhao Wei, Guohao Zhang, Liang Zhao *, Jinsen Gao, Chunming Xu
The State Key Lab of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China

A R T I C L E I N F O A B S T R A C T

Keywords: Hydroisomerization of n-alkanes has become an essential route for producing high quality fossil fuels and lu­
Hydroisomerization bricants meeting the state-of-art regulations. The hydroisomerization of light alkanes, i.e., pentane and hexane,
Metal-acid balance has been well developed. However, this process for heavier n-alkanes still has a large room for improvement.
Mechanism
Therefore, the purpose of the present work is to review similarities and differences among the hydro­
Hierarchical structure
isomerization of n-alkanes with different chain length. Attention has been paid on the effect of metal–acid
N-alkane
balance and textual modifications on the bifunctional catalysts. Besides, the mechanism of hydroisomerization
was also discussed in detail. At last, conclusions and prospects for the hydroisomerization of long-chain n-alkanes
have been made. This review could help to understand difficulties in enhancing isomers yield during the
hydroisomerization process and could benefit new researchers in this field by relating the state-of-art researches
to the reaction mechanism.

1. Introduction alkanes hydroisomerization, nowadays, the most studied and promising

Hydroisomerization of normal alkanes have drawn great attention in
petroleum industry as well as in exploiting Fischer–Tropsch oil and bio-
derived oil in recent years [1–3]. N-alkanes make up a great percentage
in distillated crude oil cuts and Fischer–Tropsch oil. As is shown in
Table 1, hydroisomerization of C4-C8 n-alkanes can greatly increase the
octane number of gasolines to compensate for the loss caused by regu­
lations of olefin contents, while the hydroisomerization of C10-C22 can
benefit the low-temperature flow properties of diesel, for example, the
cold filter plugging point, viscosity, and freezing point [4–7]. Especially
for the n-alkanes with carbon number greater than 20, which are usually
called wax, through hydroisomerization one can produce lubricants
with ultra-high viscosity index and much lower pour point [8]. There­
fore, the techniques of hydroisomerization is not only environment
friendly, but also able to gain economical profits.
Catalysts used for hydroisomerization are usually bifunctional,
containing hydrogenation-dehydrogenation function and acid catalysis
function. The former one is usually supplied by noble metals, such as
platinum and palladium, concerning their high (de)hydrogenation ac­
tivity. While the latter one is usually gifted by solid acids. For light
catalysts are zirconia-based ones and zeolites-based ones, such as Pt/
SO42− -ZrO2, Pt/WO3-ZrO2 and Pt/MOR, Pt/BEA, Pt/Y [11–17]. Plat­
inum promoted sulfated zirconia and tungsten zirconia catalysts show
great activity. The advantages of zeolites-based catalysts have great
tolerance on water and sulfur contaminants and they can be easily re­
generated. While for long-chain alkanes, the most used acid supports are
zeolites and silicoaluminophosphate molecular sieves with unidirec­
tional pore system [18]. To date, Pt/SAPO-11 and Pt/ZSM-22 are the
most investigated ones [19,20]. The first advantage of using these uni­
directional molecular sieves is their unique shape selectivity for iso-
alkanes, including reactant shape selectivity, transition state shape
selectivity and product shape selectivity [21]. The second advantage is
their stability by reducing coke formation.
In practice, the development and research status of n-alkanes
hydroisomerization with different chain length is unbalanced. For
example, hydroisomerization of n-pentane and n-hexane has been
extensively studied, and there has been several industrial applications
with isomers yield higher than 95% [19,22,23]. While there are still
limitations on the industrial application of hydroisomerization of n-
heptane and n-octane, concerning the low yield of desired multi-

* Corresponding author.
E-mail address: liangzhao@cup.edu.cn (L. Zhao).

https://doi.org/10.1016/j.fuel.2021.122809
Received 28 September 2021; Received in revised form 20 November 2021; Accepted 1 December 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.

Please cite this article as: Chenhao Wei, Fuel, https://doi.org/10.1016/j.fuel.2021.122809

C. Wei et al.
Table 1
The properties of different n-alkane molecules and their isomers. Data is adapted
from ref. [9,10].
Category Compound Properties
Gasoline n-heptane Research octane number
2-methylpentane
2,3-dimethylbutane
Diesel n-hexadecane Cetane number
n-hexadecane Melting point (◦ C)
3-methylpentadecane Cetane number
3-methylpentadecane Melting point (◦ C)
Lubricants n-hexacosane Viscosity Index
n-hexacosane Pour point (◦ C)
11-butyldocosane Viscosity Index
11-butyldocosane Pour point (◦ C)
branched products. As for the hydroisomerization of n-alkanes with
ultra-long chain, which is called isodewaxing, to produce lubricants
meeting API III and API III+ viscosity index, the existing industrial ap­
plications are still facing the challenges of low yields and high energy
consumption.
In this review, we attempt to give comparative views on the hydro­
isomerization between linear light alkanes (n-pentane and n-hexane)
and long-chain alkanes (no less than n-heptane). The first part focus on
the summary and comparison of hydroisomerization mechanism. The
effects of metal–acid balance were discussed in the second part. Then
recent development and modifications on the textual properties of cat­
alysts were summarized for the hydroisomerization of long-chain al­
kanes. Through the summarized research and comparison, we hope
lights can be shed into the development of hydroisomerization catalysts
for long-chain alkanes.
2. Mechanism of n-alkane hydroisomerization
2.1. The overall mechanism of hydroisomerization
Generally, the hydroisomerization reactions are based on bifunc­
tional catalysts, which comprise hydrogenation-dehydrogenation func­
tion and acid function. It is widely accepted that the acid sites are active
in this process only if they are in their Brønsted form instead of Lewis
form [24–26]. The most used catalysts include Pt and Pd as
hydrogenation-dehydrogenation active sites and molecular sieves as
acid supports [27–29]. Thus, the following discussion is based on
traditional bifunctional catalysts.
The classic bifunctional mechanism of n-alkane hydroisomerization
was proposed by Coonradt and Garwood [30], and is shown in Scheme
1. It contains the following 7 successive steps:
a) Diffusion of n-alkane molecules from bulk phase to the metal sites.
b) Dehydrogenation of n-alkane molecules on metal sites to form n-
olefin intermediates.
c) Diffusion of n-olefin intermediates from the metal sites to Brønsted
acid sites, which is either in the micropores or on the external surface
of molecular sieves.
d) Isomerization of n-olefin intermediates on the acid sites to form iso-
olefins.
e) Diffusion of iso-olefins from the acid sites to metal sites.
f) Hydrogenation of iso-olefins on the metal sites to form iso-alkanes.
g) Diffusion of iso-alkanes to bulk phase.
Obviously, there are 3 chemical steps and 4 physical steps. And in
these 3 chemical steps, the dehydrogenation and hydrogenation steps
are much faster than the isomerization step. Once n-alkenes were
absorbed on Brønsted acid sites, the isomerization may happen. For light
alkenes, the Brønsted acid sites inside the micropores of 10 or 12-
membered rings molecular sieves are usually accessible, considering
Fuel xxx (xxxx) xxx
Value
0
46
89
100
17.9
87
− 21.2
188
56.2
128
0
Scheme 1. Classic mechanism of n-alkane hydroisomerization over bifunc­
tional catalysts.
the less limitations on diffusion of small molecules. While for long-chain
n-alkenes, it’s not easy for the whole molecule diffuse from one side of
the micropore to another, due to the diffusion constrain imposed by the
interaction between alkene molecule and the wall of micro channels. In
such case, to explain how is the long-chain n-alkenes are isomerized, two
unique reaction mechanisms were proposed, which are so called “pore
mouth” and “key lock” mechanism [31–34]. “Pore mouth” mechanism
describes the situation in which one end of the carbon chain of n-alkene
molecule penetrates into the micropores, and it is catalyzed by the acid
sites located near the pore mouth. This unique mechanism is usually
used to explain the formation of mono-branched products whose
branching is near the terminal position. While “key lock” mechanism
describes the situation in which both two ends of the carbon chain
penetrate two adjacent pore openings simultaneously. The same as it in
“pore mouth” mechanism, the isomerization is catalyzed by the acid
sites near the pore mouth. This is used to explain the central branching
of isomer products. For light alkanes, the “key lock” mode is not favored,
because the penetration into two adjacent pore openings requires the
chain length being greater than the thickness of the pore wall. For long-
chain alkanes, it’s said the “key lock” catalysis contributes significantly
in the distribution of methyl-branched isomers. And this contribution
increases with the carbon number of reactants. Furthermore, high re­
action temperature was regarded in favor of “key lock” mechanism,
considering the adsorption entropy is lower than that in the “pore
mouth” mode [31].
In the hydroisomerization of n-alkanes, the chain length has signif­
icant influence on the products distribution. Though the overall
hydroisomerization mechanism of both light alkanes and long-chain
alkanes is very similar, the yields of isomers are much lower in the
hydroisomerization of long-chain alkanes. For example, the yields of
isomer products in C5/C6 n-alkanes hydroisomerization industrial ap­
plications, such as Hyysomer HS-10 from UOP, Hysopar 5000 from
Clariant, have reached to more than 95%, which can be regarded suc­
cessful [23]. However, compared to light alkane isomerization, the
yields of isomerized products in the hydroisomerization of long-chain n-
alkanes are much lower. In academic studies, this number range from
about 30% to 70% [35–38]. The significant difference in isomers yields
are mainly attributed to the following two reasons. The first is the
different levels of diffusion limitations imposed by catalysis materials
[39]. For alkanes, the molecular dimensions roughly increase with
carbon number, thus, the severity of spatial confinement imposed by
shape selective zeolites also increases. This will lead to higher possibility
2
C. Wei et al.
of excessive reactions during the diffusion of reactants, and further lead
to cracking. The second reason is the difference on isomerization
mechanism of alkene intermediates with different chain length.
Compared to light alkanes (C5/C6), more skeletal cleavage pathways are
available for alkanes whose carbon number is equal to or greater than 7,
and the detailed mechanism will be discussed in the next subsection.
2.2. Isomerization of alkene intermediates
To get better understanding of hydroisomerization, the isomeriza­
tion mechanism of alkene intermediates shall be discussed in detail.
Isomerization of alkenes is based on carbenium ions transformation. The
carbenium ions are formed on Brønsted acid sites by protonation.
Alvarez et al. [40] has summarized the isomerization and cracking re­
actions of carbenium ions.
The isomerization reactions of carbenium ions was classified into
two kinds: Type A isomerization occurs through alkyl shift, in which the
position of branching changes but the degree of branching does not
change. Type B isomerization is the originates of side chains. It occurs
through protonated cyclopropane (PCP) intermediates and protonated
cyclobutene (PCB) intermediates, as shown in Scheme 2 and Scheme 3.
PCP intermediate explains the formation of mono-methyl- and multi-
methyl-isomers, which can be transformed from low branching degree
to high branching degree successively [41]. While the PCB intermediate
is proposed to explain the formation of ethyl-branched isomers. Of note
is that, due to the effect of steric hindrance, PCB intermediate could
rarely format inside 10-membered ring channels. Besides, from the en­
ergetic view, the formation of protonated cyclopropane intermediates
from classical secondary carbenium have a lower energy barrier than
that of protonated cyclobutene intermediates [42]. This explains the
phenomenon that in the hydroisomerization of n-alkanes, the observed
ethyl-branched isomers are always rare compared with methyl-
branched ones [10,43,44].
These two kinds of isomerization reactions, i.e., type A and type B,
are reported to have different relative reaction rates. In hydro­
isomerization of n-decane, the methyl shift reactions were reported to be
faster than PCP branching in 70 times [45]. In n-hexane hydro­
isomerization, the transformation between mono-methylpentanes is
about 10 times faster than branching degree changes. And Alvarez et al.
[40] used approach to thermodynamic equilibrium (ATE) to get the
estimation of the relative rates of type A and type B isomerization. The
result shows, in n-decene hydroisomerization, methylnonenes formed
through protonated cycloalkane intermediates is 6–7 times slower than
through methyl shift. Though difference on those relative rates exists, it
still can be concluded that type A isomerization is much faster than type
B isomerization.
Scheme 2. Isomerization of carbenium ions via a protonated cyclopropane
intermediate.
3
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Scheme 3. Isomerization of carbenium ions via a protonated cyclobutene
intermediate.
2.3. Undesired cracking
The isomerization of carbenium ions is always accompanied with
cracking reactions, and the cracking products are undesired at most time
because of their low value. As mentioned above, the isomer yields of
light alkanes are much higher than that of long-chain alkanes in
hydroisomerization. To explain and understand this phenomenon, the
detailed discussion of cracking mechanism is necessary.
β-scission refers to the cleavage of carbon–carbon bond at the Beta
position of charged carbenium ion. The cracking reactions, i.e. β-scis­
sion, happen through 4 types of mechanisms, which are called type A,
type B, type C, and type D mechanisms. As shown in Scheme 4, these 4
types of cracking mechanisms are classified according to the different
structures of carbenium ions participated. Type A pathway includes two
tertiary carbenium ions, it is only possible when the carbon number of
isomers is no less than 8. Type B (including Type B1 and Type B2)
pathway includes one secondary and one tertiary carbenium ions, either
from secondary to tertiary or from tertiary to secondary ones. This re­
quires the reactant no less than 7 carbon atoms. Type C pathway in­
cludes two secondary carbenium ions, the original chain length should
not be less than 6. The last Type D pathway includes the formation of
unstable primary carbenium ions from secondary ones. The rate con­
stants of these 4 modes of cracking reactions keep decrease from type A
to type D [46]. From the above cracking mechanisms, one can tell that in
the hydroisomerization of n-alkanes, light alkanes (C5/C6) have less
chance of skeletal cleavage than long-chain alkanes do.
In F. Alvarez et al.’s [40] research of hydroisomerization and hy­
drocracking of n-decane, the relative rates of isomerization and cracking
reactions were evaluated according to the distribution of isomers and
cracking products under the reaction condition of T = 473 K, pH2 = 0.9
bar, pn-decane = 0.1 bar. As shown in Scheme 5, the rate constants of
successive isomerization from n-C10 to trimethyl isomers are similar.
However, there are significant differences in rates of cracking reactions
between isomers with various branching degrees. Type C and type D
cracking reactions correspond to the reactants of n-decane and mono­
branched isomers. For type D cracking, the products contain the un­
stable primary carbenium ions, and the rate is very slow. While for type
C cracking, the reaction rates are too slow compared to the successive
isomerization and other cracking reactions to be taken into account
[47]. Therefore, the value of their relative rates is not shown in the
scheme. Most of the cracking products are formed through type A and
type B cracking. And as shown in the scheme, the cracking of tri­
branched isomers is about 50 times faster than the cracking of
dibranched isomers. Of note is that, all the cracking mechanism and
their relative rates are obtained on catalysts with zeolite Y or USY as the
acid supports, and these zeolites can be considered has negligible
C. Wei et al.
Scheme 4. Classifications of cracking reactions. Adapted from [46] with permission from Elsevier.
Scheme 5. Relative rate constants of isomerization and cracking. Adapted from [40] with permission from Elsevier.
diffusion limitations on the reactants and reaction intermediates
because of their large pore size.
Through the above analysis of isomerization and cracking reactions
mechanism, the conclusion can be drawn as follows:
a) Compared to long-chain n-alkanes, light alkanes (C5/C6) can only
crack through type C and type D mechanism, which are much slower
than the rate of isomerization. Therefore, it is very promising to get
high yields of isomers in pentane and hexane hydroisomerization.
b) From n-heptane, with the increase of chain length, the overall
cracking reactions are extensively enhanced considering both the
intrinsic type A, type B cracking and the various structures of tri­
branched isomers. This indicates the precise control of branching
degree is of greater importance for reactants with longer chain length
to enhance the isomers yields.
3. Effects of metal–acid balance and the comparison between
alkanes with different chain length
As is shown in the above reaction mechanisms, the performance of
hydroisomerization is determined by both the characteristics of (de)
hydrogenation function and Brønsted acid function, i.e., metal–acid
balance. Their balance is mainly determined by the ratio of accessible
metal sites to acid sites, which is referred as nMe/nA or CMe/CA, and the
properties of acid supports, including acid strength, acid density and
acid location. However, for light alkanes and long-chain alkanes, the
effects of the balance are not totally the same. Detailed discussion was
given in this chapter.
4
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3.1. Comparison of the effects of nMe/nA value
To investigate the effects of metal–acid balance and to give a quan­
titative evaluation, the nMe/nA value is the most commonly used
parameter. This value refers to the ratio of accessible metal sites to the
accessible acid sites with given strength. For the purpose of obtaining
systematic investigation, various methods were used to tuning the
metal–acid balance. The most commonly used methods include tuning
the Si/Al ratio of molecular sieves to change the Brønsted acid density/
strength, and changing the metal loading of synthesized catalysts.
Alvarez et al. [48] prepared HY zeolites with Si/Al ratio of 3 and 9 by
calcination and SiCl4 dealumination of USYNH4, respectively. By
changing the Pt loading and Si/Al ratio, catalysts with nPt/nA from 0.002
to 0.167 were obtained. For n-hexane transformation, the effects of nPt/
nA can be divided into three stages. The first stage refers to the low
platinum content, nPt/nA < 0.006. At this stage, the (de)hydrogenation
function have not reached to the balance with acid function. The (de)
hydrogenation reactions appeared to be the rate limiting step. Hexene
produced by Pt sites could hardly compensate for the consumption on
acid sites. Furthermore, it limited the in-time hydrogenation of iso­
merized alkenes. Due to the relative excess of Brønsted acid sites, those
isomerized alkenes have a greater possibility to undergo further reac­
tion. As mentioned in the mechanism, this will lead to cracking as well as
coke formation. Therefore, the activity and stability of catalysts were
limited, and kept increase with increasing nPt/nA. Mono-branched and
di-branched isomers both appeared to be the primary products, and
cracking products appeared even at low conversion. When 0.006 < nPt/
nA < 0.1, it reached the second stage. The activity of the catalyst reached
a plateau. Moreover, only mono-branched isomers were the primary
products. However, the ratio of mono-branched to di-branched isomers
C. Wei et al.
in the products kept increasing from about 25 to 30 with increasing nPt/
nA. It seems the olefinic intermediates produced by (de)hydrogenation
sites were able to feed all the acid sites. However, in this nPt/nA range,
the stability of catalysts had not reached the maximum. It indicated
though all the acid sites have participated in reactions, some of them
were still reacting with reactants that have undergone at least one
isomerization. While for nPt/nA > 0.1, it can be regarded to the third
stage, in which it preserved most features in the second stage. However,
the ratio of mono-branched to di-branched isomers kept constant. No
deactivation caused by coke formation was observed in 3 h. The reaction
scheme seems to be perfectly obeys the successive carbenium ion
transformation introduced above. It means every olefinic intermediate
only undergoes one isomerization reaction during the diffusion from one
metal site to another. And the isomerization reactions became the rate
limiting step. Therefore, at this stage, the catalysts were called “ideal”
bifunctional catalysts.
Similar results were obtained by Lyu et al. [49] on Ni loaded SAPO-
11 catalysts. They studied the hydroisomerization of n-hexane on the
catalysts with CNi/CA range from 0 to 0.30. The result showed the ac­
tivity of the catalysts, which is represented by turnover frequency (TOF)
per acid site, kept increasing at CNi/CA less than 0.19. At this range, both
mono-branched (MP) and di-branched (DMP) isomers were primary
products. For example, on the catalyst SN-1, whose CNi/CA = 0.10, the
DMB/MP value equals to 0.02 when it is extrapolated to zero conver­
sion. These features have well met that of the first stage mentioned
above. While for CNi/CA > 0.19, DMB/MP ratio and cracking/isomeri­
zation ratio can be observed close to 0 at low conversion. This means the
hydroisomerization reaction starts to follow the consecutive scheme,
which is the same as observed from the second stage mentioned above.
Indeed, the ratio of CMe/CA values varied a lot in the comparison with it
in the last quoted research. However, it was caused by the (de)hydro­
genation activity difference of metal Pt and Ni. In comparison, each
platinum sites can feed about 170 acid sites with olefinic intermediates,
while this number is only 5 for nickel sites.
For the hydroisomerization of long-chain alkanes, e.g., n-heptane,
the effects of nPt/nA were studied by Ginenetto et al. [50]. They used the
same Pt-loaded HY zeolites with Si/Al ratio of 3 and 9 as ref. [48]. While
in the original article, the effects of nPt/nA value were discussed in the
form of nA/nPt. To get a better comparison, they were converted into the
same form as others in this review. The same as it for light alkanes, the
effects of nPt/nA for n-heptane can also be divided into three stages. At
nPt/nA < 0.029, all the isomers including monobranched, dibranched
and tribranched ones were formed directly, and cracking products
appeared at zero conversion. Till the conversion reached to 50%, the
distribution of cracking products had reached more than 90%. This
indicated both isomers and cracking products were primary products.
The lack of (de)hydrogenation function caused the excessive reaction of
each olefinic intermediates. Then the higher cracking tendency of over-
isomerized products contributed to the cracking products and limited
the isomer selectivity. Of note is that the deactivation caused by coke
formation was observed. When nPt/nA came to between 0.029 and 0.10,
from the products distribution, it seems only isomers were the primary
products. And the activity of PtHY catalysts came to be constant. Though
cracking products were also obvious, from 41.4% to 20.7% with
increasing nPt/nA at 50% conversion, the value was reduced to a large
extent. It indicated olefinic intermediates will encounter serval acid sites
and undergo more than one reaction before being hydrogenated. How­
ever, for most intermediates, those acid sites were not enough for the
formation of cracking products. At the third stage, nPt/nA > 0.10,
monobranched, dibranched, tribranched isomers and cracking products
were observed being formed step by step. At 50% conversion of n-hep­
tane, the minimum distribution of cracking products was only 5.3%.
Since each olefinic intermediates only went through one isomerization
before being hydrogenated, the formation of multi-branched isomers
with higher cracking tendency was in low possibility.
For alkanes with longer chain length, there are also similar research.
5
Fuel xxx (xxxx) xxx
Alvarez et al. [40] studied the effects of nPt/nA in the hydroisomerization
of n-decane on a series of Pt/HY catalysts with nPt/nA from 0.002 to
0.48. From the results, the effects of nPt/nA ratio still can be divided into
three stages, with the range of less than 0.03, greater than 0.03 but less
than 0.17, and greater than 0.17. All the features in those 3 stages were
the same as in ref. [50]. Batalha et al. [51] studied the effects of met­
al–acid balance and metal–acid intimacy for hydroisomerization of n-
hexadecane using HBEA zeolites as the acid support. They made three
series of Pt loaded HBEA catalysts according to the intimacy difference.
The concentration of Brønsted acid sites were represented by CH+, which
included those acid sites able to retain pyridine at 150 ◦ C. On these three
series of catalysts, similar effects of CPt/CH+ ratio were found, and the
main difference is the exact values of nodes between the first and the
second stage. Those CPt/CH+ values were 0.0040, 0.015 and 0.015 for
these three series of catalysts, respectively.
From the above results and discussion, one can get some insights
about the effects of CMe/CA (or nMe/nA): 1) For hydroisomerization of
both light alkanes and long-chain alkanes, the effects of CMe/CA ratio can
be divided into three stages. In these three stages, the activity, stability
of catalysts and products distribution varies. The best hydro­
isomerization performance of catalysts can be obtained at the third
stage. However, it is worth noting that even the high CMe/CA is necessary
for high yield of isomers and maximal stability, over loaded metal can
also cause negative effects, such as hydrolysis reaction and shadowing
acid sites [52–55]. 2) The effects of CMe/CA ratio is not the same for light
alkanes and long-chain alkanes. The difference was concluded in the
following two aspects: a) In the second stage, the cracking reaction for
light alkanes exists but not as obvious as it for long-chain alkanes. b) the
value of CMe/CA ratio is not the same. The first aspect can be attributed
to the higher reactivity of long-chain alkanes [56,57]. While the second
aspect may not only due to the reactivity gap but also attributed to the
different catalysts and reaction conditions studied.
3.2. Comparison of the effects of acid function
The effects of acid function of the catalysts have an essential role in
hydroisomerization of normal alkanes, including acid strength, acid
density and spatial distribution of acid sites. However, those effects have
remarkable difference between light alkanes and long-chain alkanes.
3.2.1. Effects of acid strength and density
In the hydroisomerization of light alkanes on zeolites-based cata­
lysts, the tuning of acidity was usually along reducing the total acid sites
but increasing the density of strong acid sites.
For n-hexane hydroisomerization, Viswanadham et al. [58] studied
the performance of dealuminated mordenite based catalysts. The parent
mordenite was dealuminated by steaming and nitric acid. Significant
loss of total acidity was observed after dealumination. However, the
strong acid sites increased from 0.36 mmol/g in HM to 0.42 mmol/g in
S3-HM. Through the catalyst evaluation in a fixed bed, the conversion of
n-hexane increased by 20% at the same reaction conditions, while the
isomers selectivity kept almost constant at close to 100%. Thus, the
maximum yield of isomers was obtained on dealuminated samples.
Similar results were obtained by Saxena et al. [59] in the hydro­
isomerization of n-hexane. In their research, mordenite was used as
parent zeolites to prepare catalysts, denoted as HM. Dealumination of
mordenite was performed by acid leaching with increasing concentra­
tion of nitric acid, the samples were denoted as HM1, HM2 and HM3
respectively. By acid leaching, the total acid density decreased following
the sequence HM > HM1 > HM2 > HM3. However, the acid density of
strong ones changed inversely. This further influenced the conversion
and cracking selectivity on Pt-loaded catalysts. Compare to Pt/HM, the
cracking selectivity on Pt/HM1 to Pt/HM3 was reduced from 47% to
2.5% maximum. The conversion was increased from 21.1% to 31.0%
minimum. Thus, the isomer yields were increased. The enhanced cata­
lytic performance was attributed to the decrease of total acid density but
C. Wei et al.
increased strong acid sites. However, the interpretation of how the
change of acidity influences the performance was still lacking, and it
requires further study. Here, we try to give some conjectures. Firstly, the
reactivity of linear light alkenes is not high enough for their reactions on
medium and weak acid sites. Only strong ones can catalyze the initial
isomerization. This explains the increased conversion on catalysts with
more strong acid sites. Secondly, however, the successive isomerization
may have a higher possibility to happen on medium and weak acid sites.
That’s why the isomers selectivity increased with the decreasing total
acid sites.
While in the hydroisomerization of long-chain alkanes, the general
idea was to lower the acid strength and acid density. Chen et al. [60]
reported a bundle-shaped ZSM-22 zeolites synthesis with modified acid
strength. Compared to conventional hydrothermal synthesis, the syn­
thesis conditions were tuned by the addition of ethanol. They found the
difference of acid strength and Al atoms coordination environment be­
tween these samples. Compared with conventional ZSM-22, the strong
acid sites of the bundle-shaped samples were reduced from 59.65 μmol
g− 1 to 36.10 μmol g− 1, and the weak ones were reduced from 74.98
μmol g− 1 to 49.99 μmol g− 1. It was regarded that the change of Al atom
coordination environment was responsible for the decrease of Brønsted
acid strength. The result of n-dodecane hydroisomerization showed that
the mild Brønsted acid strength of bundle-shaped ZSM-22 led to the
selectivity enhancement from 43.82% to 52.10%. This paper revealed
the relation between the Brønsted acid strength and the Al atom coor­
dination properties, and confirmed that the mild acid strength favored
the high selectivity. Parmar et al. [61] reported hydroisomerization of n-
hexadecane over Pt/ZSM-22 catalysts, in which the acidity of ZSM-22
was tuned by ion-exchange method. Using Group II cations, Ca2+,
Mg2+, Ba2+, in the ion-exchange of ZSM-22, remarkable drop in
Brønsted acid sites and reduction of Brønsted acidity level can be
observed. The hydroisomerization of n-hexadecane over Pt/ZSM-22
catalysts using calcium-exchanged ZSM-22 zeolites showed evidently
higher selectivity of branched isomers. For example, Ca2+ exchanged
catalysts showed Brønsted acid sites decreased by 20.4%, and the iso­
mers selectivity increased by 6–7%. The ion-exchanged ZSM-22 was said
to favor better metal and acid balance in catalysts. The mild acid
strength of catalysts after ion exchange favored the isomerization rather
than cracking of adsorbed carbenium ions [62]. Feng et al. [63] studied
the effects of dynamic and static crystallization in the synthesis of ZSM-
22 zeolites. Using different crystallization conditions, ZSM-22 zeolites
were formed from precursors with the same SiO2/Al2O3 ratios from 70
to 110. The analysis of these ZSM-22 samples showed that the differ­
ences are mainly exhibited on two aspects, namely Brønsted acidity and
crystal size. At each SiO2/Al2O3 ratio, those ZSM-22 samples crystallized
in the dynamic condition showed lower overall Brønsted acid sites
density, especially for those strong ones. The Brønsted acidity difference
was attributed to the higher framework Si/Al ratio and the decrease of
Si-O-Al bridge hydroxyl. The hydroisomerization of n-Decane using
catalysts based on dynamically formed ZSM-22 showed higher isomer
selectivity. It was attributed to the relatively weak Brønsted acidity and
more pore mouth exposure.
Niu et al. [64] reported the synthesis of siliceous ZSM-22 zeolite,
named Z-Si. The analysis of Z-Si and comparison with silica–alumina
ZSM-22 showed significant reduction of Brønsted acid density and
strength. The total Brønsted acid density was reduced from 176 μmol g− 1
on Z-40 to 13 μmol g− 1 on Z-Si, and the density of strong ones was
reduced from 146 μmol g− 1 to 3 μmol g− 1. The lowered acidity was
attributed to the existence of vicinal silanol and silanol nests in Z-Si. Pt-
loaded bifunctional catalysts were prepared with Z-Si and silica­
–alumina ZSM-22. Hydroisomerization of n-Dodecane using these cat­
alysts showed the selectivity was higher by about 10% on Pt/Z-Si
catalyst at each conversion level. These results can be attributed to the
low Brønsted acid density and weak strength introduced by the vicinal
silanol and silanol nests. The weak acid strength favors the desorption of
isomers and can suppress the successive isomerization, therefore limit
6
Fuel xxx (xxxx) xxx
the cracking.
Liu et al. [65] reported the synthesis of Fe substituted ZSM-22. The
decrease of Brønsted acidity was obtained by Fe substitution in the
framework of ZSM-22. Acidity analysis of Fe-containing ZSM-22 showed
that compared to conventional ZSM-22 zeolites, the addition of Fe had
evidently decreased the Brønsted acid density and strength. The results
of n-dodecane hydroisomerization showed higher selectivity was ob­
tained on Fe substituted catalysts. For example, the weak and strong
Brønsted acid density of H-ZF-1 was reduced by 20 μmol g− 1 and 63
μmol g− 1 compared to conventional H-ZSM-22, respectively. And the
isomers selectivity on Pt/H-ZF-1 was always higher than conventional
Pt/H-ZSM-22 by about 25% at each conversion. The reduction of
Brønsted acid density and strength was attributed to framework Al was
partially substituted by Fe which has low polarizability. And Fe-OH-Si
bridge hydroxyls inside the zeolite framework have lower Brønsted
acid strength than Al-OH-Si bridge hydroxyls. The low acid strength and
acid density were believed to have better performance on the desorption
of isomer products and can maintain better metal–acid balance, there­
fore the isomers selectivity was enhanced.
It seems for long-chain alkanes, modifications on the zeolites for
reducing the acid strength and density were efficient ways to enhance
the isomers selectivity. However, different opinion was given by Noh
et al. [66]. They studied the relation between acid strength and isom­
erization selectivity of linear alkanes, and gave their interpretation.
With the combination of theoretical calculation (DFT) and experiments,
n-heptane and its isomers were chosen as model reactants, and alumi­
nosilicates with various pore topology and acid strength (tuned by
different heteroatom substitution in the framework) were chosen as acid
supports. From the results, it was demonstrated that the intrinsic
β-scission/isomerization rate ratio on each single-sojourn acid site
decrease with the increase of acid strength. With the decrease of acid
strength, β-scission transition states became more preferentially stabi­
lized. Contradict to general impact β-scission was favored on mild or
weaker acid sites rather than isomerization. It was argued the observa­
tion that hydroisomerization of long-chain alkanes on catalysts with
strong acid strength led to higher cracking was due to the diffusion-
enhanced secondary β-scission of primary isomers. Therefore, whether
to enhance or reduce the acid strength for higher yields of isomers still
needs to be discussed. And in the future studies, it shall be accompanied
with insights to the diffusion constraints.
From above researches, it can be concluded that the tuning of acid
strength and density in hydroisomerization of light alkanes and long-
chain alkanes have great difference. For light alkanes, the goal of
enhancing isomer yields was always related to the increase of acid
strength and the strong acid density. It seems the isomerization reaction
for n-pentane and n-hexane was favored on Brønsted acid sites with
higher strength. However, for long-chain alkanes, the modifications
were aiming at reducing the acid strength and density. This significant
difference mainly addresses from two reasons. The first reason is the
reactivity of long-chain alkanes is higher, therefore, mild acid strength is
enough to catalyze the reaction. This discrepancy in reactivity is mainly
manifested in the overall conversion versus temperature under the same
condition. For example, as shown in Fig. 1, to reach the same conversion
level, the temperature needed for n-hexane, n-heptane and n-octane
follows the sequence of n-hexane > n-heptane > n-octane [67]. Similar
results were also reported from n-C5 to n-C11 [57,68–70]. The second
reason is alkanes with longer chain length suffer more severe diffusion
limitations [39]. In Fig. 2, Smit [39] has summarized the self-
coefficients of n-alkanes of different chain length according to the re­
views of Jobic and Theodorou [71,72]. It can be seen whether it is from
molecular simulation or experiment, the diffusion coefficient decreases
almost exponentially with the increase of chain length. If the acid
strength is too strong, excessive isomerization would happen during the
slow diffusion. As a result, cracking reactions will be dominant. How­
ever, the lower acid strength also causes excessive energy consumption.
For example, to reach a conversion of 50%, a reaction temperature of
C. Wei et al. Fuel xxx (xxxx) xxx

Fig. 1. Conversion of individual alkanes (nC6, nC7 and nC8) vs. the reaction temperature on a Pt (a) or Pd (b) loaded H-Beta catalyst. Adapted from [67] with
permission from Elsevier.

catalysts, efforts have been made to tune the location of acid sites.
To date, ZSM-22 is one of the most widely used and studied acid
supports in the hydroisomerization of long-chain alkanes. It’s argued
that the Brønsted acid site locations for ZSM-22 zeolites can be generally
classified as three types: on the external lateral surface of ZSM-22 rods,
on the external surface close to the pore mouth and inside the micro­
pores [77]. Those acid sites inside the micropores is claimed only
accessible for n-alkanes because of the narrow pore size of ZSM-22,
which is 0.45*0.55 nm [78]. Furthermore, n-alkanes which is going
through the micropores usually undergo β-scission due to the severe
spatial confinement. While the acid sites on the lateral surface are
usually regarded have no shape selectivity, so they will randomly absorb
branched isomers and thus cause β-scission. Only those acid sites near
the pore mouth are believed have shape selectivity due to “pore mouth”
and “key lock” mechanisms as mentioned above.
Wang et al. [79] synthesized a series of Pt/ZSM-22 catalysts with
different acid densities on different locations. In their work, two stra­
tegies were used to tune the acidity. The first strategy was based on the
protective effects of the templates during NH4+ ion exchange.
Compared to conventional fully-detemplated ZSM-22, the micropore
volume of partially-detemplated ones was reduced from 0.090 to 0.094
Fig. 2. Self-diffusion coefficients of the n-alkanes in MFI as a function of chain
cm3/g to 0.001–0.007 cm3/g. And the retained template was believed to
length at 300 K as obtained by various techniques: ●, molecular simulations; □,
have exhibited the NH4+ ion exchange within micropores, and thus
QENS; △, PFG-NMR. The asterisks correspond to extrapolations to 300 K.
Adapted from [39] with permission from ACS.
reduced the acid density inside the micropores. The second strategy was
tailoring the total Brønsted acid density by adjusting the concentration
of NH4+ in the ion exchange step. It’s shown that with the decrease of
200–250 ◦ C is required for n-pentane and n-hexane on MOR based
NH4+ concentration, the total acid density was also reduced, without
catalysts, a higher temperature of 300–400 ◦ C is necessary for long-
changing the relative acid distribution. The change of total acid density
chain alkanes on ZSM-22 and SAPO-11 based catalysts [23,58,73,74].
and accessibility factor (AF) caused by these strategies was shown in
Not to mention the hydroisomerization is equilibrium limited, which
Fig. 3. The accessibility factor (AF) was defined as the ratio between the
means high yield for isomers at higher temperature is not allowed
amount of external Brönsted acidity and total Brönsted acidity [80]. In
[68,75,76]. Thus, the mild acid strength for hydroisomerization of long-
the end, they made the catalyst Pt/230AN0.2 by combining these two
chain alkanes can be seen as a sacrifice to the diffusion limitations.
strategies. The catalytic hydroisomerization of n-dodecane on Pt/
230AN0.2 showed this combined strategy achieved the highest isomer
3.2.2. Effects of acid sites location
yields increased from 40.7% to 63.7%. It is regraded that there exists a
To the best of our knowledge, research about the effects of acid sites
kind of synergic effect with the two strategies. The reduced acid density
location for light alkanes is rare. However, its importance for long-chain
inside the micropores exhibited cracking reactions of n-alkanes diffusing
alkanes is already confirmed by some researchers. Therefore, this sub­
along the channels. While the reduced total acid density not only limited
section is mainly focused on long-chain alkanes. For long-chain alkanes,
the cracking on the external surface, but also increased the isomeriza­
it is believed only linear ones can enter the micropores rather than
tion through “key lock” mechanism.
branched ones. Indeed, it is one kind of shape selectivity and is broadly
Niu et al. [81] studied the effects of acid site distribution of ZSM-22
utilized to enhance isomer yields. However, because of the severe
on the isomers selectivity. Firstly, they synthesized a ZSM-22 with a
diffusion constraints imposed by the micropore channels, excessive
core–shell structure to tune the acid function on the external surface. In
contact time between isomers and Brønsted acid sites tends to cause
their research, the epitaxial growth method was used to fabricate the
secondary cracking. Besides, nonselective external acid sites also favor
highly siliceous shell with reduced acid density on the external surface,
secondary cracking. To deal with the secondary cracking of isomers
namely reduced by more than 50% compared to conventional ones.
trapped in the micropores or adsorbed on the external surface of

7
C. Wei et al.
Fig. 3. Correlation between Micropore Exposed and total Brönsted acidity & AF (a), and correlation between NH4+ aqueous concentration and total Brönsted acidity
& AF (b), and schematic acidity distribution. Adapted from [79] with permission from Elsevier.
Unexpectedly, using catalysts based on this ZSM-22, isomers selectivity
in n-dodecane hydroisomerization was found reduced by about
0.9–6.4% at the conversion near 90%, compared with catalysts based on
conventional ZSM-22. It was attributed to the reduced external acid
density suppressed the adsorption of reactants on the lateral surface,
thus in turn enhanced the reactants’ diffusion inside the micropore. And
the diffusion confinement, as well as the acid catalysis inside the pores,
caused excessive cracking. Therefore, another strategy was taken to
study the effects of acid sites inside the micropores. They used carbon­
ated templates to block the micropore of core–shell ZSM-22, as shown in
Fig. 4. Using n-dodecane as model reactant, the hydroisomerization
result showed that the isomers selectivity was enhanced by 2.2–2.7%
compared with catalysts based on conventional ZSM-22, at the conver­
sion near 90%. Since the Brönsted acid density on the external surface
was reduced to a relatively low value, and acid sites deep inside the
micropores were not accessible due to the blockage, the acid sites near
the pore mouth thus became dominant in the acid function. Similar
result was also obtained by Lv et al. [82]. On Pt/Z-22PF catalyst with
ZSM-22 was partially filled channels by in-situ coke deposition, the
maximum isomer yield was enhanced by 6% compared to conventional
Pt/ZSM-22 catalyst. The increased selectivity was attributed to the
highly selective “pore mouth” and “key lock” catalysis.
The same acid location effects can be observed on SAPO-11 molec­
ular sieves. Kim et al. [80] reported the hydroisomerization of n-
dodecane on mesoporous Pt/SAPO-11 catalysts with different predom­
inant locations of acid sites. With the help of organosilane templating,
Fig. 4. A schematic diagram showing the structure of core–shell ZSM-22 with micropores blockage. Adapted from [81] with permission from RSC.
8
Fuel xxx (xxxx) xxx
the acid sites of SAPO-11 were predominantly located on the external
surface. While the use of carbon templating maintained the predominant
acid location inside the micropores, and fabricated mesopores structure.
The result showed that the maximum isomer yields of n-dodecane on the
catalyst with mainly external acid sites was only 13%, while that of the
catalyst with predominantly internal acid sites was 84%. In comparison,
this number in conventional Pt/SAPO-11 without mesopores structure
was 44%. The results indicated that the nonselective external acid sites
on SAPO-11 mainly favors the cracking reaction of isomers, while the
internal acid sites are selective for isomerization. However, the effect of
removing diffusion constraints was also obvious for higher isomer
yields. Zhang et al. [83] reported the preparation of a kind of stable
SAPO-11 nanosheets with partially blocked acidic sites inside micro­
pores, named as N-SAPO-11. The synthesized N-SAPO-11 had the
thickness of 10 to 20 nm, and the acidic sites inside micropores were
partially blocked. Therefore, the acid sites near the pore mouth became
predominant. Using the Pt loaded N-SAPO-11 and conventional bulk
SAPO-11 as catalysts, the reseult of n-dodecane hydroisomerization
showed evident difference on isomers selectivity. Catalyst based on N-
SAPO-11 always had higher isomers selectivity by about 5% at each
conversion. The enhanced isomers selectivity was attributed to the in­
crease of isomerization through “pore mouth” and “key lock” catalysis.
In this section, the effects of acid sites location were discussed. First,
the key role of acid sites location on catalysts for hydroisomerization of
long-chain alkanes was proved. Acid sites located on the external surface
in some degree are responsible for secondary cracking, due to the lack of
C. Wei et al.
shape selectivity. While the acid sites near pore mouth are in favor of
isomerization through “pore mouth” and “key lock” catalysis, which are
highly selective. Therefore, high isomer yields can be obtained when the
acid sites near pore mouth become predominant. However, the effects of
acid sites inside micropores are not in good agreement. Some studies
tend to believe its negative influence on isomers selectivity, considering
the diffusion constraints inside micropores may prolong the contact time
between primary isomers and acid sites, and thus increase secondary
cracking. While others tend to regard it is benefit for selectivity
enhancement. In our view, the effects of acid sites located inside mi­
cropores may vary based on the structure of acid supports and the chain
length of reactants. Therefore, further research is necessary to acquire
valid conclusion.
3.3. Effect of metal–acid intimacy
Considering the hydroisomerization reaction is related to reactant
diffusion between hydrogenation function and acid function, it is
naturally to question how is the reaction affected by the distance of these
two functions.
Weisz et al. [84] have proposed the so-called “intimacy criterion” for
hydroisomerization by using physically mixed Pt/silica and acidic silica-
alumina catalysts with different size in the 1962. They proved that in the
range of micrometer scale and millimeter scale, isomer yield of n-al­
kanes hydroisomerization increase with the decline of metal–acid sites
distance. Beyond millimeter scale distance, the bifunctionality of the
catalysts almost disappeared. This phenomenon was ascribed to the
limited diffusion length of alkene intermediates beyond which they have
little chance to access another metal site to be hydrogenated. It was
further simplified to the principle “the close the better” for metal–acid
intimacy. Their work was recently re-confirmed by Batalha et al. [51]
They studied the effect of metal–acid intimacy in the range of micro­
meter distance using S1, S2 and S3 series catalysts which are based on
zeolites and alumina. The intimacy difference was possessed by BEA
zeolites ion exchanging with Pt precursor or mixing with Pt loaded
alumina. The distances between acid site to metal site on S1, S2, and S3
were estimated by the size of aggregates with at least 12.5 μm, 12.5
μm–300 μm and 300 μm, respectively. It was found the yield of i-C16 in
n-C16 hydroisomerization decrease with the sequence of S1 > S2 > S3
with ideal CPt/CH+ ratio. Besides, turn-over frequency (TOF) of the acid
sites varies in the same trend. These results indicate that in the intimacy
range they studied, the catalytic performance still follows the principle
of “the closer the better”. However, it has been being challenged in the
last few years.
In 2015, Zečević et al. [85] studied the metal–acid intimacy in
nanometer scale. The catalysts they used were Pt loaded extrudes of
γ-alumina binder (negligible acidity) and Y zeolites (acid site supplier).
The Pt was selectively loaded on γ-alumina or on Y zeolites through
choosing Pt precursors with different electric properties and adjusting
pH of solutions, denoted as Pt-A/Y and Pt-Y/A respectively. HAADF-
STEM and EDX were used to characterize catalyst slices with 70-nm-
thick, and the closest metal–acid intimacy of Pt-Y/A and nanometer-
scale intimacy of Pt-A/Y was confirmed. Hydroisomerization results of
n-C10 and n-C19 both showed higher isomerization selectivity on Pt-A/
Y with identical conversion, being contrary to “the closer the better”
principle. It was attributed to that Pt particles were mainly located in­
side the micropores to reach the closest intimacy in the case of Pt-Y/A,
which means alkene intermediates have to go through the zeolite
channels to access another metal site. In this process, it will suffer from
diffusion limitations and lead to higher possibility of secondary re­
actions of cracking and coking. On the other hand, on Pt-A/Y catalyst,
alkene intermediates could be isomerized on the surface of zeolite Y and
diffuse back to the metal sites on alumina. Their work not only supplied
counterexample to the conventional intimacy criterion, but also
extended the view of the long chain alkene intermediates were mainly
isomerized in the outer layer of zeolites from medium-pore ones to large-
9
Fuel xxx (xxxx) xxx
pore Y. Similar work and results were reported by Ben Moussa et al.
[86], using Pt loaded aggregates of 12-ring pore BEA zeolite and
alumina. In their research, nanoscale and microscale aggregates were
prepared, and Pt was selectively loaded on zeolite or alumina to give a
closer or farther intimacy between metal sites and acid sites. Obviously,
no matter the size of aggregates, when Pt was loaded on zeolites, the
closer metal–acid intimacy was obtained. However, hydroisomerization
results of n-heptane showed catalyst with Pt located on alumina
possessed higher isomerization selectivity at conversion at 20.5 ± 2%
and 50 ± 4%, rather than the one with Pt located on zeolites. In other
words, the best hydroisomerization performance was achieved on the
catalyst with farther intimacy other than on the one with the closest
intimacy in the range of nanometer scale. These unique behaviors were
further explained by Oenema et al. [87] using so-called “remember ef­
fect” that when the metal sites were not located inside zeolites micro­
pores, e.g. on alumina binder, linear alkene intermediates will be
catalyzed in the outer layer of zeolites and remember the entrance to
timely escape to avoid further reaction. Of note is that, in above-
mentioned studies, it has been emphasized the metal–acid intimacy
closer than nanoscale was obtained by placing Pt particles inside
channels of zeolites. In such condition, the metal–acid intimacy is not
the only variable anymore, the change of pore structure of zeolites has
also been included implicitly.
To exclude impacts imposed by pore structure, nonporous materials
were used to study the effect of metal–acid site proximity by Samad et al.
[88] Four catalysts with different metal–acid intimacy level were pre­
pared, namely PTA-11 and PTA-DI with atomic-scale, CPA-4 with
nanometer-scale, PM with micrometer-scale, and L-1 with millimeter-
scale. The atomic-scale and nanometer-scale intimacy were achieved
by selectively adsorption of Pt precursors on silica-alumina mixed oxides
or on silica. Micrometer-scale and millimeter-scale affinities were con­
ducted by physical mixing or quartz separation of Pt loaded silica and
acidic silica-alumina. The results of n-heptane hydroisomerization
showed the catalyst CPA-4 with nanometer-scale possessed ~13%
higher i-C7 selectivity than atomic-scale catalysts at conversion 22 ± 3%
conversion. This proves that even if the change in pore structure is
excluded, at nanometer and smaller scales, principle of “the closer the
better” is still not applicable.
However, the opposite results were obtained by Mendes et al. [89] in
2020. They also prepared composite catalysts with zeolite Y and
alumina, selectively deposing Pt on one of them to acquire different
distance between metal and acid sites. On Pt/HUSY-Al2O3 with
maximum acid-Pt distance of 10–20 nm, the maximum yield of i-C16 in
n-C16 hydroisomerization was much higher than it on Pt/Al2O3-HUSY
with acid-Pt distance of 100–10000 nm. Their work supported “the
closer the better” principle again. And they have pointed out the loop­
holes of the explanation given by Zečević et al. [85] for Pt loaded
bifunctional catalysts with Pt on alumina binder, i.e. larger metal–acid
distance, possessing higher isomers yield. They claimed if the place
where the isomerization reaction occurs is zeolites’ outer layer, then the
conversion of the reaction should be reduced. However, that was not the
fact.
In conclusion, the metal–acid intimacy of bifunctional catalysts plays
a crucial role in hydroisomerization of n-alkanes. Once the distance
between metal and acid sites is large enough, the activity will be reduced
dramatically for the two functions cannot cooperate or the isomer yield
will decline for undesired secondary reactions. However, no unified
point of view has been drawn on how far the intimacy should be and it
needs further study.
3.4. Recent advance in modifying metal sites
Noble metals like Pt and Pd are the most popularly used components
to endue hydroisomerization catalysts (de)hydrogenation ability in
theoretical research and industrial application. However, their high
price has also caused worry in expanding their use. Recently, efforts
C. Wei et al.
have been made on lowering their content, enhancing their hydroge­
nation efficiency and replacing them with non-noble metals, accompa­
nied by the introduction of new loading methods.
It’s generally believed high hydrogenation efficiency of Pt and Pd
can be reached by small particle size and high dispersion for the unique
electron structure of surface metal atoms and superior activity of some
crystal facets, thereby, their minimum content in catalysts can be
reduced in some degree [90–92]. In this regard, Wang et al. [93]
developed the “vacuum assistant” strategy (VA) to enhance the disper­
sion of Pt clusters on SAPO-11, thereby lowering the loading. The key
step was to exhaust gas from the micropores of SAPO-11 before
impregnating the metal precursor. In this way, they made V-0.15Pt/S-11
catalyst, namely SAPO-11 loaded with 0.15 wt% Pt. The counterpart,
catalyst C-0.5Pt/S-11 was made through conventional impregnation
procedure with Pt loading of 0.5 wt%. The hydroisomerization perfor­
mance of n-C16 has shown that V-0.15Pt/S-11 was superior to C-0.5Pt/
S-11, with a maximum i-C16 yield of 89% vs. 80%. The author ascribed
the superiority to its smaller Pt particle size (~1 nm) and better synergy
effect with acid sites achieved by the VA strategy. Intensive capillary
action of Pt precursor in the “clean” channels of SAPO-11 guaranteed
their effective adsorption, which was hindered by gas resistance inside
through conventional methods. Geerts et al. [94] applied the atomic
layer deposition (ALD) method to deposit Pt nanoparticles on ZSM-5.
Trimethyl(methylcyclopentadienyl)platinum was chosen as Pt precur­
sor in cold wall ALD. Compared to conventional incipient wetness
impregnation, a smaller size of Pt particles was obtained (2–4 nm versus
15–20 nm). Therefore, the reactivity and isomer selectivity of the
catalyst was enhanced in n-decane hydroisomerization. Al-Rawi et al.
[95] reported a supercritical CO2 (ScCO2) assisted impregnation
method, using dimethyl(1,5-cyclooctadiene) platinum as the precursor.
For comparison, the conventional wetness impregnation method was
used. Based on H-ZSM and H-MOR, they assessed the influence of the Pt
loading method on n-hexane hydroisomerization. It was found the cat­
alysts loaded by ScCO2 showed higher isomer yield and lower cracking
yield at all temperatures. Besides, for catalysts loaded by ScCO2, the
cracking reaction was much less sensitive to temperature change
compared to wet impregnated ones. The superiorities were ascribed to
the smaller and more uniformly distributed Pt particles by ScCO2 (1–2
nm vs. 6–9 nm). The function of ScCO2 in the loading process was
believed to have accelerated the nucleation rate and suppressed the
growth rate of Pt crystals, and finally the Pt size and distribution were
affected.
In addition to enhancing the hydrogenation efficiency of noble metal
sites by adjusting loading methods, attempts have also been done to
entirely replace noble metal by non-noble metals. Wang et al. [96] have
explored the application of non-noble bimetallic catalysts in hydro­
isomerization. The same “vacuum assistant” strategy was used to co-
impregnate nickel and molybdenum on SAPO-11. A series of catalysts
based on SAPO-11 with different Ni and Mo loadings were made to
optimize the metal content. The conventional 0.5 wt% Pt loaded SAPO-
11 was chosen to be compared. In the hydroisomerization of n-C16,
3.0Ni-0.5Mo/S-11 was found possessing comparable maximum i-C16
yield with Pt loaded catalyst, namely 81.4% versus 81.0%. Through
their analysis, several origins were found to have gifted 3.0Ni-0.5Mo/S-
11 high performance. Firstly, the addition of Mo enhanced the interac­
tion between Ni and SAPO-11, resulting in its smaller particle size and
higher dispersion during reduction, which is positive for enhancing
hydrogenation ability [97]. Besides, the existence of MoOx species has
drawn electron transfer between Mo and Ni due to orbital overlapping
and the tuning of surface charge was believed to enhance the intrinsic
activity of Ni, resulting in easier H activation and desorption. Harmel
et al. [98] showed the possibility of replacing Pt with molybdenum
oxide. They prepared a series of catalysts with MoOx species acting as
hydrogenation function, and the acid function was supplied by amor­
phous silica-alumina (ASA) or Al-SBA-15. By adjusting the loading
method and content, they found the best n-C7 hydroisomerization
10
Fuel xxx (xxxx) xxx
performance can be obtained on the catalyst with 13 wt% Mo loading
through physical mixing of MoO3 with ASA. The i-C7 yield on this
catalyst was comparable to the counterpart of 0.7 wt% Pt loading
(64.5% versus 65.7%). It was believed that MoO2 with a crystal size of
30–40 nm was the active phase supplying hydrogenation function, and is
coordinated to the surface oxygen and MoOx nearby. However, consid­
ering the extremely high loading of Mo, the application of this meth­
odology in the most commonly used zeolite-type catalysts might
encounter problems, such as severe blockage of micropores. To avoid the
blockage addressed by overloading and at the same time enhance the
dispersion of non-noble metal, Kim et al. [43] reported replacing Pt with
2 wt% Ni in hydroisomerization. In their research, a key catalysis ma­
terial, namely nanosponge-like ZSM-5, was synthesized with the help of
a multiammonium surfactant as a structure-directing agent. Its unique
morphology was constructed by ZSM-5 nanosheets with 2.5 nm thick­
ness along the 10-ring straight channel, and mesopores of ca. 5 nm were
evenly distributed between these sheets. Nickle was loaded on this ZSM-
5 by incipient wetness impregnation, and 1 wt% Pt was loaded to be
compared. In the hydroisomerization of n-dodecane, the Ni-loaded
catalyst with optimized content (2 wt%) showed comparable activity
and isomer yield to the Pt-loaded counterpart. The high efficiency of Ni-
loaded catalyst came from its small particle size of ca. 5.4 nm. This high
dispersion of Ni on conventional ZSM-5 can hardly be achieved since the
relatively weak interaction between Ni species and the support will
cause severe agglomeration during calcination and H2 reduction.
However, thanks to the uniform mesopores in nanosponge-like ZSM-5,
the Ni species can be stabilized by mesopore walls like a sandwich.
Therefore, the strengthened interaction prevented agglomeration during
the reduction process. This idea of controlling the structure of the sup­
port to enhance the its interaction with metal species, thereby improving
the hydrogenation efficiency of non-noble metals is promising.
From the above discussion, we can see that people have made efforts
to reduce the amount of precious metals from different aspects,
including adopting new loading methods, regulating non-precious
metals to completely replace precious metals, and so on. These efforts
are of great significance to the industrial promotion of short-chain and
long-chain n-alkane hydroisomerization technology and the production
of low-cost clean oil products.
4. Modifications on the textural structure of molecular sieves for
long-chain alkanes
Molecular sieves-based catalysts for hydroisomerization show great
shape selectivity for isomers. Since for long-chain reactants, the modi­
fications on the textural structure of molecular sieves are much more
important than it for light alkanes, due to their worse diffusivity and
higher reactivity. Meanwhile, modification of textural structure for light
alkanes isomerization is rarely reported. The effects of the textural
structure modifications only for the hydroisomerization of long-chain
alkanes will be discussed in this chapter. The most used acid supports
are unidimensional 10 MR or 12 MR microporous materials, such as,
ZSM-22 and SAPO-11, considering their unidimensional channels have
great reactant selectivity for linear alkanes. The diffusion constraints
inside the channels are always severe due to the unsuitable path length,
and it leads to undesired cracking. To overcome this disadvantage and
increase the pore mouth exposure, efforts have been made mainly in two
aspects, i.e., fabricate hierarchical pore structure and reduce the crystal
size of catalytic materials.
4.1. Effect of hierarchical pore structure
Hierarchical pore structure refers to the fabricated mesoporous and/
or macroporous channels in the microporous structure. Compared to
pure micropores, hierarchical pore structure is regarded to have better
diffusivity and shortened diffusion length. There are mainly two series of
methods used to fabricate the hierarchical pore structure, which are so
C. Wei et al.
called “top down” method and “bottom up” method.
“Bottom up” method means by using some physiochemical
methods, the hierarchical structure is fabricated directly in the synthe­
sis. Using mesoporogen and template to fabricate hierarchical structure
can be regarded as a conventional “Bottom up” method. However, the
most disappointed feature of “Bottom up” method is that it cannot be
applied to all the catalytic materials. Nevertheless, over last few years,
studies on suitable hierarchical pore structure catalysts of hydro­
isomerization based on this method are still attractive.
Fan et al. [99] reported the hydrothermal synthesis of intersecting
micropore and mesopore structural SAPO-11 by simultaneously using
tetradecylphosphoric acid (TDPA) as mesoporous template and di-n-
propylamine (DPA) as microporous template. The characterization of
high-resolution transmission electron microscopy demonstrated the
formation of mesopores with 4–7 nm pore size. N2 adsorp­
tion–desorption showed the mesopore volume of hierarchical SAPO-11
increased from 0.06 cm3/g to 0.31 cm3/g compared with conventional
sample. The catalyst was prepared by loading Pt on the hierarchical
SAPO-11 sample. The result of n-C8 hydroisomerization on this catalyst
showed the total selectivity of iso-C8 was increased from 88.5% to 97.9%
at the conversion of 43%, and the selectivity of di-branched iso-C8 was
increased by 21.5%. To explain the increased isomers selectivity, espe­
cially for di-branched ones, they proposed a novel reaction path, which
is shown in Fig. 5. It claimed that the mono-branched isomers were
mainly formed inside the micropores, however, the fabricated hierar­
chical structure shortened their path length, thus reduced the possibility
of cracking. Successively, due to the mutually penetrating between mi­
cropores and mesopores, those mono-branched isomers were further
isomerized into di-branched form without steric hindrance. In the end,
the isomers selectivity was promoted. This newly proposed reaction path
expanded the roles of mesopores in the isomer selectivity enhancement.
Tao et al. [100] reported the synthesis of inter-crystalline meso­
porous SAPO-11 using dry gel conversion, [3-(Trimethoxysilyl)propyl]
octadecyldimethylammoniumchloride (TPOAC) was added as meso­
pores template. In as-synthesized SAPO-11, mesopores centered at 4.5
nm were fabricated. Catalysts were made by loading Pt. The result of n-
dodecane hydroisomerization showed that the isomer yields increased
from 69.2% to 77.3% at the conversion of about 90% compared with on
catalysts based on conventional SAPO-11. Recently, they have devel­
oped a new way to synthesize hierarchical nanosized single-crystal
SAPO-11 without using mesoporogen [101]. By carefully adjusting the
composition of precursors and heating at elevated temperatures, the
obtained SAPO-11 was demonstrated to have ~65% of intracrystalline
mesopores accessible to the crystal surface, which is promising to
enhance hydroisomerization performance. Wen et al. [102] reported the
synthesis of mesoporous Pt/SAPO-11 catalysts using F127 and super­
critical carbon dioxide as combined mesoporous templates. The resulted
hydroisomerization reaction of n-C9 showed the high selectivity of di-
branched isomers of 33.5% and low cracking selectivity of 8.0% at the
conversion of 20%. The enhanced selectivity in the above two pieces of
research was attributed to the reduced diffusion constraints by short­
ened diffusion path. And the use of mesopores templates can be regarded
as an effective route to synthesize mesoporous molecular sieves.
Fig. 5. Reaction and diffusion pathways for n-octane isomerization in the pore
channels of H-SAPO-11-HI monocrystal. Adapted from [99] with permission
from Elsevier.
11
Fuel xxx (xxxx) xxx
Besides the conventional methods, researchers have made great ef­
forts on controlling the crystallization step of synthesis gel or precursors
to attain hierarchical pore structure. Zhang et al. [103] reported a two-
stage hydrothermal crystallization route to synthesize mesoporous
SAPO-11 with two types of mesopores, smaller ones and bigger ones,
centered at ca. 2.4 nm and at ca. 17–24 nm. The fabrication of the micro-
mesoporous structure was achieved by the addition of CTAB and F127.
The result of n-C8 hydroisomerization showed maximum isomer yields
promotion from 60.9% to 73.4%. The promotion was attributed to the
shortened path length and increased pore mouth, which favors highly
selective “pore mouth” and “key lock” catalysis. Tao et al. [104]
demonstrated a confined space approach to fabricate hierarchical
MgAPO-11 with AEL type structure which is the same as SAPO-11. By
adding furfuryl alcohol (FA) into mesoporous magnesioaluminophos­
phate (MAP) and successively carbonating FA into carbon film, the
coated carbon film can supply the space confinement during the crys­
tallization of MAP. As a result, the hierarchical MgAPO-11 with meso­
pores centered at 7 nm and 20 nm was formed. Comparison of n-
dodecane hydroisomerization was made between catalysts based on
hierarchical MAP and microporous MAP. The result showed higher
isomer yield was obtained at 90% conversion on hierarchical one
(86.6% vs 60.5%). The promoted isomer yield was attributed to the
shortened path length enhanced diffusion of multibranched isomers out
of micropores.
Recently, a novel method of affecting the crystallization and intro­
ducing mesopores in molecular sieves was applied, which is called the
oriented assembly strategy. Jin et al. [105] reported the synthesis of
hierarchical SAPO-11 by the oriented assembly of prefabricated nano­
crystallites. The SAPO-11 building blocks were prefabricated and fol­
lowed by further crystallization by particle attachment. The record
hydroisomerization performance was obtained on SAPO-11-PDDA,
whose hierarchical structure was confirmed with mesopores volume
increased from 0.13 cm3 g− 1 to 0.26 cm3 g− 1, BET surface area increased
from 134 m2 g− 1 to 302 m2 g− 1 compared with conventional SAPO-11.
The result of n-C7 hydroisomerization on Pt/SAPO-11-PDDA catalysts
showed a record yields (79%) of isomer. The advanced isomers selec­
tivity was attributed that the enhanced diffusivity and widened intrinsic
reaction-controlled regime successfully reduced the cracking possibility.
In 2018, they [106] reported another study of mesostructured SAPO-11
synthesis by oriented assembly strategy. The same method was used for
preparing the SAPO-11 building blocks [105]. In the assembly process,
they demonstrated the formation of “house of cards” structure with
mesopores that can be attained under the dynamic tumbling condition
without any additives. Besides, the addition of growth modifier cellulose
2-(2-hydroxy-3-(trimethylammonium) propoxy) ethyl ether chloride
(polyquaternium-10 or PQ-10) in the assembly process can greatly
reduce the size of SAPO-11 nanosheets from ca. 300 nm to ca. 20 nm.
BET surface area and mesopores volume of tumbling assisted (SAPO-11-
T) and PQ-10 assisted (SAPO-11-PQ) samples were increased by 41.0%-
78.4% and 23.1%-123.1% compared to conventional one (SAPO-11-C),
respectively. Fick’s second low was used to quantitatively measure and
compare the diffusion properties of SAPO-11-C, SAPO-11-T and SAPO-
PQ. The diffusion time constants of 2-methylhexane on SAPO-11-C,
SAPO-11-T and SAPO-PQ were 0.77 × 10− 3, 0.99 × 10− 3, and 1.17 ×
10− 3, respectively. As can be seen, SAPO-11-PQ has the best diffusion
properties, consistent with the highest iso-C7 yield of ca. 80% on Pt/
SAPO-11-PQ. These studies firstly confirmed the positive effects of hi­
erarchical pore structure on hydroisomerization of long-chain alkanes,
and indicated the novel oriented assembly strategy is not only a prom­
ising but also a flexible route to synthesis hierarchical pore structure as
well.
These results suggest that due to the hierarchical pore system con­
structed by both micropores and mesopores, the enhancement of isomer
selectivity for long-chain alkanes is remarkable. However, if one wants
to fabricate molecular sieves with hierarchical structure by “bottom up”
methods, the efforts on controlling the crystallization step should be
C. Wei et al.
paid. Furthermore, the usage of mesoporogen seems to be necessary at
most conditions. Therefore, development of novel routes in which the
consumption of mesoporogen can be reduced or avoided is favored in
the future.
“Top down” method means using the fresh molecular sieves as the
parent materials, and remodeling it by post-treatment strategies. In the
past few decades, people have tried dealumination with acid solutions to
post-treat molecular sieves to attain mesopores [107,108]. However,
using acid solutions will also cause undesired metal leaching and thus
influence acid function [109]. Therefore, over the last few years, re­
searchers paid more attention on alkaline desilication. The general
alkaline desilication procedures can be described as follows: First, pre­
pare alkaline water solutions with proper alkaline species and concen­
trations. In common, people use NaOH as alkaline species, and different
additives are added into the solutions, such as ethanol and surfactants.
Second, disperse the fresh molecular sieves into the alkaline solutions,
and maintain hydrothermal reaction at middle temperature for hours. In
the end, these treated molecular sieves should be washed with water or
dilute acid solutions.
The most important influencing factors of alkali desilication were
studied by Wei et al. [110] Their research was based on ZSM-12 zeolite,
and factors of NaOH concentration, alkaline treatment temperature, and
period were studied. The NaOH concentration was regarded as the most
influential in the desilication. Below the NaOH concentration of 0.2 M,
no mesopore fabrication can be observed. Higher temperature is favored
in desilication; however, its effect was not comparable to the effect of
concentration. While beyond 90 min period of desilication, changes in
the desilication rate can hardly be found anymore. The study suggested
that there exists a best NaOH concentration range and a proper treat­
ment period in generating mesopores in molecular sieves. And in further
studies of desilication of molecular sieves, all these factors should be
considered to proceed the experiments. Beyond the desilication condi­
tions, they also studied the desilication process of ZSM-12 with different
Si/Al ratios. It’s found that, in the same desilication condition, those
molecular sieves with higher Si/Al ratios favored the fabrication of
mesopores. It was attributed to that the framework Al can hinder the
extraction of Si.
Though single alkali desilication is an effective and promising way to
produce hierarchical pore structure both in the lab and in industry, it
does have some disadvantages. For example, the limited mesopores
introduction, ununiformed mesopores size, and destruction of micro­
pores [111]. In addition, a reduction of crystallinity was also found
[112–115]. To overcome these negative effects caused by single alkali
desilication in hydroisomerization of long-chain alkanes, modifications
have been made based on protective strategy or recrystallization
strategy.
Zhang et al. [116] reported the HDA-protected desilication of high
Si/Al ratio ZSM-48 zeolites. In their experiments, the desilication of
homemade ZSM-48 zeolites with a high Si/Al ratio equals to 200 was
studied using NaOH solution or NaOH+ HDA solution. Though all the
samples showed desilication of ZSM-48 zeolites caused crystallinity
reduction, the proper ratio of NaOH and HDA in the solution exhibited
the best preservation of crystallinity due to the protective effect of HDA.
So, in the hydroisomerization of n-C16, as-synthesized hierarchical Ni/
ZSM-48 catalysts with well-preserved crystallinity showed the highest
isomers selectivity. Wang et al. [117] reported the synthesis of hierar­
chical ZSM-22 with a dual-protected alkali post-treatment strategy. To
preserve the crystallinity of ZSM-22 and maintain high desilication ef­
ficiency [111] at the same time, they combined partial detemplation and
CTAB protection in alkali treatment. This unique strategy resulted in
mesopores formation centered at 3–4 nm. As shown in Fig. 6, in addition
to their uniformity, more pore mouth exposure caused by the protective
effect was confirmed. The protection effect of partial detemplation was
attributed to the template can prevent the contact between OH− 1 and Si-
O-Si linkages inside the micropores, therefore, desilication can only
happen in the template free region. While CATB micelles can stabilize
12
Fuel xxx (xxxx) xxx
Fig. 6. Brief mechanism scheme of ZSM-22 dual-protected alkali treatment.
Adapted from [117] with permission from ACS.
the Si leaching process by drilling effect and result in uniform meso­
porosity whose size is close to the CTAB micelles. The result of n-C12
hydroisomerization showed whether ZSM-22 was desilicated with or
without protection, total isomers yield on the mesoporous catalyst was
increase by 4.8%–33.6%. Besides, higher mono-branched and total
isomers yield was obtained on dual-protected ZSM-22 samples. The
enhanced catalytic performance on desilicated ZSM-48 and ZSM-22
samples was attributed to the increased pore mouth exposure and bet­
ter diffusion properties. While the better performance on samples with
protected-desilication process was addressed to that the protection
agents have overcome the uncontrollable silicon extraction.
Liu et al. [118] reported the synthesis of hierarchical ZSM-22 acid
support using the alkaline treatment and recrystallization process. In
their experiments, the H-ZSM-22 molecular sieves were treated with
different concentrations of alkaline solutions and recrystallization with
the help of CTAB. In comparison, they also synthesized the desilicated
samples using alkaline treatment alone, which was denoted as DeZEO.
The study of the textual properties showed that the samples fabricated
from simultaneous alkaline treatment and recrystallization process
attained uniform mesoporous materials on the lateral surface, while
DeZEO sample attained uniform mesopores. The uniform mesoporous
materials were demonstrated as MCM-41, which has mild Brønsted acid
strength. The results of hydroisomerization of n-dodecane showed that
catalysts using ZSM-22 with MCM-41 mesoporous structure as acid
support can evidently enhance the total isomers selectivity from 47.09%
to 91.70% at the conversion higher than 90%. This was attributed to the
mesoporous MCM-41 on the lateral surface of ZSM-22 not only can in­
crease the pore mouth acid sites, which can lead to the increase of “key-
lock” catalysis, but also can adjust the overall acid strength. Similar
positive effect caused by recrystallization on enhancing textual prop­
erties during desilication was also reported on ZSM-5 [119].
From above summarized studies, it can be seen that the mesopores
fabricated by “top down” method can evidently enhance the isomers
selectivity. It is usually attributed to the shortened diffusion path and
enhanced pore mouth exposure. However, the disadvantages caused by
single alkali desilication is very common. Therefore, to avoid the
negative effects of single alkali desilication, strategies such as protective
desilication and simultaneous desilication and recrystallization should
be considered and utilized. And from the aspect of environmental pro­
tection, the species of alkali used in desilication should be further
modified to avoid the pollution caused by broadly used NaOH.
4.2. Effect of crystal size
It is known that the process of alkene intermediates isomerizes on the
active protonic sites and the pathway length between two metal sites
play an important role in hydroisomerization of n-alkanes. Since
bifunctional catalysts with smaller crystal size allows more accessibility
of active protonic sites and shortened pathway length of alkene in­
termediates between two metal sites, downsizing the crystal is regarded
as a promising route to attain higher selectivity of isomers.
C. Wei et al.
Zhang et al. [120] studied the effect of the journey distance of alkene
intermediates within the micropores, and demonstrated that zeolite
particle size has a great influence on the final selectivity of isomers in
hydroisomerization. They synthesized micro/mesoporous Y/MCM-41
composites, comprised of mesoporous MCM-41 material on the outer
layer and the inner alkali treated Y zeolites with different crystal size.
The MCM-41 material on the outer layer on one hand is the main support
of Pt metal particles, on the other hand, it can prevent the aggregation of
Y zeolite. Therefore, on the Pt loaded catalysts, n-alkene intermediates
mainly formed on MCM-41, and the successive isomerization happened
inside inner Y zeolites. In the n-C12 hydroisomerization test of Pt loaded
catalysts with similar metal–acid balance but evidently different average
crystal size of Y zeolites, namely 653 nm (Pt/MY-0), 548 nm (Pt/MY-2),
421 nm (Pt/MY-5), respectively, the resulted selectivity of i-C12
exhibited significant difference. It is found that the smaller crystal size of
Y zeolites in the catalysts were, the higher the selectivity was. And this
result is valid in each conversion level. This was attributed to the
cracking reaction was suppressed by shortened diffusion pathlength and
reduced active acid sites the n-alkene intermediates will encounter be­
tween two metal sites.
Li et al. [121] reported the hydroisomerization of n-Decane using Pt/
Y catalysts with different crystal size. Alkali treatment was used to
downsize zeolite Y. Pt loaded catalysts based on alkali treated and
originate Y were designated as Pt/AY-akl and Pt/AY-ori, respectively.
The average particle size of alkali treated Y zeolites is 501 nm, which is
much smaller than of the origin Y zeolites with 687 nm. The hydro­
isomerization of n-Decane on Pt/AY-akl and Pt/AY-ori showed that
catalyst with smaller crystal size exhibited higher isomer yield by about
10%. It was attributed to the higher resistance to multiple branching and
skeletal cracking of Pt/Y-alk. Smaller crystal size of Y zeolites reduced
the probability of olefinic intermediates encounter more active protonic
acid sites inside the micropores and relieved the diffusion resistance.
Therefore, the selectivity of isomers was enhanced by suppressing the
undesired secondary cracking.
Ge et al. [122] studied the effect of particle size in Pt/SAPO-11
catalysts in hydroisomerization of n-dodecane. SAPO-11 molecular
sieves with different particle size were synthesized using modified dry-
gel conversion. The particle size of as-synthesized SAPO-11 can be
tuned from 65 nm to 450 nm by adjusting water content from 5% to
50%. The analysis of Pt/SAPO-11 catalysts with different particle size
also showed the amount of protonic acid sites decreased with particle
size. While the hydroisomerization of n-dodecane showed one can attain
the highest isomer yields of ~75% on catalyst 1.4PtNS with smallest
crystal size. It was attributed to the reduced crystal size not only reduces
the nH+ between two Pt sites, but also reduces the resistance time of
alkene intermediates within micropores. And the reduced nH+ between
two Pt sites and resistance avoid cracking reaction.
The studies introduced above suggest that the downsizing of acid
support crystal size is an effective way to enhance the isomers selec­
tivity. The enhanced selectivity is always attributed to the shortened
pathway for reaction intermediates; thus, the intermediates may
encounter fewer acid sites during the diffusion between two metallic
sites. However, the approach to reduce size of acid supports should be
further developed, considering the economic and environmental
aspects.
5. Conclusion and outlook
In this review, we compared the hydroisomerization of linear alkanes
of C5-C6 and long-chain ones. In the view of their mechanism, we can
find that the isomerization of alkene intermediates of long-chain alkanes
is more complicated. For light alkanes, undesired β-scission can only go
through type C and type D mechanism, which are much slower than the
type A and type B cracking of long-chain alkanes. This indicates long-
chain alkanes have stronger tendency of cracking, and it is consistent
with the lower isomer yields. The effects of metal acid balance of the
13
Fuel xxx (xxxx) xxx
catalysts are the same in principle for the both parts. There are 3 stages
of reaction scheme according to the nMe/nA ratio. For both light alkanes
and long-chain alkanes, the nMe/nA ratio should reach to the third stage
to guarantee the activity and stability of catalysts, as well as to lower the
tendency of cracking, especially for long-chain alkanes. However, due to
the difference of reactivity between light alkanes and long-chain al­
kanes, the exact number of nMe/nA ratio are not the same. Besides the
nMe/nA ratio, the acid strength of their catalysts’ acid supports also has
significant difference. For light alkanes, people tend to use zeolites with
strong acid strength. While for long-chain alkanes, emphasis is always
placed on supports with weaker acid strength. General explanation is the
high cracking tendency and weak diffusivity of the reaction in­
termediates of long-chain alkanes. The intermediates will undergo
excessive isomerization and successive cracking if the acid strength is
strong. However, there exists a dispute. Noh et al. argues the weak acid
strength will increase the intrinsic β-scission/isomerization rate ratios.
In addition, for long-chain alkanes, the so called “pore mouth” and “key
lock” mechanism plays an important role in their hydroisomerization.
Therefore, efforts have been made to tune the acid sites location to attain
higher isomer selectivity. Considering the weak diffusivity of long-chain
alkanes, researches have been made on the modifications of the textural
structure of zeolites and molecular sieves based catalysts. Emphasis are
mainly placed on two directions, i.e., fabrication of hierarchical pore
structure and downsizing of crystal size. In both ways, the enhancement
of isomer yields is remarkable, indicating more attention should be paid
on their textural properties.
In the future, hydroisomerization will still play an important role in
fuel and lubricants processing. However, whether for light alkanes or
long-chain alkanes, people should concentrate on the following aspects
to solve the emerging problems or optimize the overall process:
1. The high cost caused by loading noble metals. Efforts should be paid
on enhancing the hydrogenation efficiency of noble metals, and
finally the loading amount can be reduced. Another promising di­
rection is to partially or entirely replace it by applying a new form of
hydrogenation component.
2. The poor control of reaction degree. Since isomerization and
cracking of alkanes are consecutive reactions, the well control of
reaction degree is a key to enhance isomers selectivity, especially for
long-chain alkanes. However, it’s still a great challenge to limit the
reaction degree to stop at isomerization. The proper coupling of
separation unit may help.
3. Lack of control over the precise structure of the product. The struc­
tures of alkane isomers are closely related to their properties. For
gasoline distillates, highly branched isomers are favored for their
high octane number. However, for diesel distillates, terminal mono-
methyl-branched isomers are ideal due to their high cetane number
and outstanding low temperature flow properties. For lubricants, the
pour point and viscosity index both decrease as the branching posi­
tion is closer to the center of the straight chain. A balance between
these two properties should be considered according to situation of
practice application, with adjusting the isomerization degree and
position of side chains of the products. However, in practice, no
matter which fraction is isomerized, the product structure varies in
branching degree and side chain position. Therefore, it’s of great
importance to optimize the control of isomers structure to enhance
the quality of products.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
C. Wei et al.
Acknowledgment
This work was supported by National Natural Science Foundation of
China (No. 22021004).
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