Journal of Molecular Liquids 285 (2019) 299–313

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Review

Ionic liquids: Green catalysts for alkene-isoalkane alkylation

Shailey Singhal a, Shilpi Agarwal a, Manjeet Singh a, Sravendra Rana a, Shefali Arora a,⁎, Naveen Singhal b
a
University of Petroleum & Energy Studies (UPES), Department of Chemistry, School of Engineering, Energy Acres Building, Bidholi, Dehradun 248007, Uttarakhand, India
b
DIT University, Department of Chemistry, Dehradun 248001, Uttarakhand, India

a r t i c l e i n f o a b s t r a c t

Article history: Alkylation of isoalkane and alkene owns a note-worthy position among octane improving chemical conversions.
Received 14 August 2018 Widely adopted catalysts (H2SO4 and HF) for alkylation at industrial level suffer severe drawbacks associated
Received in revised form 6 March 2019 with environmental concerns, recycling, reactor corrosion, etc. Solid acid catalysts are good, but represent deac-
Accepted 24 March 2019
tivation issues. Compared to this, ionic liquids are considered green catalysts for obtaining alkylate as an efficient
Available online 28 March 2019
blending component for clean oil. This review article presents various ionic liquids effective for alkylation reac-
Keywords:
tion. Their structures, properties, and catalytic activities are briefed in this analysis. Impact of additives on various
Alkylation ionic liquids and their efficiencies has also been discussed. The article will help the researchers to gain a deep in-
Isobutane sight and understanding about the reaction conditions suitable for alkylation and its chemistry in detail.
Octane number © 2019 Elsevier B.V. All rights reserved.
Alkenes

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
2. Ionic liquids as alkylation catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
2.1. Lewis acidic ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
2.2. Bronsted acidic ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2.3. Lewis-Bronsted acidic ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
3. Additives for isobutane alkylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
4. Deactivation in ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
5. Alkylation chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
6. Conclusion and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312

1. Introduction
Alkylation of isoalkanes is a significant chemical process to obtain
branched hydrocarbons, especially trimethyl pentanes (TMPs) for gaso-
line pool, which can restrict/substitute the addition of chemical anti-
knocking agents to improve its octane number. The reaction is of exces-
sive connotation as Governments of various nations are also putting
emphasis on improving the fuel quality by green chemical routes. Alkyl-
ate is a very good blending component for clean motor gasoline. It con-
tains mainly isoparaffins, possesses high octane number, low vapor
⁎ Corresponding author at: Energy Acres Building, Bidholi, Dehradun 248007,
Uttarakhand, India.
E-mail addresses: shefali.arora@ddn.upes.ac.in, URL: https://www.upes.ac.in
(S. Arora).
pressure and low sulfur, olefins & aromatic hydrocarbon content. De-
creased use of methyl-tertiary-butyl ether as octane booster in many
countries has still enhanced the significance of alkylation for obtaining
high performing gasoline [1].
Alkylation production capacity installed worldwide is around
102 million tons/year [2], where conventional catalysts (sulfuric and
hydrofluoric acid) are being used since long for alkylation. Despite of
their high catalytic activity, these acids are associated with serious envi-
ronmental concern, acid sludge treatment, handling hazards, equip-
ment corrosion, high acid consumption, and high operating cost [3–8]
and thus have led the necessity of alternate material which can act as
potential catalyst for enriching the gasoline pool.
Solid acids including zeolites [9–14], polymeric acids [15],
heteropoly acids [16–20], sulfated zirconia [21–23], and others
[24–31] are strong catalytic candidates for this reaction [9–31] (Fig. 1).

https://doi.org/10.1016/j.molliq.2019.03.145
0167-7322/© 2019 Elsevier B.V. All rights reserved.
300 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313
Fig. 1. Different catalysts used for isobutane alkylation.
These materials are free from corrosivity/toxicity of mineral acids and
possess high catalytic activity for alkylation, however could not be
scaled up because of their rapid deactivation due to the deposition of
carbonaceous material, pore mouth plugging, leaching, and high regen-
eration cost [32–38]. Few technologies were developed for isobutane/
butene alkylation with a solid acid catalyst, like Alkylene™ process pre-
sented by UOP, fixed bed alkylation (FBA™) technology developed by
Haldor Topsoe A/S, Neste Oy and Conoco developed by Catalytica, and
the process developed by Chemical Research & Licensing [39], but
could not be continued due to the issues associated with the solid cata-
lysts, main being its rapid deactivation [40]. This drawback could be
overcome to a large extent by performing alkylation in a supercritical
medium, however the process involved high capital investment and
high operating cost [41–43].
Another important environmentally benign category worth for car-
rying out alkylation of isoalkane and olefins is ionic liquids [9,44–54]
(Tables 1, 2), which also find applications in liquid-liquid extraction
[55–60], electrochemistry [61–63], polymerization [64–67], catalysis
for various reactions [68–87], biocatalysis [88–90], biomass conversion
[91,92], solvent for organic & inorganic material [93–95], and others
[96–99]. Ionic liquids represent an excellent category of solvents and
catalysts being recyclable and product selective in nature; also produc-
ing the alkylate composition with low unsaturation. This review pre-
sents the significance of ionic liquids as potential catalyst for
alkylation of isoalkane and alkene for the production of high quality hy-
drocarbon, an essential constituent of gasoline.
2. Ionic liquids as alkylation catalysts
Ionic liquids are environment friendly substitutes to the conven-
tional catalysts for alkylation in the refineries. Being environmentally
benign, these are considered to be the green solvents and open up the
new challenges and opportunities for the scientists towards cleaner ca-
talysis. One more advantage associated with ionic liquids is that unlike
solid acids, these can be used in the current units in the refineries with-
out any modification [100]. They produce alkylate with higher quality
and simple product separation process, however are expensive as
compared to conventional catalysts. Potential of ionic liquids as alkyl-
ation catalysts is proved by its implementation at industrial level
[45,101].
Ionic liquids are the ionic salts of organic cations (e.g.
imidazolonium, tetraalkylammonium, tetraalkylphosphonium, N-
alkylpyridinium, 1,3-dialkylimidazolium, trialkylsulfonium, tetraalkyl
phosphonium salts) having melting points lower than the room tem-
perature [102]. Most of them are commercially available or can easily
be prepared by reacting corresponding haloalkane with amines
[103,104]. Wide range of ionic liquids with varying cations, and anions
is represented in Fig. 2.
First ionic liquid (ethylammonium nitrate; m.p. 12–14 °C) was pre-
pared by Walden in 1914 by the reaction of ethylamine and nitric acid
[105]. Strongly acidic ionic liquids are obtained by dissolving Bronsted
acids in them [106,107], wherein presence of strongly Bronsted acidic
sites, helps in inhibiting the common side reactions, such as cracking,
polymerization, and isomerization [108].
Acidic ionic liquids in combination with organometallic compounds
have also be used as an efficient medium for homogenous catalyzed re-
action [39,51,100,107,109–113]. One major advantage of ionic liquids is
their tunable chemical and physical properties, governed by the organic
cations and inorganic anions. Density, viscosity, solubility, and acidity
are important parameters of homogenous catalysts; first three being
controlled by the cationic part, while acidity by anionic metal halide in
case of ionic liquids. Ratio of metal halide to organic base is also impor-
tant to govern the acidity of the ionic liquid system [114–116]. Other
important advantages of ionic liquids are low vapor pressure, non-
inflammability, tunable acidity, and solubility, high thermal stability, re-
usability, Bronsted & Lewis acidity, superacidity (in some cases), and a
wide liquid-phase temperature range.
Based upon the type of species present in them, ionic liquids can be
categorized as Lewis acidic ILs and Bronsted acidic ILs.
2.1. Lewis acidic ionic liquids
Lewis acidic ionic liquids find main focus on chlorometallates as the
major group of attraction and applications [117]. In all the compounds
of this category, xAlCl3 is kept N0.50, as being Lewis basic in nature
[118,119], compositions with xAlCl3 b 0.50 behave as Lewis bases.
Chloroaluminates [45,47,106,120–129], composite ionic liquids [130]
and chlorogallates [131] are important Lewis acidic ionic liquids playing
an active role in isobutene alkylation. Chloroaluminates are the mix-
tures of aluminum chloride and organic moieties, such as pyridinium,
ion, imidazolium ion, etc. Halogenoaluminates based acidic ionic liquid
systems, such as 1-octyl-3-methylimidazolium bromide/AlCl3 and
triethylammonium chloride/AlCl3 are used for alkylation of isobutene
with butane-2 after tuning their acidities either by Lewis acids or
Bronsted acidic molecules [125]. Acidic chloroaluminates are useful for
the alkylation of isobutene and butene-2. Temperature, lesser than
room temperature and fine-tuning of acidity of IL, however, is recom-
mended in order to avoid side reactions, like cracking & heavy by-
product formation and to achieve around 90% conversion with N90%
TMPs selectivity [45]. It is difficult to control the acidity of
chloroaluminated ionic liquids. Presence of SbF− 6 anion drastically en-
hances the catalytic effect of non-chloroaluminate based ionic liquids
[132,133]. Composite ionic liquids contain anions in the form of ligands
with two or more metallic centres, such as [AlCuCl5]− [101,130,134].
Under appropriate reaction conditions, composite ionic liquids are
able to result in alkylation with around 92% trimethyl pentanes
(TMPs) selectively [39,49,135]. A composite ionic liquid has been suc-
cessfully developed from trimethylamine hydrochloride, anhydrous
aluminum chloride, and cuprous chloride for isobutane alkylation by
China University of Petroleum [101,136]. Chlorogallate (III) systems
are the derivatives of gallic acid and possess almost similar Lewis acidity
as chloroaluminates but are more resistant to hydrolysis than
chloroaluminate (III) ones [137,138].
 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313
2.2. Bronsted acidic ionic liquids
Bronsted acidic ILs are used for isobutene alkylation either alone or in
combination with acids, like sulfuric acid or trifluoromethanesulfonic
acid. Examples are N,N-dimethyl-N-ethanolammonium hydrogen sulfate,
N-methyl-N,N-diethanolammonium hydrogen sulfate, N,N-diethyl-N-
ethanolammonium triflate, 2-hydroxy-N,N-dimethylpropan-1-ammo-
nium triflate, etc. [139] Resins like Dowex 50 in combination with
Bronsted acidic ionic liquids containing sulfonic groups are also suitable
species for catalyzing alkylation of alkenes and isoalkanes [51,140–142].
2.3. Lewis-Bronsted acidic ionic liquids
This category is the combination of both Lewis acidic and Bronsted
acidic IL systems. In these systems, Bronsted acids or Bronsted acidic
ILs, such as 1-methyl-3-(4-sulfobutyl)-imidazolium hydrogen sulfate
[HO3Sbmim][HSO4] [51,110], alkyl halide (tert-butylchloride) [108]
and metal salt (CuCl, CuCl2, or NiCl2) [140] are used as co-catalysts to
improve the performance of Lewis acidic ILs. Combination supports in
generating a synergetic effect of both the types of acidities, resulting
in the improved activity and selectivity of the catalytic system towards
the reaction. Bui et al. reported the alkylation of isobutane in the pres-
ence of 1-methyl-3-octyl-imidazoliumbromo-chloroaluminate[Omim]
Br-AlCl3 (x = 1.5) with a selectivity of 21.3%, which could be increased
to 52.7% in the presence of 50 wt% [HO3Sbmim][HSO4] [51]. Similar re-
marks have been received from other researchers also [143–146].
Alkylation of isoalkanes in the presence of ionic liquid is homoge-
nous catalysis, which requires proper mixing of reactant and the catalyst
to cause an effective reaction. A high interfacial surface area between
acid catalyst and hydrocarbon facilitates the reaction, which is decided
by molar acid/hydrocarbon ratio, acid composition, agitation rate, and
temperature. Intensive mixing of the biphasic system is required to gen-
erate a large interfacial area and to prevent phase separation as the den-
sity difference between two phases is large (ρIL = approx. 1200 kg/m3;
ρorg = approx. 600 kg/m3) [147]. High acidity and solubility of the reac-
tants in ionic liquid are the important features governing alkylation re-
action. Solubility of hydrocarbons with the catalyst system increases
significantly with the increasing length of alkyl group [47,148–150],
which in turn facilitates the catalytic activity of ionic liquids towards al-
kylation reaction. Thus, ionic liquids bearing larger alkyl groups on the
cation, for example [C8mim] exhibit higher activity and can catalyze
larger amount of reactants under identical conditions than smaller
ones, for example [C6 or C4mim] with the same anionic composition.
This also indicates that the reaction does not only takes place at the in-
terface between ionic liquid and organic phase, but also inside the bulk
phase of the ionic liquid catalyst due to the solubility of hydrocarbons
within the catalyst phase. Anion also affects the activity of ionic liquids.
Among various ionic liquids of the type [C8mim]X-AlCl3, [C8mim]Br-
AlCl3 is most active with [AlCl3Br]− as dominant anion [47]. Increasing
acidity of anions leads to side reactions (Fig. 3), however to various
extents.
Increase in liquid hourly space velocity (LHSV) decreases the cata-
lytic activity for alkylation gradually due to decreased resident time of
the reactants, and increases the formation of olefin products due to olig-
omerization. Ionic liquids are even stronger acids than 100% sulfuric
acid, showing higher activity towards alkylation [148]. High isoalkane/
olefin ratio (around 24:1 or even 1000:1) significantly improves the al-
kylate quality with the increased distribution of C8 fractions [151]. This
is because, presence of more isobutane molecules around C+ 8 cation, de-
creases the possibility of formation of higher cations through C+ 8 amount of C9-isomer, 2,2,5-trimethyl hexane (2,2,5-TMH) due to the re-
+ CH3CH _ CHCH3 → C+ +
12, C16, minimizing the by-products. Being the
source of hydride ions, higher amount of isoalkane causes dilution ef-
fect, which increases the efficiency of hydride-transfer to the cations
formed, and suppresses the side reactions [106,152]. Some ionic liquids
also permit biphasic catalysis, i.e. active catalytic species remains
301
soluble in the solvent, but reaction products, especially heavier hydro-
carbons are not [153].
The performance of alkylation catalyst is evaluated as the ratio of
trimethylpentanes (TMPs) to dimethylhexanes (DMHs). In order to
achieve high octane number, it is desirable to obtain high TMPs/DMHs
ratio [154]. It is important to note that the selectivity of C8 product is
mainly controlled by the acidity of anionic component and is barely af-
fected by cation in the ionic liquid. This indicates the role of number of
Bronsted acid sites in acidic ionic liquid in the production of higher
amount of TMPs [45]. Highest C8 alkylates selectivity is referred at Ham-
mett acidity scale of H0 = −10.7 [155]. At acidity higher than this,
cracking reactions occur leading to the product stream enriched with
lighter components. Acidity of ionic liquids is affected by reaction tem-
perature. Increasing temperature increases the concentration of strong
acidic anion, but decomposes cationic part of ionic liquid [114], due to
which solubility of reactant in reduced in ionic liquids, thus lowering
the activity and conversion. Fragmentation of cationic component also
decreases the number of Bronsted acid sites, thus affecting the selectiv-
ity of the product during alkylation.
3. Additives for isobutane alkylation
Neat ionic liquids are not catalytically very active and promote sec-
ondary reactions, such as oligomerization & cracking, however their
performance can be enhanced by various methods, viz. (i) by adjusting
their acidity by the addition of suitable amounts of Bronsted acids
[51,100,110,140,156–159], (ii) by using promoters with them during
the reaction [160], and (iii) by their structural adjustments with the ad-
dition of transition metal salts (CuCl, CuCl2, ZnCl2, FeCl3, and NiCl2)
[49,108,131].
Among the three methods stated above, use of promoters is most
widely accepted for improving upon the efficiency of ionic liquids.
Both, inorganic (such as water and sulfuric acid) and organic (such as,
t-butyl halogenides) compounds are used as promoters [140]. These
promoters vary in initiation pathways for promoting the reaction. Inor-
ganic promoters, like water as polar molecule is partly absorbed during
the formation of acidic protons into the bulk ionic liquid; thus making
only a fraction of active species available at the surface for C4 feed. Fur-
ther, generation of active species gets slow in the presence of inorganic
promoters as it requires an additional alkene to form t-butyl cation. On
the other hand, organic promoters initially dissolve in the organic phase
and convert into t-butyl cations instantaneously when in contact with
Lewis acidic ionic liquid phase. Among various organic promoters, t-
butyl halogenides are considered as good promoters, however the activ-
ity is being governed by the choice of halogen atom present in it. t-Butyl
bromide is comparatively more active than t-butyl chloride, due to the
difference in bond dissociation energies of C\\Cl (337.1 kJ/mol) and
C\\Br (276.4 kJ/mol) bonds [161]. Sometimes, the rate of alkylation in
the presence of t-butyl bromide promoted ionic liquids is so fast that
all the TMPyl cations do not get saturated by hydride transfer from iso-
butane and thus are not converted to TMPs; instead they react with an-
other 2-butene molecule leading to the formation of high molecular
weight products, which undergo cracking to give smaller compounds
during the course of reaction [162].
Presence of promoters also helps in increasing the amount of C8 frac-
tions, also supporting the distribution of dimethyl hexanes (DMHs) to-
wards the well desired TMPs, which increases with the increased
content of promoter. This selective shift generates due to the intermo-
lecular hydride and methyl shifts within 2,2,3-TMPyl cation. t-Butyl bro-
mide promoted ionic liquids also lead to the formation of a significant
action of isopentyl cation with 2-butene followed by a consecutive hy-
dride transfer [162].
Addition of Bronsted acids or promoters accelerates carbocation for-
mation and also affects alkylate distribution. These measures enhance
the reaction rate and improve both TMP selectivity and alkylate RON,
 302
Table 1
Various ionic liquids for alkylation of alkene-isoalkane.

S. Catalyst Category Additive Rea. Rea. I/O Molar ionic LHSVtotal Press. Conversion C8 in the TMPs in DMHs in TMPs/DMH RON Ref.
no. of temp. time ratio liquid/olefin (h−1) (bar) of butene product the the ratio
ionic (°C) (min.) ratio (%) (wt%) product product
liquid (wt%) (wt%)

1. [C4mim]Br-AlCl3 (x = 0.52) LAIL# – 80 30 20 – 24 – 32.1 27.6 8.8 18.8 0.47 – [47]

2. [C6mim]Br-AlCl3 (x = 0.52) LAIL# – 80 30 20 – 24 – 73.2 27.4 9.4 18.0 0.52 – [47]
3. [C8mim]Cl-AlCl3 (x = 0.52) LAIL# – 80 30 20 – 24 – 69.5 29.6 6.9 22.7 0.30 – [47]
4. [C8mim]I-AlCl3 (x = 0.52) LAIL# – 80 30 20 – 24 – 52.4 15.9 2.3 13.6 0.17 – [47]
5. [C8mim]Br-AlCl3 (x = 0.52) LAIL# – 80 30 20 – 24 – 91.0 27.4 9.3 18.1 0.51 – [47]
6. [C8mim]Br-AlCl3 (x = 0.48) LAIL# – 80 10 20 – 240 – 18.0 30.3 0.7 7.3 0.09 – [47]
7. [C8mim]Br-AlCl3 (x = 0.48) LAIL# – 80 300 20 – 240 – 17.4 31.4 0.7 7.2 0.09 – [47]
8. [C8mim]Br-AlCl3 (x = 0.52) LAIL# – 80 10 20 – 240 – 40.5 45.2 9.4 18.2 0.52 – [47]
9. [C8mim]Br-AlCl3 (x = 0.52) LAIL# – 50 300 20 – 240 – 30.2 46.2 1.8 4.7 0.38 – [47]
10. [C8mim]Br-AlCl3 (x = 0.52) LAIL# – 80 300 20 – 24 – 84.1 46.1 9.2 18.1 0.51 – [47]
11. [C8mim]Br-AlCl3 (x = 0.52) LAIL# – 80 300 20 – 60 – 57.1 44.6 9.4 18.7 0.50 – [47]
12. [C8mim]Br-AlCl3 (x = 0.52) LAIL# – 80 300 20 – 240 – 39.6 45.4 9.2 18.2 0.51 – [47]
LAIL# – – – –

S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313

13. [C8mim]Br-AlCl3 (x = 0.52) 120 300 20 240 27.8 44.2 4.1 3.5 1.17 [47]
14. [C8mim]Br-AlCl3 (x = 0.58) LAIL# – 80 10 20 – 240 – 70.4 23.7 8.7 8.3 1.05 – [47]
15. [C8mim]Br-AlCl3 (x = 0.58) LAIL# – 80 300 20 – 240 – 35.1 22.7 5.7 8.9 0.64 – [47]
16. [C4mim]Cl-[AlCl4] (xAlCl3 = 0.64) LAIL# – −20 75 13.25 0.4 – 6 25 15 17 70 0.24 [140]
17. [C4mim]Cl-[AlCl4] (xAlCl3 = 0.64) LAIL# Water (0.12 mol%) −20 80 13.25 0.4 – 6 90 20 70 28 2.5 [140]
18. [C4mim]Cl-[AlCl4] (xAlCl3 = 0.64) LAIL# t-Butyl chloride (0.2 mol%) −20 8 13.25 0.4 – 6 99 18 90 9 10 [140]
19. [C4mim]Cl-[AlCl4] (xAlCl3 = 0.64) LAIL# t-Butyl bromide (0.05 mol%) −20 75 13.25 0.4 – 6 40 19 58 23 2.52 [140]
20. [C4mim]Cl-[AlCl4] (xAlCl3 = 0.64) LAIL# t-Butyl bromide (0.09 mol%) −20 45 13.25 0.4 – 6 70 26 72 26 2.77 [140]
21. [C4mim]Cl-[AlCl4] (xAlCl3 = 0.64) LAIL# t-Butyl bromide (0.17 mol%) −20 5 13.25 0.4 – 6 90 – – – – [140]
22. [C4mim]Cl-[AlCl4] (xAlCl3 = 0.64) LAIL# t-Butyl bromide (0.5 mol%) −20 4 13.25 0.4 – 6 100 21 89 11 8.1 [140]
23. [DMIPA][HSO4] BAIL## – 10 10 10 – – 5 100 88.9 82.1 6.8 12.1 97.4 [148]
24. [DMEA][HSO4] BAIL## – 10 10 10 – – 5 100 89.6 – – 12.9 97.7 [148]
25. [MEA][HSO4] BAIL## – 10 10 10 – – 5 100 87.9 – – 10.4 97.0 [148]
26. [DEEA][HSO4] BAIL## – 10 10 10 – – 5 100 87.3 81.3 6 13.5 97.4 [148]
27. [MDEA][HSO4] BAIL## – 10 10 10 – – 5 100 92.1 – – 12.0 97.8 [148]
28. [TEA][HSO4] BAIL## – 10 10 10 – – 5 100 91.5 85.1 6.4 13.3 98.0 [148]
29. [DMIPA][CF3SO3] BAIL## – 10 10 10 – – 5 100 86.3 79.7 6.6 12.1 96.4 [148]
30. [TEA][CF3SO3] BAIL## – 10 10 10 – – 5 100 87.2 79.9 7.3 10.9 96.9 [148]
31. [C8mim]Br-AlCL3 (x = 0.6) LAIL# [HO3S-C4mim][HSO4]{0.24 g/g 5 60 13 – – 6 N98 ~58 53 – – 95 [51]
[C8mim]Br-AlCl3}
32. [Et3NH]Cl-AlCl3 (x = 0.67) LAIL# CuCl 15 0.33 54 1 – 6 100 88.9 82 6.89 11.9 97.3 [39]
33. PVPHF* BAIL## None 36 3 24 – – – – 81.8 38.8 – – 94 [106]
34. PVPHF* BAIL## None 36 10 12 – – – – 70 31.7 – – 91.3 [106]
35. PVPHF* BAIL## None 36 10 12 – – – – 73.7 32.3 – – 93 [106]
36. PVPHF* BAIL## None 36 10 24 – – – – 68.8 27.4 – – 93.4 [106]
37. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# CuCl (1 g/3 ml) 30 30 7 – – – 60.8 5.5 11.1 – – 94.7 [152]
38. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# AgCl (1 g/3 ml) 30 30 7 – – – 62.8 4.3 14.6 – – 95.3 [152]
39. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# ZnCl2 (1 g/3 ml) 30 30 7 – – – 60.1 7.0 8.6 – – 93.9 [152]
40. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# NiCl2 (1 g/3 ml) 30 30 7 – – – 67.3 4.4 15.3 – – 96.1 [152]
41. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# CeCl3 (1 g/3 ml) 30 30 7 – – – 67.8 4.5 15.1 – – 95.8 [152]
42. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# SnCl2 (1 g/3 ml) 30 30 7 – – – 60.2 4.9 12.3 – – 93.8 [152]
43. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# CuO (1 g/3 ml) 30 30 7 – – – 58.3 3.4 17.1 – – 93.9 [152]
44. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# ZnO (1 g/3 ml) 30 30 7 – – – 50.0 4.9 10.2 – – 91.0 [152]
45. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# Tb4O7 (1 g/3 ml) 30 30 7 – – – 54.7 4.8 11.4 – – 92.4 [152]
46. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# CeO2 (1 g/3 ml) 30 30 7 – – – 64.7 5.0 12.9 – – 95.1 [152]
47. [C4mim]Cl-AlCl3-CuCl LAIL# None 30 30 7 – – – 71.8 4.8 15.0 – – 97.3 [152]
48. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# ZnCl2 (1 g/3 ml) 30 30 7 – – – 55.6 7.1 7.8 – – 92.0 [152]
49. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CuCl (1 g/3 ml) 30 30 7 – – – 61.8 16.2 3.8 – – 92.8 [152]
50. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CeCl3 (1 g/3 ml) 30 30 7 – – – 59.2 15.7 3.8 – – 93.2 [152]
51. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CuCl2 (1 g/3 ml) 30 30 7 – – – 49.3 12.1 4.1 – – 90.3 [152]
52. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# ZnO (1 g/3 ml) 30 30 7 – – – 44.9 12.4 3.6 – – 88.4 [152]
53. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CuO (1 g/3 ml) 30 30 7 – – – 45.6 13.3 3.4 – – 90.6 [152]
54. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CeO2 (1 g/3 ml) 30 30 7 – – – 52.2 15.0 3.5 – – 91.9 [152]
55. [Et3NH]Cl-AlCl3-CuCl LAIL# None 30 30 7 – – – 68.0 8.3 8.2 – – 95.1 [152]
56. [Et3NH]Cl-AlCl3 LAIL# None 30 30 7 – – – 49.8 7.9 6.3 – – 90.0 [152]
57. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CuAlCl4 (2.5 g/15 ml) 30 30 7 – – – 71.7 6.8 10.5 – – 96.4 [152]
58. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CuAlCl4 (5 g/15 ml) 30 30 7 – – – 87.5 5.0 17.5 – – 100.5 [152]
59. [Et3NH]Cl-AlCl3 (x = 0.64) LAIL# CuAlCl4 (10 g/15 ml) 30 30 7 – – – 64.9 4.7 13.8 – – 93.1 [152]
60. [C4mim]Br-AlCl3 (x = 0.64) LAIL# None 30 30 7 – – – 51.9 9.4 5.5 – – 91.8 [152]
61. [C4mim]Br-AlCl3 (x = 0.64) LAIL# CuAlCl4 (2.5 g/15 ml) 30 30 7 – – – 70.1 4.6 15.2 – – 96.1 [152]
62. [C4mim]Br-AlCl3 (x = 0.64) LAIL# CuAlCl4 (5 g/15 ml) 30 30 7 – – – 83.1 4.7 17.7 – – 98.6 [152]
63. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# None 30 30 7 – – – 53.1 6.4 8.3 – – 92.1 [152]
64. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# CuAlCl4 (2.5 g/15 ml) 30 30 7 – – – 70.6 7.3 9.7 – – 96.3 [152]
65. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# CuAlCl4 (5 g/15 ml) 30 30 7 – – – 85.2 4.6 18.5 – – 98.8 [152]
66. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# CuAlCl4 (10 g/15 ml) 30 30 7 – – – 65.4 6.4 10.2 – – 93.6 [152]
67. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# AgAlCl4 (1 g/3 ml) 30 30 7 – – – 83.4 5.7 14.6 – – 98.3 [152]
68. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# AgBF4 (1 g/3 ml) 30 30 7 – – – 81.3 4.6 17.7 – – 98.2 [152]
69. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# AgClO4 (1 g/3 ml) 30 30 7 – – – 78.6 5.4 14.6 – – 97.9 [152]
70. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# Ni(AlCl4)2 (1 g/3 ml) 30 30 7 – – – 75.9 3.3 23.0 – – 97.3 [152]
71. [C4mim]Cl-AlCl3 (x = 0.64) LAIL# ZnCl2-AlCl3 (1 g/3 ml) 30 30 7 – – – 77.8 1.7 45.8 – – 97.7 [152]
72. H2SO4 BAIL## – 8 10 7.5 – – 2 97.3 61.7 – – 6.1 – [107]

S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313

73. CF3SO3H BAIL## – 8 10 7.5 – – 2 98.7 41.1 – – 1.4 – [107]
74. [Hmim][Tf2N] BAIL## – 8 30 7.5 – – 2 0.3 15.4 – – 0.5 – [107]
75. [Hmim][Tf2N] + H2SO4 (93.6:6.4, LBAIL## – 8 10 7.5 – – 2 2.2 15.9 – – 0.6 – [107]
w/w)
76. [Hmim][Tf2N] + H2SO4 LBAIL## – 8 30 7.5 – – 2 59.0 19.2 – – 5.8 – [107]
(60.8:39.2, w/w)
##
77. [Hmim][Tf2N] + H2SO4 LBAIL – 8 20 7.5 – – 2 89.4 31.1 – – 4.8 – [107]
(42.0:58.0, w/w)
78. [Hmim][Tf2N] + H2SO4 (8.7:91.3, LBAIL## – 8 20 7.5 – – 2 89.7 60.2 – – 5.1 – [107]
w/w)
79. [MPSim][OTf] BAIL## – 8 20 7.5 – – 2 6.3 11.0 – – 0.8 – [107]
80. [MPSim][OTf] + H2SO4 LBAIL## – 8 20 7.5 – – 2 93.7 43.6 – – 3.6 – [107]
(43.6:56.4, w/w)
81. [MPSim][OTf] + H2SO4 LBAIL## – 8 20 7.5 – – 2 92.2 63.9 – – 5.1 – [107]
(26.8:73.2, w/w)
82. [MBSim][OTf] BAIL## – 8 20 7.5 – – 2 2.2 6.6 – – 0.0 – [107]
83. [MBSim][OTf] + H2SO4 LBAIL## – 8 20 7.5 – – 2 8.2 31.2 – – 2.7 – [107]
(70.4:29.6, w/w)
84. [MBSim][OTf] + H2SO4 LBAIL## – 8 20 7.5 – – 2 91.3 41.0 – – 3.8 – [107]
(46.7:53.3, w/w)
##
85. [MBSim][OTf] + H2SO4 LBAIL – 8 20 7.5 – – 2 91.1 57.0 – – 4.8 – [107]
(28.1:71.8, w/w)
86. [Bmim][HSO4] BAIL## – 8 20 7.5 – – 2 11.4 8.7 – – 0.1 – [107]
87. [Bmim][HSO4] + H2SO4 LBAIL## – 8 20 7.5 – – 2 51.8 22.4 – – 5.2 – [107]
(67.6:32.4, w/w)
88. [Bmim][HSO4] + H2SO4 LBAIL## – 8 20 7.5 – – 2 91.0 60.3 – – 4.9 – [107]
(41.7:58.3, w/w)
##
89. [Bmim][HSO4] + H2SO4 LBAIL – 8 20 7.5 – – 2 90.4 41.0 – – 7.9 – [107]
(20.9:79.1, w/w)
90. [Omim][HSO4] + H2SO4 LBAIL## – 8 10 7.5 – – 2 98.0 51.3 – – 6.6 – [107]
(16.0:84.0, w/w)
91. [BSim][HSO4] LBAIL## – 8 20 7.5 – – 2 5.4 62.0 – – 7.2 – [107]
92. [BSim][HSO4] + H2SO4 LBAIL## – 8 20 7.5 – – 2 12.1 27.2 – – 8.1 – [107]
(63.9:36.1, w/w)
93. [BSim][HSO4] + H2SO4 LBAIL## – 8 20 7.5 – – 2 89.5 25.9 – – 2.6 – [107]
(40.9:59.2, w/w)
94. [BSim][HSO4] + H2SO4 LBAIL## – 8 20 7.5 – – 2 95.6 62.3 – – 6.4 – [107]
(26.0:74.0, w/w)
95. [BSim][OTf] + CF3SO3H (96.6:3.4, LBAIL## – 8 20 7.5 – – 2 1.1 59.5 – – 8.8 – [107]

303
(continued on next page)
 304
Table 1 (continued)

S. Catalyst Category Additive Rea. Rea. I/O Molar ionic LHSVtotal Press. Conversion C8 in the TMPs in DMHs in TMPs/DMH RON Ref.
no. of temp. time ratio liquid/olefin (h−1) (bar) of butene product the the ratio
ionic (°C) (min.) ratio (%) (wt%) product product
liquid (wt%) (wt%)

w/w)
96. [BSim][OTf] + CF3SO3H LBAIL## – 8 10 7.5 – – 2 68.3 57.9 – – 6.2 – [107]
(81.3:18.7, w/w)
##
97. [BSim][OTf] + CF3SO3H LBAIL – 8 10 7.5 – – 2 95.2 64.7 – – 5.1 – [107]
(48.3:51.7, w/w)
98. [BSim][OTf] + CF3SO3H LBAIL## – 8 10 7.5 – – 2 93.3 72.1 – – 5.7 – [107]
(33.3:66.7, w/w)
99. [Bmim][HSO4] + CF3SO3H LBAIL## – 8 10 7.5 – – 2 98.1 72.4 – – 8.1 – [107]
(23.2:76.8, w/w)
##
100. [Omim][HSO4] + CF3SO3H LBAIL – 8 10 7.5 – – 2 85.1 61.9 – – 6.2 – [107]
(67.6:32.4, w/w)
##
101. [Omim][HSO4] + CF3SO3H LBAIL – 8 10 7.5 – – 2 91.2 65.6 – – 6.8 – [107]
(59.6:40.4, w/w)
LBAIL## – – – – – –

S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313

102. [Omim][HSO4] + CF3SO3H 8 10 7.5 2 96.3 75.8 6.8 [107]
(23.7:76.3, w/w)
##
103. [Bmim][HSO4]-CuSO4 LBAIL H2SO4 15 – 12 – – – 96 77.8 – – 4.8 – [174]
104. [Bmim][HSO4]-CuCl LBAIL## CF3SO3H 15 – 12 – – – 96 83.7 – – 4.3 – [174]
105. [Emim][HSO4] LBAIL## H2SO4 15 – 12 – – – 96 56.8 – – 11.3 – [174]
106. [Et3NH][HSO4] BAIL## H2SO4 15 – 12 – – – 96 64.8 – – 10.8 – [174]
107. [Bmim][HSO4] LBAIL## H2SO4 15 – 12 – – – 96 58.9 – – 6.2 – [174]
108. [Omim][HSO4] LBAIL## H2SO4 15 – 12 – – – 96 55.2 – – 6.7 – [174]
109. [BSmim][HSO4] LBAIL## H2SO4 15 – 12 – – – 96 62.5 – – 7.0 – [174]
110. [Emim][HSO4] LBAIL## CF3SO3H 15 – 12 – – – 96 56.0 – – 10.5 – [174]
111. [Emim][HSO4]-CuCl LBAIL## H2SO4 10 – 12 – – – 98 – 78.9 5.5 14.3 99.0 [174]
112. [Et3NH][HSO4]-CuCl LBAIL## H2SO4 10 – 12 – – – 98 – 77.2 6.3 12.3 98.7 [174]
113. [Emim][OTf]-CuCl BAIL## CF3SO3H 10 – 12 – – – 98 – 79.6 5.3 15.0 99.1 [174]
114. [Emim][Tf2N]-Cu(OTf2) BAIL## CF3SO3H 10 – 12 – – – 98 – 72.1 8.5 8.5 97.1 [174]
115. [Et3NH]Cl-GaCl3 (xGaCl3 = 0.65) LAIL# – 15 15 – – – 5 – 41.2 34.6 6.3 5.5 89.4 [131]
116. [Et3NH]Cl-GaCl3 (xGaCl3 = 0.65) LAIL# 2% CuCl 15 15 – – – 5 – 54.4 42.9 11.3 3.8 90.4 [131]
117. [Et3NH]Cl-GaCl3 (xGaCl3 = 0.65) LAIL# 5% CuCl 15 15 – – – 5 – 70.1 50.5 11.4 3.5 91.3 [131]
118. [Et3NH]Cl-GaCl3 (xGaCl3 = 0.65) LAIL# 8% CuCl 15 15 – – – 5 – 52.1 4.5 1.3 3.6 88.8 [131]
119. [Et3NH]Cl-GaCl3 (xGaCl3 = 0.65) LAIL# 5% CuBr 15 15 – – – 5 – 48.4 37.7 10.2 3.7 89.4 [131]
120. [Et3NH]Cl-GaCl3 (xGaCl3 = 0.65) LAIL# 5% CuBr 15 15 – – – 5 – 48.3 38.6 9.2 4.2 89.1 [131]
121. Et3NHCl-AlCl3 (x = 1.0) LAIL# – 30 – 10 – – – 0 – – – – – [100]
122. Et3NHCl-AlCl3 (x = 1.25) LAIL# – 30 – 10 – – – 95 45.6 – – 2.2 – [100]
123. Et3NHCl-AlCl3 (x = 1.5) LAIL# – 30 – 10 – – – 98 48.8 – – 2.7 – [100]
124. Et3NHCl-AlCl3 (x = 1.8) LAIL# – 30 – 10 – – – 99 52.5 – – 2.6 – [100]
125. Et3NHCl-AlCl3 (x = 2.0) LAIL# – 30 – 10 – – – 99 49.6 36.5 13.1 2.8 88.4 [100]
126. Et3NHCl-AlCl3 (x = 2.0) LAIL# C6H6 (0.8 wt%) 30 – 10 – – – 98 76.2 – – 8.8 – [100]
127. Et3NHCl-AlCl3 (x = 2.0) LAIL# C6H6 (1.0 wt%) 30 – 10 – – – 98 76.2 72.0 8.9 8.1 95.6 [100]
128. Et3NHCl-AlCl3 (x = 2.0) LAIL# C6(CH3)6 (0.8 wt%) 30 – 10 – – – 99 78.6 – – 9.7 – [100]
129. Et3NHCl-AlCl3 (x = 2.0) LAIL# C6H5NO2 (0.8 wt%) 30 – 10 – – – 98 43.4 – – 1.1 – [100]
130. Et3NHCl-AlCl3 (x = 2.0) LAIL# C6H5Cl (0.8 wt%) 30 – 10 – – – 99 47.5 – – 1.3 – [100]
131. AlCl3 (1 g) LAIL# – 30 – 10 – – – 96 56.2 – – 1.9 – [100]
132. AlCl3 (1 g) LAIL# C6H6 (0.20 g) 30 – 10 – – – 95 66.7 – – 4.8 – [100]
133. AlCl3 (1 g) LAIL# C6H6 (0.39 g) 30 – 10 – – – 95 76.2 – – 7.6 – [100]
134. AlCl3 (1 g) LAIL# C6H6 (0.59 g) 30 – 10 – – – 95 73.1 – – 7.7 – [100]
135. [C4mim]Cl/2AlCl3-0.5CuCl LAIL# – 15 30 11–14 – – – – 85.6 – – 13.5 – [175]
136. [C6mim]Cl/2AlCl3-0.5CuCl LAIL# – 15 30 11–14 – – – – 88.7 – – 13.8 – [175]
137. [C8mim]Cl/2AlCl3-0.5CuCl LAIL# – 15 30 11–14 – – – – 89.6 – – 14.7 – [175]
138. [N222H]CF3SO3 (x = 0.69) BAIL## – 5 10 – 30:50 500 – – 86.23 78 8 9.75 97.3 [160]
139. [N222H]CF3SO3 (x = 0.69) BAIL## – 10 10 – 30:50 500 – – 84.5 75 7.5 10 96 [160]
140. [N222H]CF3SO3 (x = 0.69) BAIL## – 15 10 – 30:50 500 – – 78.5 74 6 12.3 94.5 [160]
141. [N222H]CF3SO3 (x = 0.69) BAIL## – 20 10 – 30:50 500 – – 75 54 8 6.75 93 [160]
 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313 305

as octane number of alkylate is direct function of its TMP content. CuCl is

[160]
[160]
[59]
[59]
[59]
[59]
[59]
[59]
[59]
[59]
one of the best additives for alkylation resulting in the formation of
TMPs with around 65% selectivity. Appropriate combination of ionic liq-
91.3
89.8

94.7
96.2
99.1
92

uid and additive is also important for driving the reaction in desired di-
rection. For example, [BMIm]Cl-AlCl3 in the presence of CuCl produces
TMP as the major product [152]. Aromatic compounds also serve as ef-
15.7
4.9
4.1
2.8
3.0
2.8
2.8
2.9
6.5
7.7
fective additives for the improved selectivity towards C8 in the product,
where its addition leads to the modification in electronic properties of
Lewis acid sites in the catalyst due to π-complexation of Lewis acid
sites with the π-cloud of aromatic ring. The process stabilizes alkyl
10.5
14.8

10.1
9.4
5.4
10

carbenium ion through its addition to the aromatic ring and inhibits
the side reactions. Further, presence of electron donating groups in
the aromatic ring increases trimethyl pentane to dimethyl hexane
41.4

64.8
72.5
85.0

(TMP/DMH) ratio, while the presence of electron withdrawing groups

49
44

show poor catalytic performance [100]. Organosulfur compounds,

such as thioalcohol in combination with ionic liquids improve product
distribution of isobutane alkylation during alkylation [50].
64.1
56.2
50.4
56.1
57.0
57.5
74.8
72

Triflic acid is also a promising promoter used as catalyst for alkyl-

ation reaction in combination with ionic liquids [157], however pro-
duces alkylate with lesser C8 selectivity due to its strong acidic nature
(H0 = −14.1) [155]. It is generally used as a 1:1 mixture with ionic liq-
97
97
96
96
96
96
–
–

uid at a desired temperature under the flow of a noble gas like argon. If
compared, triflate anion/ionic liquid combination shows lesser reactiv-
ity and selectivity than triflic acid/ionic liquid combination as it reduces
–
–

isoalkane/alkene ratio in the system, which is required for the reaction

with higher conversion.
Here it is important to note that without promoters amount of TMPs
500
500

increases with time, whereas in the presence of promoters initially the

amount of TMPs is much higher than the product obtained in the ab-
sence of promoters, but decreases with time, probably due to the deac-
30:50
30:50

tivation of catalyst [147].

4. Deactivation in ionic liquids

10
10
10
10
10
10
26
26
–
–

As compared to solid acids, most of the ionic liquids maintain high

catalytic activity during the reaction without any carbon deposition,
10
10

however undergo deactivation with time due to their moisture sensitive

nature, which causes decomposition of organic components and forma-
25
30
30
30
30
30
30
30
30
15

tion of hydroxyl chloroaluminates [50,114,163].

Rate of deactivation of catalyst depends upon the size of organic
droplets in ionic liquid medium. Larger droplets formed as a result of
low interfacial area between organic and catalyst phase lead to slow hy-
dride transfer, deactivating the catalyst more. Thickness of ionic liquid
layer, in which alkylation takes place, is up to few micrometers only,
and varies in the order for C4 N C5 N C6 alkylation [164]. Ionic liquids un-
ZnCl2
SnCl4

NiCl2
CuCl
CuCl
CuCl
HCl
–
–
–

dergo deactivation mainly due to structural changes resulting in solid

product formation [165,166]. In case of triflic acid particularly, increas-
ing sulfur content with time decreases the acidity of the system
resulting in decreased selectivity of C8 products. It also results in the for-
mation of higher amount of acid soluble oils (ASOs) containing polycy-
clic olefin structures [122,167,168]. The deactivation of ionic liquids is
caused by the decrease in their acid strength by ASOs through the for-
BAIL##
BAIL##
LAIL#
LAIL#
LAIL#
LAIL#
LAIL#
LAIL#
LAIL#
LAIL#

mation of complexes between olefins and chloroaluminate species

[130,169–171].
LBAIL## Lewis-Bronsted acidic ionic liquids.

Recovery and reusability of catalyst is important for making the pro-

[N222H]CF3SO3 (x = 0.69)
[N222H]CF3SO3 (x = 0.69)

cess economical, however efficiency reduces after few cycles due to

BAIL## Bronsted acidic ionic liquids.

quick decline in their acidity [148,172], whereas in few cases, catalyst

Et3NH·HCl-AlCl3
Et3NH·HCl-AlCl3
Et3NH·HCl-AlCl3
Et3NH·HCl-AlCl3
Et3NH·HCl-AlCl3
Et3NH·HCl-AlCl3
Et3NH·HCl-AlCl3
Et3NH.HCl-AlCl3

has been reused till 36 cycles without obvious loss of activity, probably
LAIL# Lewis acidic ionic liquids.

due to buffering action of the anion clusters [173].

5. Alkylation chemistry

Isobutane alkylation is a chain reaction proceeding via carbocation

mechanism regardless of the type of catalyst used (sulfuric acid,
142.
143.
144.
145.
146.
147.
148.
149.
150.
151.

hydrofluoric acid, solid acid or ionic liquid) [134,176]. Strong acidic

strength is crucial for maintaining a stable activity for alkylation
306 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313

Table 2
Structures of ionic liquids mentioned in the article.

S. no. Ionic liquid Abbreviation Structure

1. 1-Butyl-3-methylimidazolium bromide [C4mim]Br

2. 1-Hexyl-3-methylimidazolium bromide [C6mim]Br

3. 1-Octyl-3-methylimidazolium chloride [C8mim]Cl

4. 1-Octyl-3-methylimidazolium iodide [C8mim]I

5. 1-Octyl-3-methylimidazolium bromide [C8mim]Br

6. 1-Butyl-3-methylimidazolium chloride [C4mim]Cl

7. Triethyl ammonium chloride [Et3NH]Cl

8. Poly(4-vinylpyridinium) poly(hydrogen fluoride) PVPHF

9. 1-Hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [Hmim][Tf2N]

 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313 307

Table 2 (continued)

S. no. Ionic liquid Abbreviation Structure

10. 3-Methyl-1-(3-sulfopropyl)-imidazolium trifluoromethylsulfonate [MPSim][OTf]

11. 3-Methyl-1-(3-sulfobutyl)-imidazolium trifluoromethylsulfonate [MBSim][OTf]

12. 1-Butyl-3-methyl-imidazolium hydrogen sulfate [Bmim][HSO4]

13. 1-Octyl-3-methyl-imidazolium hydrogen sulfate [Omim][HSO4]

14. 1-(3-Sulfobutyl)-imidazolium hydrogen sulfate [BSim][HSO4]

15. 1-(3-Sulfobutyl)-imidazolium trifluoromethylsulfonate [BSim][OTf]

16. 1-Ethyl-3-methyl-imidazolium hydrogen sulfate [Emim][HSO4]

17. Triethylamine hydrogen sulfate [Et3NH][HSO4]

18. 1-(3-Sulfobutyl)-3-methyl-imidazolium hydrogen sulfate [BSmim][HSO4]

19. 1-Ethyl-3-methyl-imidazolium trifluoromethylsulfonate [Emim][OTf]

20. 1-Ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl) imide [Emim][Tf2N]

21. 1-Hexyl-3-methylimidazolium chloride [C6mim]Cl

(continued on next page)

308 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313

Table 2 (continued)

S. no. Ionic liquid Abbreviation Structure

22. Triethylammonium trifluoromethane sulfonate [N222H]CF3SO3

23. Triethyl ammonium hydrogen chloride Et3NH.HCl

24. Ethanolammonium hydrogen sulfate [MEA][HSO4]

25. N,N-Dimethyl-N-ethanolammonium hydrogen sulfate [DMEA][HSO4]

26. N,N-Diethyl-N-ethanolammonium hydrogen sulfate [DEEA][HSO4]

27. N-Methyl-N,N-diethanolammonium hydrogen sulfate [MDEA][HSO4]

28. 2-Hydroxy-N,N-dimethylpropan-1-ammonium hydrogen sulfate [DMIPA][HSO4]

29. Triethylammonium hydrogen sulfate [TEA][HSO4]

30. Triethylammonium trifluoromethyl sulfonate [TEA][CF3SO3]

31. N,N-Diethyl-N-ethanolammonium trifluoromethyl sulfonate [DEEA][CF3SO3]

32. 2-Hydroxy-N,N-dimethylpropan-1-ammonium trifluoromethyl sulfonate [DMIPA][CF3SO3]

 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313 309

reaction [177]. The reaction initiates with the protonation of olefin gen-
erating t-butyl carbocation. This carbocation attacks on another mole-
cule of 2-butene to form 2,2,3-trimethyl pentane carbocation (2,2,3-
TMP+), some of which isomerize to 2,2,4-TMP+. An intermolecular hy-
dride shift takes place between isobutane and 2,2,4-TMP+ yielding
2,2,4-TMP as desired the product [162]. Hydride transfer also generates
a new t-butyl carbocation, which reacts with another 2-butene mole-
cule to continue with the chain reaction. Acid strength and catalyst com-
position affect the formation of t-butyl cation (t-C+
4 ) and rate of hydride
transfer, which is a key step during the reaction [154] (Fig. 4).
Isomerization in TMP carbonium ions via hydride or methyl shift
may also result in the formation of different TMPs in the mixture
[33,34,176], however it is proved from density functional theory
method (DFT) [177] that stability of different TMP+ follows the order:
2,2,4-sec-TMP+ N 2,3,4-tert-TMP+ N 2,2,3-tert-TMP+ [178] (Fig. 5).
It should be noted that above stated mechanism of isobutane alkyl-
ation is applicable with mineral acids.
In case of ionic liquids, different routes have been suggested by re-
searchers. While using [C4mim]Cl-AlCl3 and [C4mim]Cl-AlCl3/CuCl as
catalyst, the 2-butene alkylation was done using deuterated isobutane
in continuous flow equipment and the induction period was b4 min.
One of the product was TMPs-132 (with molecular weight 132)
(C8H18) which could be formed through self alkylation (pathway 1) of
deuterated isobutanes in the ionic liquid systems [178–180] (Fig. 6).
The other pathway (pathway 2) suggests the formation of TMP-123
(C8H9D9) according to the following mechanism (Fig. 7):
However, in the products the amount of TMP-123 was much lower
than that of TMP-124 (C8H8D10), suggesting the sequence of reaction
series to form the product (pathway 3) (Fig. 8).
Another proposed pathway (pathway 4) suggests the isomerization
of 2-butene to isobutene first before reaction with isobutene to form
TMPs (Fig. 9).
Other than the above mentioned products, TMP-116 was also
formed in major amount and accounted 30% fraction of total TMPs.

Cations
R
N
+ + +
N P S

N N

R
R
N-alkylpyridinium 1,3-dialkylimidazolium tetraalkylammonium tetraalkylphosphonium trialkylsulfonium

Anions
- - -
F F F

F F
F F
B F P Sb
F
F F F F
F F F
tetrafluoroborate hexafluorophosphate hexafluoroantimonate
O
CH3
-
N -
F3C S O
O C C

-
S O N N
O

O dicyanoimide trifluoromethyl sulfonate

4-tolylsulfonate
O -
- CF3 O
F3C N
S - C9H19 C
S OR S O
O
O O O O
O
bis(trifluorosulfonyl) imide alkylsulfate decanoate
- -
O O
- -
Br F3C C H3C C
Cl
chloride bromide O O
trifluoroacetate acetate

Fig. 2. Variety of ions present in ionic liquids.

310 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313

+ +

Fig. 6. Self alkylation of isobutene (pathway 1).

CD3
CD3
+
CH3CH2CH CH3 + CH3CH2CHC CD3
D
CD3
CD3 CD3
CH3

C8H9D9 (123)

Fig. 7. Formation of TMP-123 (C8H9D9) (pathway 2).

Along with it, rapid oligomerization of non-deuterated 2-butene

Fig. 3. Side reactions during isobutane alkylation.
followed by cracking, hydrogen transfer reactions etc. lead to various
TMPs with fewer deuteriums (pathway 5, Fig. 10).

+ H+ 6. Conclusion and future prospects

Ionic liquids familiarize new dimensions to clean and green homog-

2,2,4-TMP enous catalysis for isobutane alkylation producing high octane blending
components of gasoline. Ionic liquids in combination with strong acids,
additives, and promoters represent excellent catalytic activity for isobu-
Intermolecular hydride shift tane alkylation, resulting in high butene conversion with desired TPM
+ selectivity and research octane number (RON). Type of cations & anions
present in ionic liquids and their concentration play a key role in
attaining the acidity to the required limit. Thorough study indicates
that ionic liquids have various advantages as homogenous catalysts,
but few concerns are there too. Like, ionic liquids are very expensive
and chloroaluminates, in particular are sensitive to moisture. This
causes deactivation of ionic liquids due to release of HCl as a result of hy-
2,2,4-TMP+
2,2,3-TMP+ drolysis. In case of ILs associated with Bronsted acid functions, such as –
SO3H & [HSO4]−, sufficient acidity is not obtained to catalyze the reac-
Intramolecular hydride shift tion, along with existing problem like reactor corrosion, environmental
issues, high operating costs due to recycling, etc. These problems can be
Fig. 4. Catalytic alkylation of alkene-isoalkane [140]. overcome by adopting appropriate measures. Acidity of the ionic liquids

+ +

2,2,3-TMP+ 2,3,4-TMP+ 2,2,4-TMP+ 2,3,3,-TMP+

+ + +

2,2,4-TMP 2,3,4-TMP 2,2,3-TMP 2,3,3-TMP

Fig. 5. Formation of various TMPs in the product.

 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313 311

CD3 CD3
CH3CH2CH+CH3 + CH3CH2CH(D)CH3 + +
D
CD3 CD3 CD3 CD3

CH3CH=CHCH3

CD3 CD3

CD3 C CH+ CH CH3 CD3 C CH CH+ CH3

CD3 CD3
CH3 CH3

CH3CH2CH(D)CH3

CD3 D

CD3 C HC CH CH3

CD3
CH3

C8H8D10 (124)
Fig. 8. Formation of TMP-124 (pathway 3).

can be enhanced by increasing the number of acidic sites, such as

\\COOH, [HnPW12O40]−(3−n), etc. in the structure. Development of new
synthetic methods and appropriate scaling up technologies can help in re-
ducing the cost of ionic liquids also. Recyclability of used ionic liquids can
also make the process more economic. Discussions suggest that wisely
+ managing all the parameters and concerns, use of ionic liquids can act
as an outstanding homogenous catalyst for isobutane alkylation, present-
Fig. 9. Formation of TMPs through pathway 4. ing a sustainable route for obtaining clean oil in the refineries.

3 C12H24 + H+ C12H25+

C12H25+ + + C8H16

CD3 CD2

+ C8H16 C8H16D2 (TMP - 116) +

CD C
CD3
CD3 CD3 CD3

CD3 CD2

C8D18 (TMP - 132)

+
C
CD
CD3
CD3 CD3
CD3
Fig. 10. Formation of TMPs through pathway 5.
312 S. Singhal et al. / Journal of Molecular Liquids 285 (2019) 299–313
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