Revisión de La Tecnología de Alquilación de Isobutano Utilizando Catalizadores Iónicos Basados en Líquidos - Dónde Nos Encontramos - 2020

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org/IECR Review
Review of Isobutane Alkylation Technology Using Ionic Liquid-

Based CatalystsWhere Do We Stand?
Rajkumar Kore, Aaron M. Scurto, and Mark B. Shiflett*
Cite This: Ind. Eng. Chem. Res. 2020, 59, 15811−15838 Read Online
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ABSTRACT: Conventional strong liquid acids such as H2SO4 and

HF are used for the majority of current commercial isobutane
alkylation processes to produce motor fuel alkylates, but these
acids can have significant safety and sustainability concerns. Ionic
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liquid (IL) catalyst technologies offer potential advantages over

current processes due to the negligible vapor pressure and
molecularly tunable properties that can optimize both the
chemistry and engineering for alkylate production. In this review,
IL-based catalysts used in isobutane alkylation are reviewed. ILs
are categorized and discussed by type: (1) metal-based Lewis
acidic ILs, (2) metal-based Brönsted−Lewis acidic ILs, (3)
nonmetal-based Brönsted acidic ILs, and (4) immobilized/supported ILs. A critical perspective on the use of these ILs in
alkylation is presented, focusing on the effect of speciation and physicochemical properties on chemical reaction. Further, a summary
of IL speciation is provided and examples of how the tunability of ILs can be used to overcome current limitations in alkylation
chemistry. The reaction conditions and performance (e.g., conversion, C8 selectivity, and trimethylpentane:dimethylhexane ratio) of
literature reports are summarized. A comparison of IL-based catalysts with the incumbent H2SO4 process and the new ISOALKY
Chevron process are also discussed. Gaps in the literature (e.g., mass transfer rates, material compatibilities, and phase equilibrium)
associated with IL-based alkylation technology and our perspectives on solving the relevant issues in this field are summarized.
1. INTRODUCTION that accumulate in the catalyst pores. Once this carbonaceous

Alkylation of isobutane (C4 alkylation) with short-chain olefins material is formed, it is very difficult to remove from the
(C3−C5) is industrially important in the production of alkylate micropores. In addition, the cost of solid-acid catalysts is
as motor fuel additives.1−9 The most desirable components in higher compared with H2SO4 and HF, and there is no
the alkylate gasoline are trimethylpentanes (TMPs), which technically proven method for regenerating spent solid-acid
have research octane numbers (RONs) greater than 100. catalysts.10,11
Alkylate is a clean-burning fuel additive and is considered an Ionic liquids (ILs) have attracted significant attention from
ideal blending component for gasoline with advantages such as researchers due to their tunable physicochemical properties
high RON, no aromatics, and no sulfur-containing compounds. and have been widely investigated in multidisciplinary research
Conventionally strong liquid acids such as H2SO4 and areas.9,14−25 ILs are especially attractive for catalysis due to
anhydrous HF are currently used for commercial alkylation, their extremely low vapor pressure, easy recovery, and reuse.
but there are significant safety and environmental concerns due Due to significant safety and environmental concerns using
to the handling of large quantities of spent H2SO4 acid and the traditional acids such as anhydrous HF and large volumes of
potential for hazardous emissions of HF (Figure 1).2 Both H2SO4 in the commercial C4 alkylation technology, many IL-
technologies also require additional processing steps to remove based catalysts have been extensively studied.8,9,26 These ILs
either sulfates (H 2 SO 4 technology) or fluorides (HF are categorized by the type of IL and includes (1) metal-based
technology) from the alkylate. Lewis acidic ILs (usually chloroaluminates), (2) metal-based
Researchers have also developed and investigated solid acid Brönsted−Lewis (bifunctional) acidic ILs, (3) nonmetal-based
catalysts for the alkylation process that are less hazardous than
liquid catalysts, and a few industrial implementations have
recently been reported.10,11 However, there are some inherent Received: July 11, 2020
drawbacks for solid-acid-catalyzed alkylation such as rapid Revised: August 11, 2020
deactivation of the catalyst, which results in low product yield Accepted: August 11, 2020
and selectivity.12,13 The rapid deactivation of solid-acid Published: August 11, 2020
catalysts is due to the accumulation of carbenium ions on
active sites that lead to high molecular weight hydrocarbons
© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c03418

15811 Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Review
Figure 1. Catalyst used in alkylation of isobutane/alkene technologies (TMPs and DMHs represent trimethylpentanes and dimethylhexanes,
respectively).
Brönsted acidic ILs, and (4) immobilized/supported ILs. alkylation technologies is the lack of understanding of the
Metal-based ILs are one of the important classes of ILs that are chemistry and physicochemical IL properties. A critical and
formed by reacting a metal halide with an organic halide systematic correlation of speciation and mass transfer of ILs
salt.15,27 Among metal-based ILs, chloroaluminate ILs exhibit and their effects on the C4 alkylation technology is presented.
unique chemistry due to the anionic speciation (eqn 1), which Furthermore, a comparison of mechanisms for IL-based
can be fine tuned by varying the mole fraction, resulting in processes vs the incumbent H2SO4 process under similar
distinctive properties, (e.g., low melting point, viscosity, operating conditions is discussed. The current problems
acidity, and high conductivity).16 These chloroaluminate ILs associated with alkylation technologies and our perspectives
show great potential as Lewis acids and have been evaluated as for solving these issues are presented here.
an industrial-scale replacement for HF and H2SO4.28,29 Nobel
laureate Chauvin first reported the isobutane alkylation 2. MECHANISM OF ALKYLATION REACTIONS
reaction using AlCl3-based IL catalysts in 1994,30 which 2.1. Conventional Strong Acid-Catalyzed Process.
showed similar catalytic activity to that of H2SO4. Afterward, The traditional HF- or H2SO4-catalyzed isobutane/2-butene
various types of IL catalysts with (metal-based ILs) and alkylation reaction is believed to follow a carbonium ion
without metals have been reported for the alkylation mechanism that is summarized in Scheme 1.42 Initially, 2-
reaction.9,14,16−18,20,31−35 Our group has also studied binary butene is rapidly protonated to form the sec-butyl carbocation,
mixtures of acidic- and neutral-based ILs with acids (e.g., which then reacts with isobutane to form the tert-butyl
H2SO4 or CF3SO3H) to produce alkylates with high selectivity carbocation via hydride transfer. The tert-butyl carbocation
for TMPs and good stability.36,37 In the case of AlCl3-based IL reacts with 2-butene quickly to form the TMP carbocation,
catalyst development, various types of additives such as metal which then is converted to TMP (major product in alkylate)
halides (e.g., Cu, Zn, Sn, Ni, and Fe), HCl acid, Brönsted via hydride transfer from isobutane, and the tert-butyl
acidic IL, and solvents have been investigated along with AlCl3- carbocation is restored. In the intermediate step, TMP
based IL (composite IL catalyst) in the alkylation reaction. carbocation can isomerize and form different forms of TMPs
These composite catalysts have interesting catalytic behavior through hydride and methyl shifts.43−45 Wang et al.46 studied
due to their metal anionic speciation (e.g., [AlCl4CuCl]−) the C4 alkylation mechanism using density functional theory
which depends on the relative amounts of the IL chloride to and found the stability of TMP cations (2,2,4-sec-TMP+ >
AlCl3 (and additives).38,39 Generally, when the mole percent of 2,3,4-tert-TMP+ > 2,2,3-tert-TMP+) trend in accordance with
AlCl3 becomes greater than 50%, the IL has enough acidity for the TMPs selectivity in the obtained alkylate.47
the C4 alkylation reaction. Above 67% mole, the IL becomes 2.2. IL-Catalyzed Process. As discussed in the catalysis
super acidic. section below, IL-based catalysts can produce a better quality
AlCl3 AlCl3 of alkylate (especially, composite IL [C4C1im][Cl]−AlCl3−
[Cation]Cl ⎯⎯⎯⎯→ [Cation][AlCl4] HooooI [Cation][Al 2Cl 7] CuCl produced enhanced TMP selectivity). To study the
AlCl3 reaction mechanism, 2-butene and deuterated isobutane were
HooooI [Cation][Al3Cl10] (1) used in the presence of a chloroaluminate IL (e.g., [C4C1im]-
[Cl]−AlCl3 or [C4C1im][Cl]−AlCl3−CuCl) catalyst in
Recently, Chevron and Honeywell UOP announced a new continuous flow equipment, and the induction period was
liquid phase alkylation technology (ISOALKY) based on a less than 4 min.48,49 On the basis of the alkylate distribution of
tunable acidic chloroaluminate IL catalyst.28,40,41 The technol- TMPs from both ILs, various routes have been suggested by
ogy has been demonstrated in a 10 barrel per day (BPD) researchers (Scheme 2).
demonstration plant at Chevron’s Salt Lake City refinery using 2.3. Route-I: Self-Alkylation. In the product alkylate,
a proprietary AlCl3-based IL catalyst that requires separation of TMPs-132 (with molecular weight 132; C8D18) were detected,
alkyl-chloride byproducts.28 One of the main factors which could be formed through the self-alkylation of only
contributing to the difficulty of scale-up for this and other IL deuterated isobutane (without 2-butene) in the presence of IL.
15812 https://dx.doi.org/10.1021/acs.iecr.0c03418
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Scheme 1. Strong Acid (H2SO4/HF)-Catalyzed Mechanism for C4 Alkylation Reaction
This route was entirely different than the conventional acid- solvents) in the isobutane alkylation, but rarely have they
catalyzed reaction mechanism. studied the effect of physicochemical properties of ILs in their
2.4. Route-II: Similar to the H2SO4 Catalyzed Process. work. These metal-based ILs generally have much higher
This route was similar to the mechanism of the H2SO4- viscosity than H2SO4 and especially liquid HF. These viscous
catalyzed system.47 In the alkylate, TMP-123 (with molecular ILs can affect the C4 alkylation reaction, reducing mass
weight 123; C8H9D9) was detected, which could be due to the transport even with vigorous mixing. Liu et al.38 studied
direct alkylation between deuterated isobutane and 2-butene. It agitation in a liquid phase alkylation reaction using an IL
should be noted that the amount of TMP-123 product (from catalyst and confirmed that agitation speed affects the alkylate
Route-II) was significantly lower than that of TMP-124 quality (Figure 2). When the agitation was increased from 600
product (with molecular weight 124; C8H8D10). Therefore, to 1700 rev/min, the TMP product selectivity was also
another route was proposed based on the obtained product increased from 85 to 89 wt %, which indicates that agitation
TMP-124 (see Route-III, Scheme 2). affects the alkylate quality (agitation directly proportional to
2.5. Route-IV: Isomerize 2-Butene and Then React the TMP yield) (Figure 2). This suggests that the reaction was
with Isobutane. It should be noted that the amount of TMP- mass transfer limited. Therefore, the physicochemical proper-
123 (from Route-II) was significantly lower than that of TMP- ties of ILs become very important when studying liquid phase
124 (with molecular weight 124; C8H8D10) (from Route-III), alkylation reactions. A recently published patent application by
suggesting that 2-butene was converted to isobutylene (before Martins et al. measured the viscosity of a series of [Al2Cl7]−
alkylation) followed by reacting with deuterated isobutane. anion-based ILs used for the C4 alkylation reaction as shown in
This route was different than the conventional acid-catalyzed Figure 3.50 The increasing alkyl chain length from C1 to C8 in
reaction mechanism. the phosphonium cation-based IL [P444‑n][Al2Cl7] resulted in
2.6. Route-V: Oligomerization of 2-Butene and Then an increase in viscosity due to the increase in hydrophobicity.
React with Isobutane. The composite IL produced a lower However, a further increase in alkyl chain length from C8 to
amount of TMP-123 and TMP-124 compared to the
C12 actual led to a decrease in viscosity due to the
[C4C1im][Cl]−AlCl3 IL system in the C4 alkylation reaction.
disorganization of the IL structure. Overall the viscosity
However, TMP-116 was also formed in a larger amount and
trend for the [P444‑n]+ cation with the same anion [Al2Cl7]−
accounted for ∼30% of the total TMPs. This could be due to
-based ILs follows this trend: [P444−8]+ > [P444−12]+ > [P444−6]+
the rapid oligomerization of 2-butene, followed by cracking
and deuterated transfer reactions that lead to various TMPs > [P444−5]+ > [P444−1]+. Furthermore, the viscosity for various
with fewer deuteriums. This route was different than the cations with the same anion [Al2Cl7]−-based ILs follows this
conventional acid-catalyzed reaction mechanism. trend: [P444−5]+ > [C4Py]+ > [C4C1im]+. The imidazolium
cation-based chloroaluminate ILs have a lower viscosity
compared with the pyridinium cation-based ILs.51,52 These
3. MASS TRANSFER EFFECTS IN IONIC IL viscosity differences can have a significant effect on the C4
LIQUID-CATALYZED ALKYLATION alkylation reaction, and the related discussion is summarized in
Many researchers developed chloroaluminate ILs alone and in the catalysis section 5.1.2. Mass transfer effects often become
combination with other additives (e.g., metal salt/oxide and the key factor whether a given catalytic IL system can be scaled
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Scheme 2. IL-Catalyzed Mechanisms for C4 Alkylation Reaction48,49
up economically. However, as is shown here, the vast majority to Lewis acidity, depends on controlling their metal
of literature studies focus on the reaction chemistry rather than speciation.27 Key aspects of metal processing and electro-
these transport phenomena. chemical characteristics, including solubility and redox proper-
ties are a function of metal speciation. The main factors for
4. SPECIATION IN IONIC LIQUID-BASED CATALYSTS tuning the metal speciation (Lewis acidity) in halometallate
4.1. Metal-Based ILs Speciation. The physicochemical ILs include (1) the type of metal (e.g., Al, Ga, and Zn), (2) the
properties of halometallate ILs, from viscosity and conductivity mole fraction of metal chloride to organic chloride salt (χMCl),
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
becomes basic or neutral, and the dominant anion is [MCl4]−.

If χMCl is between 0.52−0.64, the melt becomes moderately
acidic with a mixture of anions like [MCl4]− and [M2Cl7]−.
However, if χMCl > 0.67, the melt becomes super acidic and is
mainly composed of [M2Cl7]−, although [AlCl4]−, [Al3Cl10]−,
and other acidic higher-order anions can also be present in
small quantities (Figure 4 and Table 1).14,27 The metal
speciation in both Al, as well as Ga, are similar but the
difference in their Lewis acidity is modified by the metal
present in the anion, following the trend Ga > Al. To tune the
metal speciation (eventually Lewis acidity) of the halometallate
ILs, various additives (listed in Table 1) have been added as a
cocatalyst/solvent/impurity with the halometallate ILs during
the C4 alkylation reaction. In a few cases, significant catalytic
activity was confirmed by the formation of new mixed metal
speciation. For example, [AlCl4CuCl]− mixed metal speciation
was confirmed by 27Al NMR and ESI-MS by simple mixing of
Figure 2. TMP selectivity as a function of I/O ratio and agitation in CuCl with imidazolium or ammonium cation-based chlor-
liquid phase isobutane alkylation.38 oaluminate ILs.38,39 In one case, the proposed new species
[Cu−N222][Al2Cl7] was given without any analytical verifica-
(3) additives such as water, solvent, and metal salts/oxides tion. In several other cases, the reactions have been carried out,
(e.g., metals can be Cu, Fe, Sn, and Ni), and (4) the nature of but the speciation was undetermined because of metal
the base in liquid coordination complexes (LCCs). The complexity.
catalytic activity of the halometallate ILs in C4 alkylation relies Generally, chloroaluminate ILs are prepared by the reaction
primarily on the type of metal, and the characterization of the of halide salts with AlCl3 and are composed of only anionic Al
ions is crucial although tedious. A large amount of information species. Recently, simple mixing of AlCl3 with base (or ligand)
has been collected on the speciation of halometallate ILs, leads to the formation of both cationic as well as anionic Al
which has been recently summarized in a critical overview of species (analogous to IL systems), which are called LCCs
metal speciation.15,27 Many modified or new halometallate ILs (Scheme 3).15,21,27 Usually, the ligands (N-/O-/S-donor) can
have been used in the C4 alkylation reaction. To correlate be, for example, acetamide, methylacetamide (NMA), N,N-
metal speciation in halometallate ILs and to understand their dimethylacetamide (DMA), and N-methyl formamide (NMF).
effect on C4 alkylation reaction, the metal speciation has been The solid AlCl3 reacts with any type of ligand at χAlCl3 = 0.5
examined and is summarized in Table 1. There are many (χAlCl3 represents a mole fraction of AlCl3 in the IL/LCC
combinations of catalysts that have been used in the C4 system) to form a liquid with Al species like [AlCl2L2]+ and
alkylation reaction, but only a few cases have studied metal [AlCl4]− (Table 1). If AlCl3 reacts with the ligand at χAlCl3 =
speciation and the effect on activity. Most literature studies 0.6, the liquid becomes super acidic (even greater than
either do not discuss speciation or infer from literature conventional chloroaluminate IL)21,58 due to Al present in
references. both cationic as well as anionic species like [AlCl2L2]+ and
For the conventional halometallate IL category, different [Al2Cl7]− (Table 1). These LCCs are emerging as alternatives
chlorometallate anions ([MCl4]−, [M2Cl7]−, and [M3Cl10]−; M to halometallate ILs. In general, LCCs are easy to prepare, are
= Al/Ga) are detected at different molar ratios of MCl3 to generally less expensive, and can have higher Lewis acidity
organic chloride salts. Generally, when χMCl < 0.5, the melt compared to conventional chloroaluminate ILs. With the
Figure 3. Effect of chloroaluminate ionic liquid viscosity at 25 °C on catalytic activity in liquid phase isobutane alkylation.
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 1. Catalyst Combinations Used in Isobutane Alkylation and Their Metal Speciationa
IL/LCC
[P444−12][Cl]−
Additive [HN222][Cl]−AlCl3 [CnC1im][Cl]−AlCl3 AlCl3 (χAl 0.67) AlCl3/L (L = NMA)
− χAl 0.5 χAl 0.6−0.64 χAl 0.67 χAl 0.5 χAl 0.6−0.64 χAl 0.67 χAl 0.5 χAl 0.57−0.61
− − − − − − − −
[AlCl4] [AlCl4] & [Al2Cl7] [Al2Cl7] [AlCl4] [AlCl4] & [Al2Cl7] [Al2Cl7] [AlCl2(L)2]+ & [AlCl2(LA)2]+ &
[Al2Cl7]− [AlCl4]− [Al2Cl7]−
HCl53 × × n.d. × × × × × ×
CuCl38,39,53−55 [AlCl4CuCl]− or Assumed Complex of CuCl with × [AlCl4CuCl]− × × × [AlCl2(L)2]+ &
[Cu−N222][Al2Cl7] [AlCl4]− &/or [Al2Cl7]− [AlCl4CuCl]−
SnCl453 × × n.d. × × × × × ×
CuCl2 × n.d. n.d. × × × × × ×
ZnCl239,53,56 × × n.d. × n.d. × × × n.d.
NiCl239,53,54 × n.d. Assumed × n.d. × × × ×
[Ni(AlCl4)3]−
AgCl/SnCl2/ × × × × n.d. × × × ×
CeCl339
Industrial & Engineering Chemistry Research
CuO/ZnO/ × n.d. × × n.d. × × × ×

Tb4O7/CeO239
Dowex resin54 × × × × n.d. × × × ×
H2O38,57 × × Assumed × × × × × ×
[Al2Cl6OH]−
Organic solvents × × n.d. × × n.d. × × ×
a
15816
χAl, mole fraction of AlCl3 in IL; n.d., not determined; ×, not reported.
pubs.acs.org/IECR
Review
Ind. Eng. Chem. Res. 2020, 59, 15811−15838

https://dx.doi.org/10.1021/acs.iecr.0c03418
C4 alkylation reaction, but rarely have they studied the effect of

speciation and viscosity. Using these binary mixture catalysts,
significant catalytic activity was obtained compared with only
the neat IL or neat acid. Simple mixing of the IL and acid
should not have led to a significant increase in activity;
therefore, what is the reason behind this significant activity? Is
there any synergetic effect of IL and acid in terms of reaction
chemistry or other physical properties (e.g., thermodynamic
and mass transport)? To understand the reason behind this
increase in activity using a trace amount of IL in acid, Zhang et
al.’s59 research group studied the mixture of perfluorinated
anion containing ILs (e.g., 0.5 wt % [C4C1im][PF6] or 0.66 wt
% [C4C1im][SbF6]) and H2SO4 systems. Acid strength is one
of the most crucial factors affecting C4 alkylation. Therefore,
the Hammett acidity H0 values of H2SO4, ILs, and a mixture of
IL−H2SO4 were measured using NMR techniques with a
Figure 4. Phase diagram for the [C4C1im][Cl]−AlCl3 system.14
mesityl oxide spectroscopic probe. The Hammett acid values
of the binary mixtures ([C4C1im][PF6]−H2SO4 (H0 =
−10.087) and [C4C1im][SbF6]−H2SO4 (H0 = −10.104))
further addition of CuCl into LCC to control Lewis acidity, were slightly enhanced or similar to H2SO4 compared to every
new species like [AlCl2L2]+ and [AlCl4CuCl]− have been single component in the system (e.g., H0 = ∼−7 for ILs and
characterized. −10.063 for H2SO4). This enhanced Hammett acidity was
Many ZnCl2-based ILs with either Lewis acidic or both proposed due to either the small amount of HF deriving from
Brönsted−Lewis acidic systems have been investigated for C4 the acidolysis of anions or the generation of super acidic
alkylation, but there is no discussion for either the viscosity or species.59,60 These systems were investigated by using 19F and
Zn speciation of the system. The lack of discussions around Zn 31
P NMR and confirmed the formation of a small amount of
speciation can be attributed to the involved complexity. The new species with the general formula
inconsistencies in the characterization of chlorozinkate ILs [AF6‑x‑2y(HSO4)x(SO4)y]− (where A = P/Sb) and also HF
between mass and Raman spectroscopic analyses indicate the generation from the perfluorinated anion containing an IL and
possible existence of different anionic species. For more details H2SO4 binary system. Further, these types of binary mixture
on these specifics, we recommend the published review article catalyses in C4 alkylation reactions and the related discussion
by Estager et al.27 are summarized in the catalysis section 5.3.1. To the best of
Still, many interesting combinations can lead to new our knowledge, there is no evidence for the speciation report
catalysts for isobutane alkylation. The summary provided in from other binary systems containing nonperfluorinated anion-
Table 1 can help readers in the field of catalysis gain a better based ILs (e.g., [HSO4]−, [CF3SO3]−, [NTf2]−) and acid.
understanding of how to design new catalysts in the future.
The information can also help those who want to study the
fundamental new chemistry involved in this class of ILs.
5. ISOBUTANE/BUTENE ALKYLATION CATALYZED BY
4.2. Nonmetal-Based ILs Speciation. Several research IONIC LIQUIDS
groups (including ours) have used a binary mixture of different The alkylation of isobutane with short-chain olefins (e.g., 1-/2-
acidic/neutral ILs and acids (e.g., H2SO4 or CF3SO3H) in the butene) in the presence of an acidic catalyst is used to produce
Scheme 3. Comparison of Halometallate ILs and LCCs and Their Composites with CuCl along with Their Speciations (L =
N-/O-/S-Donor Ligands)
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 2. Alkylation of Isobutane with Butene Using Various Kinds of Lewis Acidic Chloroaluminate-Based ILsa
Weight
percentage in
product
(wt %)
IL TMP/
IL Speciation Viscosity T Time I/O P Conv. DMH
E.N. Catalyst Additive Technique (cST) (°C) (min) Ratio (MPa) (%) C8 TMP Sel. RON Ref
Chloroaluminate-Based ILs
1 [C4C1im][Cl]−AlCl3 None n.d n.d 5 − 15:1 − 100 − 29.0 7.1 87.5 30
(χAl 0.55)
(χAl 0.60)
(χAl 0.65)
4 [C8C1im][Cl]−AlCl3 None 27
Al NMR n.d. 80 30 20:1 − 69.5 50.3 6.9 0.30 − 20
(χAl 0.52)
5 [C8C1im][Br]−AlCl3 None 27
Al NMR n.d. 80 30 20:1 − 91.0 45.4 9.3 0.51 − 20
(χAl 0.52)
6 [C8C1im][I]−AlCl3 None 27
Al NMR n.d. 80 30 20:1 − 52.4 50.5 2.3 0.17 − 20
(χAl 0.52)
Al NMR n.d. 80 30 20:1 − 73.2 45.9 9.4 0.52 − 20
(χAl 0.52)
Al NMR n.d. 80 30 20:1 − 32.1 45.1 8.8 0.47 − 20
(χAl 0.52)
Al NMR n.d. 80 10 20:1 − 18.0 30.3 0.7 0.10 − 20
(χAl 0.48)
Al NMR n.d. 80 10 20:1 − 40.5 45.2 9.4 0.52 − 20
(χAl 0.52)
Al NMR n.d. 80 10 20:1 − 70.4 23.7 8.7 1.05 − 20
(χAl 0.58)
Al NMR n.d. 80 300 20:1 − 35.1 22.7 5.7 0.64 − 20
(χAl 0.58)
13 [C4C1im][Br]−AlCl3 None n.d. n.d. 35 30 10:1 0.4 − 40.1 20.2 1.0 80.9 61
(χAl 0.67)
14 [(C1OC2)C1im][Br]− None n.d. n.d. 35 30 10:1 0.4 − 66.6 56.6 7.3 93.0 61
AlCl3 (χAl 0.67)
15 [(C1OC2)C1im] None n.d. n.d. 35 30 10:1 0.4 − 48.4 31.2 1.8 86.0 61
[NTf2]−AlCl3
(χAl 0.75)
16 [(C1OC2)N111] None n.d. n.d. 35 30 10:1 0.4 − 57.6 41.8 3.5 89.0 61
[NTf2]−AlCl3
(χAl 0.75)
Effect of Cations on Chloroaluminate-Based ILs

17 [P444−1][Al2Cl7] None n.d. 55 25 − 10.3:1 3.4 100 85.0 − 10.6 96.1 50
18 [P444−5][Al2Cl7] None n.d. 65 25 − 11.1:1 3.4 100 87.0 − 25.4 98.4 50

19 [P444−6][Al2Cl7] None n.d. 160 25 − 10.4:1 3.4 100 84.0 − 18.0 97.2 50
20 [P444−8][Al2Cl7] None n.d. >300 25 − 10.6:1 3.4 100 82.0 − 22.6 97.5 50
21 [P444−10][Al2Cl7] None n.d. − 25 − 9.5:1 3.4 100 80.0 − 17.3 96.5 50
22 [P444−12][Al2Cl7] None n.d. 230 25 − 10.3:1 3.4 100 77.0 − 13.7 95.7 50
23 [P333−6][Al2Cl7] None n.d. 100 25 − 9.6:1 3.4 100 78.0 − 8.2 94.4 50
24 [C4C1im][Al2Cl7] None n.d. 15 25 − 9.1:1 3.4 100 83.0 − 8.4 94.9 50
25 [C8C1im][Al2Cl7] None n.d. 25 25 − 11.2:1 3.4 100 79.0 − 7.7 94.3 50
26 [C4Py][Al2Cl7] None n.d. 20 25 − 11.2:1 3.4 100 84.0 − 7.5 94.6 50
27 [C16Py][Al2Cl7] None n.d. 110 25 − 10.4:1 3.4 100 69.0 − 10.8 93.6 50
a
T, temperature; I/O, ratio of isobutane (I) to olefins (O); P, pressure; Sel., selectivity; Ref, reference; χAl, mole fraction of AlCl3 in IL; n.d., not
determined/discussed.
alkylated products for applications such as motor fuel additives. the catalytic activity were adjusted by the molar fraction of
As discussed in Section 1, due to significant safety and AlCl3. With an increasing mole fraction of AlCl3 from 0.55 to
environmental concerns four-types of IL-based catalyst 0.6 in [C4C1im][Cl]−AlCl3 (controlled acidity), the concen-
categories are described in this section tration of the main product (TMP) in the alkylate increased.
5.1. Metal-Based Acidic Ionic Liquids (or Halometal- However, further increasing the mole fraction of AlCl3 from
late ILs). 5.1.1. Chloroaluminate-Based ILs. Chauvin first 0.6 to 0.65 (stronger acidity) led to the TMP concentration
reported the chloroaluminate IL-based catalyst [C4C1im]- decreasing. Later, Yoo et al.20 investigated C4 alkylation using
[Cl]−AlCl3 for liquid phase C4 alkylation (Table 2, entries 1− different Lewis acidic chloroaluminate ILs, which included
3) in 1994.30 In this report, both the acidity of the IL as well as variations such as (1) halides (Cl, Br, and I), (2) alkyl groups
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 3. Alkylation of Isobutane with Butene Using Various Kinds of Additives along with Lewis Acidic Metal-Based ILsa
Weight
percentage in
product (wt %)
IL IL TMP/
Speciation Viscosity T (° Time I/O P Conv. DMH
E.N. Catalyst Additive Technique (cST) C) (min) Ratio (MPa) (%) C8 TMP Sel. RON Ref
Effect of Additives on Chloroaluminate-Based ILs:
1 [HN222][Cl]− None Inferred62 n.d. 30 − 10:1 − 97 56.2 − 2.8 − 53
AlCl3 (χAl 0.67)
2 [HN222][Cl]− HCl Inferred62 n.d. 30 − 10:1 − 97 50.4 − 3.0 − 53
AlCl3 (χAl 0.67)
3 [HN222][Cl]− SnCl4 (5 mol %) Inferred62 n.d. 30 − 10:1 - 96 56.1 − 2.8 − 53
AlCl3 (χAl 0.67)
4 [HN222][Cl]− ZnCl2 (5 mol %) Inferred62 n.d. 30 − 10:1 − 96 57.0 − 2.8 − 53
AlCl3 (χAl 0.67)
5 [HN222][Cl]− NiCl2 (5 mol %) Inferred62 n.d. 30 − 10:1 − 96 57.5 − 2.9 − 53
AlCl3 (χAl 0.67)
6 [HN222][Cl]− CuCl (5 mol %) Inferred62 n.d. 30 − 10:1 − 96 74.8 − 6.5 − 53
AlCl3 (χAl 0.67)
7 [HN222][Cl]− None 27
Al NMR, n.d. 15 30 10:1 − − 48.3 33.3 − 88.1 38
AlCl3 (χAl 0.63) ESI-MS
8 [HN222][Cl]− None 27
Al NMR, n.d. 15 30 10:1 − − 48.0 33.5 − 88.5 38
AlCl3 (χAl 0.63)- ESI-MS
CuCl (χCu 0.4)
9 [HN222][Cl]− None 27
Al NMR, n.d. 15 30 10:1 − − 97.3 92.0 − 99.5 38
AlCl3 (χAl 0.63)- ESI-MS
CuCl (χCu 0.5)
10 [HN222][Cl]− None Inferred63 n.d. 15 30 10:1 − − 46.8 − − − 38
AlCl3 (χAl 0.55)
AlCl3 (χAl 0.60)
AlCl3 (χAl 0.67)
13 [HN222][Cl]− H2O (∼50 ppm) n.d. n.d. 15 30 10:1 − − 39.5 − − − 38
AlCl3 (χAl 0.67)
14 H2SO4 (96%) None − n.d. 15 30 10:1 − − 72.1 − − − 38
15 [HN222][Cl]− None Inferred64 n.d. −5 60 13:1 0.6 − 46.7 42.1 − 94.5 54
AlCl3 (χAl 0.6)
16 [C8C1im][Br]− None Inferred64 n.d. −5 60 13:1 0.6 − 23.3 21.3 − 90.5 54
AlCl3 (χAl 0.6)
17 [C8C1im][Br]− H2O (30 ppm) Inferred 64
n.d. −5 60 13:1 0.6 − 45.6 41.4 − 93.7 54
AlCl3 (χAl 0.6)
18 [C8C1im][Br]− H2O (90 ppm) Inferred64 n.d. −5 60 13:1 0.6 − 59.0 49.2 − 93.7 54
AlCl3 (χAl 0.6)
19 [C8C1im][Br]− H2O (120 ppm) Inferred64 n.d. −5 60 13:1 0.6 − 32.0 28.9 _ 92.0 54
AlCl3 (χAl 0.6)
20 [C8C1im]Br]− None n.d. n.d. −5 60 13:1 0.6 − 23.3 21.3 _ 90.5 54
AlCl3 (χAl 0.6)
21 [C8C1im][Br]− CuCl (0.67 n.d. n.d. −5 60 13:1 0.6 − 34.5 32.1 _ 92.6 54
AlCl3 (χAl 0.6) mol %)
22 [C8C1im][Br]− CuCl2 (0.67 n.d. n.d. −5 60 13:1 0.6 − 29.0 26.9 − 91.2 54
23 [HN222][Cl]− None n.d. n.d. −5 15 13:1 0.6 − − 58.9 6.5 95.2 54
AlCl3 (χAl 0.6)
24 [HN222][Cl]− CuCl (0.67 Al−Cu n.d. −5 15 13:1 0.6 − − 72.3 13.6 98.0 54
AlCl3 (χAl 0.6) mol %) complex
25 [HN222][Cl]− CuCl2 (0.67 n.d. n.d. −5 15 13:1 0.6 − − 61.2 7.5 95.5 54
26 [HN222][Cl]− NiCl2 (0.67 n.d. n.d. −5 15 13:1 0.6 − − 63.5 8.8 95.9 54
27 [HN222][Cl]− None 27
Al NMR n.d. 30 30 7:1 0.4 − − 37.1 3.4 86.8 39
AlCl3 (χAl 0.64)
28 [HN222][Cl]− CeCl3 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 59.2 3.8 93.2 39
AlCl3 (χAl 0.64) mL IL)
29 [HN222][Cl]− CuCl (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 61.8 3.8 92.8 39
30 [HN222][Cl]− CuCl (χCu 0.33) 27
Al NMR n.d. n.d. 30 7:1 0.4 − − 68.0 8.2 95.1 39
AlCl3 (χAl 0.64) (CIL)
31 [HN222][Cl]− CuO (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 45.6 3.4 90.6 39
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 3. continued
Weight
percentage in
product (wt %)
IL IL TMP/
32 [HN222][Cl]− ZnO (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 44.9 3.6 88.4 39
33 [HN222][Cl]− CeO2 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 52.2 3.5 91.9 39
34 [C4C1im][Cl]− None 27
Al NMR 30 30 7:1 0.4 − − 43.7 4.4 90.6 39
AlCl3 (χAl 0.64)
35 [C4C1im][Cl]− AgCl (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 62.8 14.6 95.3 39
36 [C4C1im][Cl]− ZnCl2 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 60.1 8.6 93.9 39
37 [C4C1im][Cl]− NiCl2 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 67.3 15.3 96.1 39
38 [C4C1im][Cl]− CeCl3 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 67.8 15.1 95.8 39
39 [C4C1im][Cl]− SnCl2 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 60.2 12.3 93.8 39
40 [C4C1im][Cl]− CuCl (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 60.8 11.0 94.7 39
41 [C4C1im][Cl]− None 27
Al NMR n.d. 30 30 7:1 0.4 − − 71.8 15.0 97.3 39
AlCl3 (χAl 0.64)-
CuCl (χCu 0.33)
42 [C4C1im][Cl]− CuO (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 58.3 17.1 93.9 39
43 [C4C1im][Cl]− ZnO (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 50.0 10.2 91.0 39
44 [C4C1im][Cl]− Tb4O7 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 54.7 11.4 92.4 39
45 [C4C1im][Cl]− CeO2 (1 g per 3 n.d. n.d. 30 30 7:1 0.4 − − 64.7 12.9 95.1 39
Effect of Additives on Chlorogallate-Based ILs

46 [HN222][Cl]− None Raman n.d. 15 15 10:1 0.5 − 41.2 34.6 5.5 89.4 65
GaCl3 (χGa 0.65)
47 [HN222][Cl]− CuCl (2 mol %) n.d. n.d. 15 15 10:1 0.5 − 54.4 42.9 3.8 91.3 65
GaCl3 (χGa 0.65)
GaCl3 (χGa 0.65)
GaCl3 (χGa 0.65)
50 [HN222][Cl]− CuBr (5 mol %) n.d. n.d. 15 15 10:1 0.5 − 48.4 37.7 3.7 91.3 65
GaCl3 (χGa 0.65)
51 [HN222][Cl]− CuCl2 (5 mol %) n.d. n.d. 15 15 10:1 0.5 − 48.3 38.6 4.2 91.3 65
GaCl3 (χGa 0.65)
52 H2SO4 (98%) None − n.d. 15 15 10:1 0.5 _ ∼36.0 28.9 _ 87.8 65
Effect of Organic Additives on Chloroaluminate-Based ILs

53 [HN222][Cl]− None 27
Al NMR n.d. 30 30 10:1 − 99.0 49.6 36.5 2.8 88.4 66
AlCl3 (χAl 0.67)
54 [HN222][Cl]− Benzene (0.6 wt n.d. n.d. 30 30 10:1 − − 66.3 − 8.4 − 66
AlCl3 (χAl 0.67) %)
55 [HN222][Cl]− Benzene (0.8 wt n.d. n.d. 30 30 10:1 − 98.0 76.2 − 8.8 − 66
AlCl3 (χAl 0.67) %)
56 [HN222][Cl]− Benzene (1 wt %) n.d. n.d. 30 30 10:1 − 99.0 80.9 72.0 8.1 95.6 66
AlCl3 (χAl 0.67)
57 [HN222][Cl]− Benzene (2 wt %) n.d. n.d. 30 30 10:1 − − 76.2 − 8.7 − 66
AlCl3 (χAl 0.67)
58 [HN222][Cl]− HMB (0.8 wt %) n.d. n.d. 30 30 10:1 − 99.0 78.6 − 9.7 − 66
AlCl3 (χAl 0.67)
59 [HN222][Cl]− Nitrobenzene n.d. n.d. 30 30 10:1 − 98.0 43.4 − 1.1 − 66
AlCl3 (χAl 0.67) (0.8 wt %)
60 [HN222][Cl]− Chlorobenzene n.d. n.d. 30 30 10:1 − 99.0 47.5 − 1.3 − 66
AlCl3 (χAl 0.67) (0.8 wt %)
61 [HN222][Cl]− Benzene (Fresh) n.d. n.d. 20 − 10:1 − − 82.8 − 13.5 − 66
AlCl3 (χAl 0.67) (0.8 wt %)
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 3. continued
Weight
percentage in
product (wt %)
IL IL TMP/
62 [HN222][Cl]− Benzene (3rd n.d. n.d. 20 − 10:1 − − 52.8 − 2.9 − 66
AlCl3 (χAl 0.67) cycle) (0.8 wt
%)
63 IL from 3rd recycle Benzene (0.8 wt n.d. n.d. 20 − 10:1 − − 75.6 − 11.2 − 66
%)
64 [C4C1im][Cl]− None n.d. n.d. 30 40 10:1 − 99.0 − 37.3 2.6 − 67
AlCl3 (χAl 0.67)
65 [C4C1im][Cl]− Butyl thioalcohol n.d. n.d. 30 40 10:1 − 99.0 − 65.9 6.6 − 67
AlCl3 (χAl 0.67)
66 [C4C1im][Cl]− Butyl thioether n.d. n.d. 30 40 10:1 − 99.0 − 36.9 2.5 − 67
AlCl3 (χAl 0.67)
a
T, temperature; I/O, ratio of isobutane (I) to olefins (O); P, pressure; Sel., selectivity; Ref, reference; χM, mole fraction of metal halide in IL; n.d.,
not determined/discussed.
(C4, C6, and C8) on imidazolium cation, and (3) mole fraction same [Al2Cl7]− anion-based ILs for C4 alkylation at a variety of
of AlCl3 (χ = 0.48−0.58) as shown in Table 2, entries 4−12. temperatures (Table 2, entries 17−27). A systematic study of
The halide salt variation in the chloroaluminate IL at χ = 0.52 the alkyl chain length from C1 to C12 in phosphonium cations
resulted in different catalytic activity (Table 2, entries 4−6). with the same [Al2Cl7]− anion-based ILs [P444‑n][Al2Cl7] was
The [C8C1im][Br]−AlCl3 IL at χ = 0.52 ([AlCl3Br]− anion investigated for C4 alkylation (Table 2, entries 17−22). Upon
species confirmed by 27Al NMR) was found to be a more increasing the alkyl chain length from C1 to C5 in the
effective catalyst compared to [C8C1im][Cl]−AlCl3 at χ = 0.52 [P444‑n][Al2Cl7] IL, the quality of alkylate increased (C8
([AlCl4]− and [Al2Cl7]− anions confirmed by 27Al NMR) or selectivity from 85% to 87% and RON from 96.1 to 98.4).
[C8C1im][I]−AlCl3 at χ = 0.52 ([AlCl4]−, [AlCl3I]−, and However, further increasing the alkyl chain length from C5 to
[AlCl2I2]− anions confirmed by 27Al NMR). The increasing C12, the quality of alkylate decreased (C8 selectivity from 87%
alkyl chain length from C4 to C8 in the [CnC1im][Cl]−AlCl3 to 77% and RON from 98.4 to 95.7), possibly due to the
IL at χ = 0.52 increases the catalytic activity (both conversion increased viscosity of the IL (see Figure 3, plot of viscosity vs
as well as TMP selectivity) (Table 2, entries 5, 7, and 8). The catalytic activity of ILs). In case of long chain ILs, there could
increasing mole fraction of AlCl3 from 0.48 to 0.58 in the be the possibility of emulsion formation in the reaction system.
[C4C1im][Br]−AlCl3 IL increased the conversion as well as While emulsions may help isobutane mass transfer, the
the TMP/DMH ratio due to the strong acidic [Al2Cl6Br]− increased residence time of iso-octane may actually lead to
species generated at the 0.58 mole fraction (confirmed by 27Al cracking reactions and other side reactions which decrease the
NMR and FT-IR). It should be noted that with longer reaction RON. In addition, the activity of the phosphonium cation-
times the strongly acidic, active [Al2Cl6Br]− anion deactivates based ILs was compared with imidazolium and pyridinium
(Table 2, entry 12). cation-based ILs and found to follow this catalytic trend in C4
Lu et al.61 investigated various ether group-containing alkylation activity
chloroaluminate ILs ([(C1OC2)C1im][Br]−AlCl3, [(C1OC2)-
C1im][NTf2]−AlCl3, and [(C1OC2)N111][NTf2]−AlCl3) for [P444 − 5] > [P444 − 6]+ > [P444 − 8]+ > [P444 − 1]+ > [P444 − 10]+
C4 alkylation (Table 2, entries 13−16). The ether group-
> [P444 − 12]+ > [C4 C1im] > [C4 Py] > [C8C1im]
containing IL [(C1OC2)C1im][Br]−AlCl3 was found to be a
more efficient catalyst compared with those with no ether > [C16Py]
group in the IL [C4C1im][Br]−AlCl3. Further, isobutane
solubility was measured to understand the difference in It should be noted that the higher viscous-containing ILs
catalytic activity. It was found that ether containing ILs had (e.g., [C16Py]+ and [P444−12]+ cations with the same anion
higher solubility (by mass basis), which could be the reason for [Al2Cl7]−) found lower activity when compared with less
the high catalytic activity. The [(C1OC2)C1im][NTf2]−AlCl3 viscous ILs (e.g., [C4C1im]+, [C4Py]+, and [P444−5]+ cation-
IL at χ = 0.75 was also investigated in C4 alkylation, but the based ILs). By increasing the reaction temperature from 25° to
activity was significantly lower than [(C1OC2)C1im][Br]− 50 °C in C4 alkylation, imidazolium and pyridinium cation-
AlCl3 at χ = 0.67. Furthermore, the [(C1OC2)C1im][Br]− based ILs produce lower quality alkylate (RON < 90), but the
AlCl3 IL was recycled and reused for up to five cycles. After the phosphonium cation-based ILs produce higher quality alkylate
fifth cycle, the C8 selectivity was decreased from 66.6% to (RON > 95). The higher temperature ranges from room
62.2% (RON reduced from 93.0 to 88.0). The decrease in the temperature up to 50 °C could provide an economic advantage
catalytic activity was due to the formation of acid-soluble when designing alkylation processes compared with the
compounds and decomposition of the IL when exposed to traditional H2SO4 technology because a refrigeration system
moisture air/hydrocarbon in the separation process of oil from would not be required (typically operating temperature for
the catalyst. H2SO4 alkylation is ≤10 °C).
5.1.2. Effect of Cations on Chloroaluminate-Based ILs. 5.1.3. Effect of Additives on Chloroaluminate-Based ILs.
Martins et al.50 investigated a series of phosphonium, Generally, imidazolium-based chloroaluminate ILs are more
imidazolium, and pyridinium cation combinations with the expensive,9 which limits the use in large-scale C4 alkylation.
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Therefore, less expensive, acidic chloroaluminate ILs, such as TMP selectivity was significantly enhanced from 21.3% (neat
[HN222][Cl]−AlCl3, have been developed by mixing triethyl- IL) to 49.2%, due to the formation of super acidic species
amine hydrochloride ([HN222][Cl]) and AlCl3. It has been (assumed [Al2Cl5BrOH]−) (Table 3, entries 16−18). How-
confirmed that [HN222][Cl]−AlCl3 IL at χ = 0.67 was an ever, with further increasing the H2O concentration from 90 to
efficient catalyst for C4 alkylation. To improve the alkylate 120 ppm (stronger acidity), the TMP concentration decreased
quality, another additive such as HCl or metal chloride was (Table 3, entries 18 and 19). With the addition of CuCl/
added along with the [HN222][Cl]−AlCl3 IL at χ = 0.67 in C4 CuCl2/NiCl2 salt into both imidazolium- and ammonium
alkylation (Table 3, entries 1−6).53 Using a Brønsted acid such cation-based chloroaluminate ILs, the TMP selectivity was
as HCl with the Lewis acidic [HN222][Cl]−AlCl3 IL (χ = 0.67) significantly improved (Table 3, entries 20−26). CuCl was
in C4 alkylation had no effect on conversion, but the C8 found to have the greatest effect, in accordance with the work
selectivity decreased from 56.2% to 50.4%, indicating an reported by Huang et al.53 and Liu et al.38
increase in the side-cracking reactions due to the super acidity Further, the different metal chloride/oxides (such as CuCl,
of the IL. In this report, speciation was not discussed, so it is AgCl, ZnCl2, SnCl2, CeCl3, CuO, ZnO, and CeO2) were added
uncertain to what extent the properties of the catalyst depend to different acidic chloroaluminate ILs (χAl 0.64) (Table 3,
on the speciation of the chloroaluminate anions. In the case of entries 27−45, the effect of IL composition). In this review,
adding metal chlorides such as ZnCl2, NiCl2, and SnCl4 with two strategies were used that included (1) adding 1 g of
the [HN222][Cl]−AlCl3 IL, the combination had no significant additive to 3 mL of IL at the beginning of the C4 alkylation
effect on the catalytic activity. However, when CuCl was added reaction (in situ composite IL synthesis) and (2) dissolving 0.5
to the IL, the C8 selectivity in the alkylate was increased mol of CuCl (χCu 0.33) in one mole of IL to obtain a
significantly from 56.2% to 74.8% (TMP/DMH ratio increased homogeneous composite IL that was then used for the
from 2.8 to 6.5). The presence of CuCl along with a reaction. After adding the metal salt to the IL, a significant
chloroaluminate IL could inhibit the occurrence of side enhancement in TMP selectivity was observed (Table 3,
reactions such as oligomerization of butene and cracking. entries 27−29 and 34−40). When the composite IL
Liu et al.38 prepared an Al−Cu composite IL by mixing the [C4C1im][Cl]−AlCl3−CuCl or [HN222][Cl]−AlCl3−CuCl
[HN222][Cl]−AlCl3 IL (χ = 0.63) with different mole fractions was used in C4 alkylation, a significant improvement in TMP
of CuCl ((χcu 0.4 and 0.5) and studied the effect on C4 selectivity as well as the TMP/DMH ratio occurred, due to the
alkylation (Table 3, entries 7−9). The composite IL made formation of a unique species [AlCl4CuCl]− as confirmed by
27
from [HN222][Cl]−AlCl3 (χAl 0.63) and CuCl (χCu 0.5) was a Al NMR (Table 3, entries 30 and 41). It should also be noted
significant improvement in alkylate quality compared with that the composite IL achieved higher performance than a
CuCl (χCu 0.4 or 0) under the same reaction conditions. The mixture of the IL and additive used in C4 alkylation (Table 3,
composite IL even showed higher activity than H2SO4 in C4 compare entry 30 with 29 and entry 41 with 40). This is a
alkylation (Table 3, compare entry 9 with 14). The significant result of the active species [AlCl4CuCl]− formed in the
increase in activity was primarily due to the presence of a new composite IL synthesis. The difference in catalytic activity
species [AlCl4CuCl]−, as confirmed by spectroscopic techni- between the case of [C4C1im]+ and [Et3NH]+ cation-based ILs
ques (such as 27Al NMR, ESI-MSand FT-IR). This new Al was likely due to a lower isobutane solubility in [HN222]+ than
species was not detected in the composite IL made from in the [C4C1im]+ cation-based IL. The Chevron U.S. patent
[HN222][Cl]−AlCl3 (χAl 0.63) and CuCl (χCu 0.4) and also did claimed a process for jet fuel production by reacting an
not show any significant improvement in the catalytic activity. isobutane stream with a process stream containing butene
These results suggest that the composite anion played an under C 4 alkylation conditions in the presence of a
important role in improving the alkylate quality. It was noted chloroaluminate IL catalyst coupled with a halide-containing
from the report that the isobutane solubility in the composite additive.69 The produced jet fuel meets the boiling point, flash
IL was low (no data provided). point, smoke point, freezing point, and heat of combustion
A significant enhancement in activity was observed using the requirements for Jet A-1 fuel.
composite IL when compared to conventional H2SO4 under 5.1.4. Composite IL Recovery and Reuse. During the
identical reaction conditions (Table 3, entry 9 compared with operation of the C4 alkylation reaction using composite IL
14). Furthermore, the agitation in the C4 alkylation reaction [HN222][Cl]−AlCl3−CuCl, solids were formed.70 In this
using the composite IL was studied, and it was confirmed that report, the obtained recycled solids were characterized by
agitation did affect the alkylate quality (Figure 2), suggesting NMR, X-ray diffraction, X-ray photoelectron spectroscopy, and
that the reaction was mass transfer limited (see discussion in elemental analysis. These spectroscopic results indicated that
Section 3). Chloroaluminate ILs could catalyze C4 alkylation the major component of the solids was cuprous chloride, with
efficiently, but they are quite sensitive to moisture and would about 1 wt % acid-soluble oil. The AlCl3 loss and precipitation
be hydrolyzed to release HCl gas upon contact with a trace of CuCl, potentially as the [HN222][Cl]−AlCl3−CuCl IL,
amount of H2O.18,68 To see the effect of H2O on the resulted in a decrease of catalyst acidity and therefore
[HN222][Cl]−AlCl3 (χAl 0.67) IL, 50 ppm of H2O was added decreased catalytic activity. During the recycling experiments,
to the isobutane during C4 alkylation, and it was found that the these solids accumulated in the reactor and could plug pipes.
TMP selectivity decreased from 43.5 to 39.5, which may be Various methods (e.g., filtration, centrifugation, and precip-
due to the change in Al speciation (Al speciation was not itation) were tried for the separation of the solid from the IL
discussed) (Table 3, entries 12 and 13). phase, but the removal of the solid was difficult because of the
To improve the quality of alkylate, Bui et al. investigated high viscosity of the IL. Furthermore, Klusener et al.71 claimed
various additives (such as H2O, resin, and metal salts) along a process for the separation of the solid from the IL phase by
with moderate acidic chloroaluminate ILs (χAl 0.6) (Table 3, mixing with organic solvents such as dichloromethane,
entries 15−26).54 With increasing H2O from 0 to 90 ppm in acetonitrile, benzene, and toluene. The IL phase can be
the [C8C1im][Br]−AlCl3 IL at χ = 0.6 (moderate acidity), the separated easily from the solids by extraction with organic
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
solvents. The acidity of the recycled IL can be recovered by enhanced catalytic activity in C4 alkylation, whereas the
introducing HCl gas, and the obtained catalyst could be reused electron-poor π-cloud in chlorobenzene and nitrobenzene led
further in C4 alkylation. to the decrease in the activity. To understand Al speciation in
5.1.5. Chlorogallate-Based ILs. Similar to chloroaluminate the IL−benzene mixture, 27Al NMR experiments were
ILs, chlorogallate-based ILs such as [HN222][Cl]−GaCl3 were collected for benzene dissolved IL and compared with neat
synthesized by reacting [Et3NH][Cl] with different mole IL. The data led to the assumption that there were interactions
fractions of GaCl3 from 0.6 to 0.75.65 As discussed in Section between the aromatics and Al species. There remains the need
4, speciation in chlorogallate-based ILs is similar to the to study further the Al speciation and the interactions with
chloroaluminate-based ILs; however, the Lewis acidity of aromatics. Furthermore, the [HN222][Cl]−AlCl3 (χ = 0.67) IL
chlorogallate ILs is the same or slightly higher than the with the benzene (0.8 wt %) additive catalyst system was
chloroaluminate ILs, which could have an affect on the C4 recycled and reused in C4 alkylation. The data confirmed that
alkylation reaction. With an increasing mole fraction of GaCl3 the recycled catalyst (after the third cycle) had lower catalytic
from 0.6 to 0.65 in [HN222][Cl]−GaCl3 (controlled acidity), performance than the fresh catalytic system due to partial loss
the alkylate quality was improved. However, further increasing of benzene into the product phase (Table 3, compare entry 62
the mole fraction of GaCl3 from 0.65 to 0.75 decreased the with 61). To retain (or recover) the catalytic activity, 0.8 wt %
alkylate quality due to the stronger acidic nature of the catalyst of benzene was introduced into the reused catalyst from the
(Table 3, entry 46). Furthermore, when adding CuCl (5 mmol third cycle, and the alkylate quality increased (Table 3,
%) to the [HN222]Cl−GaCl3 (χ = 0.65) IL, the C8 selectivity in compare entry 63 with 61). The loss of catalytic activity in
the alkylate increased significantly from 41.2% to 70.1% (RON recycling experiments may be due to weak complexation
from 89.4 to 91.3). The IL [HN222][Cl]−GaCl3 combination between benzene and the Al species, which causes a partial loss
with CuCl showed higher activity than H2SO4 in C4 alkylation of benzene into the product. However, the good catalytic
(Table 3, compare entry 48 with 52). The addition of metal performance in a continuous alkylation process can be
halide additives like CuCl into chlorogallate IL could form maintained by the regular replenishment of the benzene.
similar species obtained in the composite chloroaluminate IL Besides aromatics, organosulfur compounds such as butyl
(Table 3, entries 47−51), which could be the reason for the thioalcohol and butyl thioether were used as an additive with
significant enhancement in catalytic activity. [C4C1im][Cl]−AlCl3 (χ = 0.67) IL for C4 alkylation (Table 3,
5.1.6. Effect of Organic Additives on Chloroaluminate- entries 64−66).67 The addition of butyl thioalcohol to IL led
Based ILs. Another strategy to modify the acidity of to an increase in the alkylate quality (TMP selectivity increased
chloroaluminate ILs is to add organic additives. The organic from 37.3 to 65.9 wt %), whereas no improvement in alkylate
aromatics were used as an additive with the [HN222][Cl]− quality was observed with the addition of butyl thioether to the
AlCl3 (χ = 0.67) IL in the isobutane alkylation reaction (Table IL. Furthermore, the sulfur content in the alkylate was
3, entries 53−61).66 The small addition of benzene (0.8 wt %) measured to see if any leaching had occurred. No sulfur was
to the [HN222][Cl]−AlCl3 (χ = 0.67) IL gave a significant found in the alkylate, which indicates that the sulfur remained
improvement in alkylate quality that was observed when in the IL due to some type of interactions. The reason behind
compared with only IL activity (C8 selectivity increased from the enhanced catalytic activity using a mixture of IL−
49.6 to 76.2% and the TMP/DMH ratio increased from 2.8 to thioalcohol in C4 alkylation was proposed, but speciation was
8.8) (Table 3, compare entry 55 with 53). In this report, the not investigated.67 The super acidic homogeneous IL
authors assumed the π-complexation of Lewis acid sites for the [C4C1im][Cl]−AlCl3 (χ = 0.67) could be in equilibrium
IL with the π-cloud of the benzene ring that results from the between the neutral [C4C1im][Cl]−AlCl3 (χ = 0.5) IL and the
modification of the electronic properties of Lewis acid sites, Lewis acidic AlCl3. AlCl3 is regarded as the efficient active
which could be the reason for the improvement in alkylate catalyst to catalyze C4 alkylation. Typically, the C4 alkylation
quality. Also, benzene can stabilize alkyl carbenium inter- reaction is catalyzed by the Brönsted acid. In the case of the
mediates through the addition of an alkyl carbenium ion to the chloroaluminate IL, AlCl3 should be transformed into a
aromatic ring, which could inhibit side reactions. Furthermore, Brönsted acid through interactions between AlCl3 and HCl,
various aromatics were investigated with different electronic which came from the reaction of the IL anion with a trace of
environments (electron-donating/withdrawing group on ben- H2O in the feedstock. The interaction of AlCl3 and HCl at 1:1
zene) as additives in the [HN222][Cl]−AlCl3 (χ = 0.67) IL for molar ratio could occur only in the presence of a proton
C4 alkylation (Table 3, entries 58−60). The addition of acceptor and could form the complex species like
benzene or hexamethyl benzene (electron-donating substi- [HA]+[AlCl4]− (without experimental proof; “A” represents
tuted) in the IL provided an improvement in alkylate quality. proton acceptor).72 It was believed that the resulting complex
The addition of chloro/nitro-benzene (electron-withdrawing [HA]+[AlCl4]− acts as the Brönsted acid site to catalyze the
substituted) in the IL provided a lower quality alkylate. The alkylation reaction.73 In the chloroaluminate IL−butyl
electronic effect of the substituent can influence the π-cloud of thioalcohol-catalyzed C4 alkylation reaction, both butene and
the benzene ring. For nitrobenzene and chlorobenzene, a butyl thioalcohol were the proton acceptors due to their
negative electric charge is concentrated into C−NO2 or C−Cl, unshared electrons. Among these proton acceptors, butyl
with the delocalization of the π-cloud electron to the thioalcohol, which acts as a stronger electron donor was more
substituent, confirming the strong electron-withdrawing effect basic than butene and tended to bind to the AlCl3 and HCl
of these groups. A methyl group exhibits an electron-donating more strongly, forming a carbonium ion (with lower acid
effect through hyperconjugation and thus increases the strength): [HC4H8S]+[AlCl4]−. This complex could control
electron density in the π-cloud of hexamethyl benzene the acidity of the IL and thereby inhibit the occurrence of side
increasing its basicity over that of benzene. This suggests reactions.
that the coordination of the electron-rich π-cloud of benzene Aschauer et al.74 investigated tert-butyl halides as the
or hexamethyl benzene with the Lewis acid sites led to the promoter to enhance the activity of IL [C4C1im][Cl]−AlCl3
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
(χAl 0.64) in C4 alkylation at −20 °C to observe the effects at nate ILs due to the unique feature of Al speciation present in
lower reaction rates (Figure 5). The catalytic activities (in both the cationic as well as anionic forms (Scheme 3). This
unique Al species can have advantageous properties in
catalysis. Recently, AlCl3/base LCCs (analogs of chloroalumi-
nate ILs) were investigated for C4 alkylation (Table 4, entries
1−7).55 Upon increasing the mole fraction of AlCl3 from 0.51
to 0.57 in AlCl3/NMA LCC, the quality of alkylate increased
significantly (C8, TMP selectivity and RON). However, further
increasing the mole fraction from 0.57 to 0.61, the quality of
alkylate decreased, possibly due to increased acidity of the
LCC (similar to the conventional chloroaluminate IL).
Changing the base in the LCC can affect the acidity due to
the asymmetric splitting of AlCl3 in the final LCC composition.
C4 alkylation was conducted by testing four AlCl3/base LCCs
(AlCl3/acetamide, AlCl3/NMA, AlCl3/DMA, and AlCl3/
NMF) that were all found to be more active than the
conventional [HN222][Cl]−AlCl3 (χ = 0.61) under identical
conditions (Table 4, entries 5−7 compared with 9). The
catalytic activity trend in LCCs was as follows: AlCl3/NMA >
AlCl3/DMA > AlCl3/NMF > AlCl3/acetamide. The isobutane
Figure 5. 2-Butene conversion vs reaction time for [C4C1im][Cl]− solubility in the LCCs also followed a similar trend. The high
AlCl3 (χAl 0.64) with and without promoters (I/O = 13/1, T = −20 isobutane solubility (in AlCl3/NMA LCC) reduced the
°C, 0.2 mol % of additive; for H2SO4, T = 5 °C). contact time with the 2-butene at the interface, which
increased the rate of hydrogen transfer between C8+ cation
terms of 2-butene conversion) of ILs with promoters were and isobutane. To enhance the alkylate quality, a composite
compared with neat IL (without promoter) and H2SO4 as LCC (LCC−CuCl) was developed by mixing the AlCl3/NMA
shown in Figure 5. The addition of tert-butyl chloride or tert- (χ = 0.57; best performed) LCC with CuCl for the C4
butyl bromide in the IL provided an improvement in alkylation reaction (a similar approach which was used in the
conversion from ∼20% (without promoter: neat IL or synthesis of composite IL). The composite LCC AlCl3/NMA−
H2SO4) to ∼100% (with promoter within 5−8 min). The C8 CuCl was found to have higher catalytic activity than AlCl3/
selectivity was also enhanced from less than 10% to 26% when NMA LCC (Table 4, entry 8). The higher catalytic activity for
tert-butyl bromide was used as an additive in the IL. Increasing the composite LCC could be due to the formation of a unique
the promoter amount in the IL led to the TMPs fraction Al species like [AlCl4CuCl]− that was detected using 27Al
becoming the dominant component in the C8 selectivity. NMR along with other cationic Al species like
Furthermore, the catalytic activity of the IL with tert-butyl [AlCl2(NMA)2].
halide promoters was investigated in a continuous process. At Various amide derivative-based AlCl3 LCCs (χAl 0.61) such
the beginning of the reaction, 2-butene conversions were as AlCl3/formamide, AlCl3/acetamide, AlCl3/urea, and AlCl3/
higher; later, the conversion dropped rapidly to 5% with time- methylurea were investigated, and all were found to be active
on-stream and remained constant. Chevron also disclosed that in C4 alkylation (Table 4, entries 10−13).56 These LCC are
alkyl halides can promote C4 alkylation catalyzed by not deep eutectic solvents (DES) as seen with similar mixtures
chloroaluminate ILs (Figure 6);28,75 however, they must be of salts with urea and others due to the coordination with
removed from the alkylate in a separate unit operation. aluminum. Among these, AlCl3/urea LCC produced the
5.1.7. Chloroaluminate-Based LCCs. As discussed in the highest alkylate quality, which may be due to the controlled
Section 4, LCCs are different than conventional chloroalumi- acidity. The effect of AlCl3 content on AlCl3/urea LCC was
Figure 6. Overall ISOALKY technology process.28
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 4. Alkylation of Isobutane with Butene Using Various Kinds of Chloroaluminate-Based LCCsa
Weight
percentage in
product (wt
%)
IL Speciation IL Viscosity T Time I/O P Conv. TMP/
E.N. Catalyst Additive Technique (cST) (°C) (min) Ratio (MPa) (%) C8 TMP DMH Sel. RON Ref
1 AlCl3/NMA None n.d. n.d. 15 − 20:1 − − 30.5 17.7 1.6 72.1 55
(χAl 0.51)
2 AlCl3/NMA None n.d. n.d. 15 − 20:1 − − 58.2 34.0 1.6 79.3 55
(χAl 0.54)
3 AlCl3/NMA None 27
Al NMR n.d. 15 − 20:1 − − 76.2 61.5 4.7 91.2 55
(χAl 0.57)
4 AlCl3/NMA None n.d. n.d. 15 − 20:1 - - 63.8 38.3 1.9 84.3 55
(χAl 0.61)
5 AlCl3/acetamide None n.d. n.d. 15 − 20:1 − − 57.6 32.9 1.6 83.8 55
(χAl 0.61)
6 AlCl3/DMA None n.d. n.d. 15 − 20:1 − − 63.4 34.1 1.4 82.3 55
(χAl 0.61)
7 AlCl3/NMF None n.d. n.d. 15 − 20:1 − − 60.5 32.5 1.5 81.9 55
(χAl 0.61)
8 AlCl3/NMA None 27
Al NMR n.d. 15 − 20:1 − − 94.6 88.6 15.0 98.4 55
(χAl 0.57)- CuCl
9 [HN222][Cl]−AlCl3 None n.d. n.d. 15 − 20:1 − − 59.0 28.2 1.1 80.4 55
(χAl 0.61)
10 AlCl3/formamide None n.d. n.d. 15 15 15:1 − 99.5 48.2 24.1 1.3 85.4 56
(χAl 0.61)
11 AlCl3/acetamide None n.d. n.d. 15 15 15:1 − 97.7 44.4 26.1 1.8 86.7 56
(χAl 0.61)
12 AlCl3/urea None n.d. ∼170 15 15 15:1 − 97.1 50.7 32.3 2.1 87.5 56
(χAl 0.61)
13 AlCl3/methylurea None n.d. n.d. 15 15 15:1 − 99.3 46.6 29.6 2.1 87.4 56
(χAl 0.61)
14 AlCl3/urea None n.d. n.d. 15 15 15:1 − 15.5 − − − − 56
(χAl 0.50)
15 AlCl3/urea None n.d. n.d. 15 15 15:1 − 91.0 54.8 39.3 2.7 89.2 56
(χAl 0.54)
16 AlCl3/urea None n.d. ∼170 15 15 15:1 − 97.3 50.7 32.3 2.1 87.5 56
(χAl 0.61)
(χAl 0.64)
(χAl 0.67)
19 AlCl3/urea None n.d. ∼170 15 15 15:1 − 97.1 50.7 32.3 2.1 87.5 56
(χAl 0.61)
20 AlCl3/urea CuCl n.d. 600 15 15 15:1 − 97.9 57.6 46.2 4.2 90.7 56
(χAl 0.61)
21 AlCl3/urea FeCl3 n.d. n.d. 15 15 15:1 − 95.9 54.6 38.8 2.8 89.6 56
(χAl 0.61)
22 AlCl3/urea ZnCl2 n.d. n.d. 15 15 15:1 − 95.2 52.1 38.3 3.0 89.0 56
(χAl 0.61)
23 AlCl3/urea SnCl2 n.d. n.d. 15 15 15:1 − 74.4 47.6 30.6 2.0 85.9 56
(χAl 0.61)
a
T, temperature; I/O, ratio of isobutane (I) to olefins (O); P, pressure; Sel., selectivity; Ref, reference; χAl, mole fraction of AlCl3 in IL; n.d., not
determined/discussed; NMA, N-methylacetamide; DMA, dimethylacetamide; NMF, N-methyl formamide.
investigated in C4 alkylation, and a similar result was found to Lewis acidic characteristics in the same molecule are known as
the system mentioned above for AlCl3/NMA LCC (Table 4, dual/bifunctionalized ILs or Brönsted−Lewis acidic ILs. These
entries 14−18). As expected, the further addition of metal types of acidic ILs are particularly useful as catalysts for some
additives such as CuCl, FeCl3, ZnCl2, and SnCl2 in AlCl3/urea catalytic processes that require both types of acidities in one or
LCC produced enhanced alkylate quality for all additives more steps of the reaction. To understand the effect of
except SnCl2 (Table 4, entries 19−23). The difference in the Brönsted−Lewis acidic ILs on C4 alkylation, the Brönsted
catalytic activity of LCCs with various metals was explained by acidic IL [(HO3SC4)C1im][HSO4] (0.24 g/g of IL) was mixed
the difference in Brönsted and Lewis acidic strengths. The with the Lewis acidic IL [C8C1im][Br]−AlCl3 (χAl 0.6) and
synergetic effect of Brönsted and Lewis acid sites could be the used in C4 alkylation.54,64 The IL [(HO3SC4)C1im][HSO4]
key to improving the catalytic performance of the AlCl3/urea− has low inherent C4 catalytic activity under identical
CuCl system. conditions. As compared to the [C8C1im][Br]−AlCl3 IL,
5.2. Metal-Based Brönsted−Lewis (Bifunctional) Brönsted−Lewis acidic ILs (mixture of [C8C1im][Br]−AlCl3
Acidic ILs. The acidic ILs with both Brönsted as well as and [(HO3SC4)C1im][HSO4]) produced a significant en-
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 5. Alkylation of Isobutane with Butene Using Various Kind of Brönsted−Lewis Acidic Metal-Based ILs
Weight
percentage in
product (wt %)
IL Speciation IL Viscocity T (° Time I/O P Conv. TMP/DMH
1 [C8C1im][Br]−AlCl3 (χAl 0.6) None Inferred64 n.d. −5 60 13:1 0.6 − 23.3 21.3 − 90.5 54, 64
2 [C8C1im][Br]−AlCl3 (χAl 0.6) [(HO3SC4)C1im][HSO4] (0.24 n.d. n.d. −5 60 13:1 0.6 >98 ∼58.0 53.0 − 95.0 64
g/g IL)
3 [(HO3SC3)N222][Cl] H2O (0.43 g/g IL) n.d. n.d. 60 120 10:1 2.0 40.5 − 44.7 8.1 − 76
4 [(HO3SC3)N222][Cl]−ZnCl2 H2O (0.43 g/g IL) n.d. n.d. 60 120 10:1 2.0 99.7 − 85.3 63.1 − 76
(χZn 0.67)
(χZn 0.75)
(χZn 0.80)
(χZn 0.83)
8 [(HO3SC3)N222][Cl]−ZnCl2 None n.d. n.d. 60 120 10:1 2.0 45.2 − 88.6 59.1 − 76
(χZn 0.83)
(χZn 0.86)
10 [HN222][Cl]−ZnCl2 (χZn 0.83) H2O (0.43 g/g IL) n.d. n.d. 60 120 10:1 2.0 99.8 − 49.6 16.5 − 76
11 [(HO3SC3)N222][Cl]−CuCl2 H2O (0.43 g/g IL) n.d. n.d. 60 120 10:1 2.0 57.3 − 69.4 19.8 − 76
(χZn 0.83)
15826
12 [(HO3SC3)N222][Cl]−CuCl H2O (0.43 g/g IL) n.d. n.d. 60 120 10:1 2.0 56.8 − 78.4 31.4 − 76
(χZn 0.83)
13 [(HO3SC3)N222][Cl]−FeCl3 H2O (0.43 g/g IL) n.d. n.d. 60 120 10:1 2.0 99.7 − 63.9 16.8 − 76
(χZn 0.83)
14 [(HO3SC3)N222][Cl]−FeCl2 H2O (0.43 g/g IL) n.d. n.d. 60 120 10:1 2.0 73.4 − 53.3 12.1 − 76
(χZn 0.83)
15 [(HO3SC3)N222][Cl]−AlCl3 None n.d. n.d. 60 120 10:1 2.0 85.5 − 30.4 4.5 − 76
(χZn 0.83)
16 [(HO3SC3)C1im][Cl] H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 51.3 − 64.7 4.2 − 77
17 [(HO3SC3)C1im][Cl]−ZnCl2 H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 61.2 − 63.2 4.4 − 77
(χZn 0.5)
pubs.acs.org/IECR
18 [(HO3SC3)C1im][Cl]−ZnCl2 H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 86.4 − 75.4 8.9 − 77
(χZn 0.6)
19 [(HO3SC3)C1im][Cl]−ZnCl2 H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 100 − 80.5 15.2 − 77
(χZn 0.67)
20 [(HO3SC3)C1im][Cl]−ZnCl2 None n.d. n.d. 80 240 10:1 2.0 66.8 − 72.3 11.7 − 77
(χZn 0.67)
(χZn 0.71)
(χZn 0.75)
23 [(HO3SC3)C1im][Cl]−ZnCl2 None n.d. n.d. 80 240 10:1 2.0 66.8 − 72.3 11.7 − 77
(χZn 0.67)
24 [C4C1im][Cl]−ZnCl2 (χZn 0.67) H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 66.0 − 64.1 8.2 − 77
25 [(HO3SC3)C1im][Cl]−CuCl2 H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 54.2 − 62.3 6.0 − 77
Review
Ind. Eng. Chem. Res. 2020, 59, 15811−15838

(χZn 0.67)
Table 5. continued
Weight
percentage in
product (wt %)
IL Speciation IL Viscocity T (° Time I/O P Conv. TMP/DMH
26 [(HO3SC3)C1im][Cl]−CuCl H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 48.9 − 58.0 5.7 − 77
(χZn 0.67)
27 [(HO3SC3)C1im][Cl]−FeCl3 H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 100 − 71.5 8.7 − 77
(χZn 0.67)
28 [(HO3SC3)C1im][Cl]−FeCl2 H2O (0.43 g/g IL) n.d. n.d. 80 240 10:1 2.0 70.3 − 68.9 8.0 − 77
(χZn 0.67)
29 [(HO3SC3)C1im][Cl]−AlCl3 None n.d. n.d. 80 240 10:1 2.0 65.2 − 39.6 4.4 − 77
(χZn 0.67)
Immobilized/Supported ILs
30 Impregnated [C4C1im][Al2Cl7] on n.d. n.d. 70 60 0.56:1 − ∼65.0 ∼47.0 − − − 78
SiO2
31 Graphted [SiC3C1im][Al2Cl7] on n.d. n.d. 80 270 110:1 − 97.0 59.7 − − − 78

MCM-41
32 [C4C1im][Al2Cl7] None n.d. n.d. 80 270 110:1 − 100 61.9 − − − 78
33 [P666−14][Al2Cl7] None n.d. n.d. 80 180 110:1 − 100 68.9 − − − 78
34 [C8C1im][Br]−AlCl3 (χAl 0.6) None Inferred64 n.d. −5 60 13:1 0.6 − 23.3 21.3 − 90.5 54, 64
35 [C8C1im][Br]−AlCl3 (χAl 0.6) Dowex resin 0.08 mol n.d. n.d. −5 60 13:1 0.6 − 36.8 30.3 − 92.4 54
15827
a
T, temperature; I/O, ratio of isobutane to olefins; P, pressure; Sel., selectivity; Ref, reference; χM, mole fraction of metal halide in IL; n.d., not determined/discussed.
pubs.acs.org/IECR
Review
Ind. Eng. Chem. Res. 2020, 59, 15811−15838

Table 6. Alkylation of Isobutane with Butene Using Various Kind of Brönsted Acidic ILsa
Weight
percentage in
product (wt %)
IL Viscosity T (° Time I/O P Conv. TMP/
E.N. Catalyst (cST) C) (min) Ratio (MPa) (%) C8 TMP DMH Sel. RON Ref
1 H2SO4 n.d. 8 10 10:1 0.2 97.3 61.7 − 6.1 − 36
2 CF3SO3H n.d. 8 10 10:1 0.2 98.7 41.1 − 1.4 − 36
3 [C6C1im][NTf2] n.d. 8 30 10:1 0.2 0.3 15.4 − 0.5 − 36
4 [C6C1im][NTf2] + H2SO4 (93.6:6.4, w-w) n.d. 8 10 10:1 0.2 2.2 15.9 − 0.6 − 36
5 [C6C1im][NTf2] + H2SO4 (60.8:39.2, w-w) n.d. 8 30 10:1 0.2 59.0 19.2 − 5.8 − 36
6 [C6C1im][NTf2] + H2SO4 (42.0:58.0, w-w) n.d. 8 20 10:1 0.2 89.4 31.1 − 4.8 − 36
7 [C6C1im][NTf2] + H2SO4 (8.7:91.3, w-w) n.d. 8 20 10:1 0.2 89.7 60.2 − 5.1 − 36
8 [C4C1im][HSO4] n.d. 8 20 10:1 0.2 11.4 8.7 − 0.1 − 36
9 [C4C1im][HSO4] + H2SO4 (67.6:32.4, w-w) n.d. 8 20 10:1 0.2 51.8 22.4 − 5.2 − 36
10 [C4C1im][HSO4] + H2SO4 (41.7:58.3, w-w) n.d. 8 20 10:1 0.2 91.0 60.3 − 4.9 − 36
11 [C4C1im][HSO4] + H2SO4 (20.9:79.1, w-w) n.d. 8 20 10:1 0.2 90.4 41.0 − 7.9 − 36
12 [C8C1im][HSO4] + H2SO4 (16.0:84.0, w-w) n.d. 8 20 10:1 0.2 98.0 51.3 − 6.6 − 36
13 [C8C1im][HSO4] + CF3SO3H n.d. 8 10 10:1 0.2 85.1 61.9 − 6.2 − 36
(67.6:32.4, w-w)
14 [C8C1im][HSO4] + CF3SO3H n.d. 8 10 10:1 0.2 91.2 65.6 − 6.8 − 36
(59.6:40.4, w-w)
15 [C8C1im][HSO4] + CF3SO3H n.d. 8 10 10:1 0.2 96.3 75.8 − 6.8 − 36
(23.7:76.3, w-w)
16 [C4C1im][HSO4] + CF3SO3H n.d. 8 10 10:1 0.2 98.1 72.4 − 8.1 − 36
(23.2:76.8, w-w)
17 [C4SO3HC1im][HSO4] n.d. 8 20 10:1 0.2 5.4 62.0 − 7.2 − 36
18 [(HO3SC4)C1im][HSO4] + H2SO4 n.d. 8 20 10:1 0.2 12.1 27.2 − 8.1 − 36
(63.9:36.1, w-w)
(40.9:59.1, w-w)
(26.0:74.0, w-w)
21 [(HO3SC3)C1im][CF3SO3] n.d. 8 20 10:1 0.2 6.3 11.0 − 0.8 − 36
22 [(HO3SC4)C1im][CF3SO3] n.d. 8 20 10:1 0.2 2.2 6.6 − 0.0 − 36
23 [(HO3SC4)C1im][CF3SO3] + H2SO4 n.d. 8 20 10:1 0.2 8.2 31.2 − 2.7 − 36
(70.4:29.6, w-w)
(46.7:53.3, w-w)
(28.1:71.9, w-w)
26 [(HO3SC4)C1im][CF3SO3] + CF3SO3H n.d. 8 20 10:1 0.2 68.3 57.9 − 6.2 − 36
(81.3:18.7, w-w)
(48.3:51.7, w-w)
(33.3:66.7, w-w)
29 [(HO3SC4)C1im][CF3SO3] n.d. 25 30 10:1 − 67.2 − 40.6 1.5 − 81
30 [(HO3SC4)C1im][CF3SO3] + Cu(CF3SO3)2 n.d. 25 30 10:1 − 95.1 − 69.8 7.4 − 81
(0.2 mol/mol of IL)
Effect of Perfluorinated Anion-based ILs

31 [C4C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 59.6 − 5.2 89.8 82
(66.7:33.3, w-w)
32 [C4C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 76.2 − 5.4 92.6 82
(49.7:50.3, w-w)
33 [C4C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 64.9 − 4.5 90.5 82
(29.7:70.3, w-w)
34 [C6C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 76.5 − 5.4 92.6 82
(68.9:31.1, w-w)
35 [C6C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 80.1 ∼68.0 7.2 95.6 82
(47.9:52.1, w-w)
36 [C6C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 48.6 − 2.5 87.8 82
(31.8:68.2, w-w)
37 [C8C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 70.7 − 5.3 91.7 82
(64.1:35.9, w-w)
38 [C8C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 70.1 − 6.1 92.1 82
(46.8:53.2, w-w)
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 6. continued
Weight
percentage in
product (wt %)
39 [C8C1im][SbF6] + CF3SO3H n.d. 10 10 10:1 0.5 − 63.8 − 4.2 90.7 82
(27.4:72.6, w-w)
40 [C6Py][SbF6] + CF3SO3H (50.0:50.0, w-w) n.d. 10 10 10:1 0.5 − 79.0 ∼68.0 − 94.0 82
41 [(HO3SC4)Py][BF4] + CF3SO3H (1:1, v-v) n.d. 10 20 10:1 0.5 − 31.8 − 2.6 84.4 83
42 [(HO3SC4)Py][BF4] + CF3SO3H (1:3, v-v) n.d. 10 20 10:1 0.5 − 70.6 − 7.6 93.1 83
43 [(HO3SC4)Py][CF3SO3] + CF3SO3H n.d. 10 20 10:1 0.5 − 13.0 − 1.9 82.4 83
(1:1, v-v)
44 [C4SO3HC1im][CF3SO3] + CF3SO3H n.d. 10 20 10:1 0.5 − 13.6 − 2.2 81.4 83
(1:1, v-v)
45 [(HO3SC4)C1im][CF3SO3] + CF3SO3H n.d. 10 20 10:1 0.5 − 81.1 − 8.4 95.3 83
(1:3, v-v)
46 [(HO3SC4)C4im][BF4] + CF3SO3H n.d. 10 20 10:1 0.5 − 58.7 − 5.4 90.2 83
(1:3, v-v)
47 [C4C1im][BF4] + CF3SO3H (1:3, v-v) n.d. 10 20 10:1 0.5 − 83.9 − 7.2 94.9 83
48 [C6C1im][BF4] + CF3SO3H (1:3, v-v) n.d. 10 20 10:1 0.5 − 80.2 − 7.8 94.7 83
49 H2SO4 − 10 8.5:1 0.4 − 58.4 49.0 − 91.7 84
50 [C4C1im][SbF6] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 63.0 54.1 − 92.4 84
51 [C4C1im][PF6] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 60.9 51.6 − 92.1 84
52 [C4C1im][BF4] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 59.1 50.1 − 92.0 84
53 [C4C1im][CF3SO3] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 58.8 50.0 − 91.8 84
54 [N2222][PF6] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 60.6 51.7 − 92.2 84
55 [N2222][BF4] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 59.3 50.2 − 91.9 84
56 [N2224][PF6] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 61.4 51.6 − 91.8 84
57 [N2224][SbF6] + H2SO4 (0.5:100, w-w) n.d. − 10 8.5:1 0.4 − 59.0 49.6 − 91.8 84
58 H2SO4 − 5 10 4.7:1 0.4 − 63.4 52.7 5.0 − 59
59 [C4C1im][PF6]-H2SO4 (before HF release) n.d. 5 10 4.7:1 0.4 − 68.0 57.3 5.5 − 59
60 [C4C1im][PF6]-H2SO4 (after HF release) n.d. 5 10 4.7:1 0.4 − 63.7 53.4 5.3 − 59
61 [C4C1im][SbF6]-H2SO4 (before HF release) n.d. 5 10 4.7:1 0.4 − 68.0 57.2 5.4 − 59
62 [C4C1im][SbF6]-H2SO4 (after HF release) n.d. 5 10 4.7:1 0.4 − 62.6 52.2 5.1 − 59
Effect of hydrophobic Cations with Perfluorinated Anions

63 H2SO4 − 1.5 10 10:1 − − 81.9 73.3 10.8 96.6 85
64 [C4C1im][SbF6] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 82.3 75.7 13.9 97.1 85
65 [NA11−12][SbF6] + H2SO4 (0.25:100, w-w) n.d. 1.5 10 10:1 − − 83.2 77.5 13.7 98.0 85
66 [NA11−12][SbF6] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 84.5 80.1 21.3 98.6 85
67 [NA11−12][SbF6] + H2SO4 (0.75:100, w-w) n.d. 1.5 10 10:1 − − 83.7 79.3 20.8 98.4 85
68 [NA11−12][SbF6] + H2SO4 (1.0:100, w-w) n.d. 1.5 10 10:1 − − 84.5 79.2 18.5 98.3 85
69 [NA11−4][SbF6] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 78.3 71.8 15.1 95.7 85
70 [NA11−8][SbF6] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 73.8 68.0 13.7 95.2 85
71 [NA11−12][SbF6] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 84.5 80.1 21.3 98.6 85
72 [NA11−16][SbF6] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 82.3 77.0 19.4 96.9 85
73 [NA11−12][PF6] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 86.2 80.7 16.3 98.2 85
74 [NA11−12][NTf2] + H2SO4 (0.5:100, w-w) n.d. 1.5 10 10:1 − − 85.9 80.9 19.4 97.8 85
75 H2SO4 n.d. − − 15:1 0.4 − 62.5 52.9 5.8 92.2 86
76 [N111−12][Cl] + H2SO4 (Surfactant 12.5 n.d. − − 15:1 0.4 − 86.0 75.9 7.5 96.4 86
mmol/L)
77 [N111−12][Cl] + H2SO4 (Surfactant 25 n.d. − − 15:1 0.4 − 87.4 77.1 7.5 96.6 86
mmol/L)
78 [N111−12][HSO4] + H2SO4 (Surfactant 12.5 n.d. − − 15:1 0.4 − 88.9 77.8 8.7 96.5 86
mmol/L)
79 [N111−12][PF6] + H2SO4 (Surfactant 12.5 n.d. − − 15:1 0.4 − 74.7 65.3 7.2 94.8 86
mmol/L)
80 [P666−14][Cl] + H2SO4 (Surfactant 200 n.d. − − 15:1 0.4 − 69.0 58.6 5.8 93.0 86
mmol/L)
IL/polymer−HF Complex
81 Pyridine/HF (1:22) n.d. 36 3 12:1 1.38 − 41.3 − 85.9 80
82 Poly(ethylenimine)/HF (1:22) n.d. 36 10 12:1 1.38 − 67.3 − 91.7 80
83 PVPHF (ionic solid) n.d. 22 10 12:1 − − 73.7 − 93.0 80
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 6. continued
Weight
percentage in
product (wt %)
Effect of Hydroxy-Functionalized Cations

86 [(HOC2)2N01][HSO4] + CF3SO3H (15:85, n.d. 10 10 10:1 0.5 100 92.1 − 12.0 97.8 87
v-v)
87 [(HOC2)N011][HSO4] + CF3SO3H (15:85, n.d. 10 10 10:1 0.5 100 89.6 − 12.9 97.7 87
v-v)
88 [(HOiC3)N011][HSO4] + CF3SO3H (15:85, n.d. 10 10 10:1 0.5 100 88.9 − 12.1 97.4 87
v-v)
89 [(HOiC3)N011][HSO4] + CF3SO3H n.d. 10 10 10:1 0.5 100 86.3 79.7 12.1 96.4 87
(25:75, v-v)
90 [(HOC2)NH3][HSO4] + CF3SO3H n.d. 10 10 10:1 0.5 100 87.9 − 10.4 97.0 87
(15:85, v-v)
91 [(HOC2)N022][HSO4] + CF3SO3H n.d. 10 10 10:1 0.5 100 87.3 81.3 13.5 97.4 87
(15:85, v-v)
92 [(HOC2)N022][CF3SO3] + CF3SO3H n.d. 10 10 10:1 0.5 100 86.2 80.4 13.9 97.0 87
(25:75, v-v)
93 [HN222][HSO4] + CF3SO3H (25:75, v-v) n.d. 10 10 10:1 0.5 100 91.5 85.1 13.5 98.0 87
94 [HN222][CF3SO3] + CF3SO3H (40:60, v-v) n.d. 10 10 10:1 0.5 100 87.2 79.9 10.9 96.9 87
Base−Acid (In Situ IL and Acid Mixture)
95 H2SO4 − 12 10.5 100:1 − − 78.5 − − − 88
96 Caprolactam + H2SO4 (0.5:99.5, w-w) n.d. 12 10.5 100:1 − − ∼85 − − − 88
97 Caprolactam + H2SO4 (1.0:99.0, w-w) n.d. 12 10.5 100:1 − − 88.1 − − − 88
100 H2SO4 n.d. 12 10.5 8:1 − − 36.8 − − − 88
101 Caprolactam + H2SO4 (1.0:99.0, w-w) n.d. 12 10.5 8:1 − − 62.4 − − − 88
102 H2SO4 − 5 10 9:1 0.4 − 68.8 58.6 5.8 93.5 89
103 Pyridine + H2SO4 (1:99, w-w) n.d. 5 10 9:1 0.4 − 68.0 57.9 5.7 93.4 89
104 Thiophene + H2SO4 (1:99, w-w) n.d. 5 10 9:1 0.4 − 82.0 73.2 8.4 96.2 89
105 Thiophene + H2SO4 (1:99, w-w)* n.d. 5 10 9:1 0.4 − 92.3 84.6 11.1 98.6 89
106 Taurine (Tau) or PEG-200 n.d. 80 60 10:1 − 0 0 − − − 90
107 CF3SO3H n.d. 60 20 10:1 − 100 32.5 − − − 90
108 [CF3SO3H]3[Tau] n.d. 60 40 10:1 − 100 37.2 − − − 90
109 [CF3SO3H]/[PEG-200] n.d. 80 40 10:1 − 86.0 75.1 − − − 90
110 [CF3SO3H]3[Tau]/PEG-200 n.d. 80 60 10:1 − 82.6 85.5 − − − 90
111 [CF3SO3H]3[Ala]/PEG-200 n.d. 90 60 10:1 − 57.3 82.2 − − − 90
112 [CF3SO3H]3[ChCl]/PEG-200 n.d. 90 60 10:1 − 53.7 85.3 − − − 90
a
T, temperature; I/O, ratio of isobutane (I) to olefins (O); P, pressure; Sel., selectivity; Ref, reference; n.d., not determined/discussed; Tau,
taurine; Ala, alanine.
hanced alkylate quality (TMP selectivity increased from 21.3 improved (TMP selectivity increased from 44.7% (without
to 53.0 wt %) (Table 5, compare entry 2 with 1). It was metal) to 90.5%) (Table 5, entries 3−7). However, further
proposed that the significant activity can be due to the increasing the mole fraction of ZnCl2 from 0.83 to 0.86, the
formation of super acidic species. These results indicate that TMPs selectivity was slightly decreased from 90.5% to 88.6%
the addition of a Brönsted acidic IL to the Lewis acidic because of the stronger acidic nature of the catalyst (Table 5,
chloroaluminate IL was an effective way to improve the entry 9). The catalytic activity was compared with and without
alkylate quality. However, the chloroaluminate ILs hydrolyze sulfonic-functionalized ILs. The significant improvement in
easily to release HCl vapor due to moisture sensitivity, and it is TMPs selectivity (from 49.6% to 90.5%) was observed using a
difficult to recover HCl vapor together with the IL during the sulfonic-functionalized acidic IL when compared with a
recycling of the catalyst, which leads to an irreversible nonsulfonic group-functionalized Lewis acidic IL (Table 5,
deactivation of the catalytic system. compare entry 7 with 10). In addition, to tune the Lewis
Therefore, Liu et al. synthesized moisture stable Brönsted− acidity in the Brönsted−Lewis acidic ILs, the Lewis acidic
Lewis acidic ILs to use in C4 alkylation.76 In this report, a ZnCl2 salt was replaced with other metal salts (such as CuCl,
sulfonic acid-functionalized Brönsted acidic IL [(HO3SC3)- CuCl2, FeCl3, and FeCl2). It was found that the catalyst
N222]Cl was used in combination with different mole fractions combination of ZnCl2 (Lewis acid) with [(HO3SC3)N222][Cl]
of Lewis acidic salt ZnCl2. With an increasing mole fraction of (Brönsted acid) produces better performance in C4 alkylation
ZnCl2 from 0 to 0.83 in [(HO3SC3)N222][Cl]−ZnCl2 along than other metal combinations with the [(HO3SC3)N222][Cl]
with H2O content, the alkylate quality was significantly IL (Table 5, compare entry 7 with entries 11−15). Further, Liu
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
et al. extended the development of Brönsted−Lewis acidic ILs pure acids even for up to as many as 25 recycling runs. These
from ammonium cations to imidazolium cations with different results suggest a significant reduction in acid consumption is
mole fractions of metal chlorides.77 Increasing the mole possible compared with commercial alkylation using H2SO4.
fraction of ZnCl2 from 0 to 0.67 in [(HO3SC3)C1im][Cl]− The results also suggest that ILs offer the ability to produce
ZnCl2 (in the presence of H2O content) significantly increased liquid acid catalysts with tuned acidity, higher reactant
the catalytic activity (both conversion as well as alkylate solubilities, good alkylate production, and improvements in
quality) (Table 5, entries 16−21). Further increasing the mole alkylate/acid separation.
fraction of ZnCl2 from 0.67 to 0.75, decreased the TMP Furthermore, Liu et al.81 also investigated various ILs such
selectivity from 80.5% to 58.5%, which may be due to the as [C4C1im][HSO4], [C4C1im][CF3SO3], [C6C1im][NTf2],
stronger acidic nature of the catalyst (Table 5, entries 19−22). and their mixtures with strong acids (H2SO4 or CF3SO3H) in
Among the investigated metals in [(HO3SC3)C1im][Cl]− C4 alkylation and found similar conclusions to the study
MCln (χM 0.67) (M = Zn, Cu, Fe, Al), the Zn combination IL reported by Tang et al.36 In this report, 20 mol % of
produced a better quality of alkylate (Table 5, compare entry Cu(CF3SO3)2 was added to the [(HO3SC4)C1im][CF3SO3]
19 with entries 25−29). It is hard to compare both ammonium IL, and the activity was improved significantly (conversion
and imidazolium cation-based Brönsted−Lewis acidic ILs due increased from 67.2% to 95.1% and TMPs from 40.6% to
to the differences in the reaction conditions and mole fractions 69.8%) (Table 6, compare entry 30 and 29).
of metal chlorides in the IL system. 5.3.1. Effect of Perfluorinated Anion-Based ILs. Kim et al.91
5.3. Nonmetal-Based Acidic Ionic Liquids (or Non- reported that the presence of ILs containing weakly
halometallate ILs). As mentioned above, most of the coordinating anions like [SbF6]− or [PF6]− could dramatically
halometallate ILs deactivate after a few recycling experiments enhance the catalytic activity of scandium trifluoro-methane-
due to the moisture sensitivity. To overcome this problem, sulfonate in the Diels−Alder reaction, due to the in situ
there is a need to develop air, moisture-stable ILs that are still formation of a strong Lewis acid through anion exchange.
acidic enough to catalyze the C4 alkylation reaction. Therefore, Soltner et al. 9 2 prepared the highest acidic salt
Tang et al. (our group) developed a new IL-based binary [CF3SO3A2]+[SbF6]− (A = H or D) (H0= −18.5) by reacting
mixture system by mixing a Brönsted acidic (or neutral) IL triflic anhydride with the super acidic solutions AF/SbF5.
with a strong acid (e.g., H2SO4 or CF3SO3H) for use in C4 Inspired by these compounds, Xing et al. mixed the [SbF6]−
alkylation.36 To provide direct comparison as well as anion containing ILs and CF3SO3H at different ratios and
benchmarks for the IL-based systems, C4 alkylation was investigated for C4 alkylation.82 For the acidic IL [C6C1im]-
performed with conventional catalysts such as H2SO4 and [SbF6]−CF3SO3H system, the best alkylate quality (C8
CF3SO3H (Table 6, entries 1 and 2). The results obtained selectivity 80.1% with 7.2 TMP/DMH ratio) was obtained
using H2SO4 acid were consistent with the alkylate quality of a when the IL to acid ratio was close to 1:1 (Table 6, entry 35).
typical commercial plant (60%−65% C 8 with ∼4−6 Furthermore, alkyl chain length was varied in the [CnC1im]-
TMP:DMH ratio).79 The results obtained using pure [SbF6]−CF3SO3H system (where n = 4, 6, and 8), and the
CF3SO3H were similar to those reported by Olah and co- following general trend was found: [C6C1im] > [C8C1im] >
workers.80 Here, three different types of acidic ILs were [C4C1im]. This difference in activity could be due to the
synthesized, where the Brönsted acidic group is found in either difference in isobutane solubility and IL viscosity. By using a
the anion (e.g., [C4C1im][HSO4]), cation, or both the cation pyridinium cation-based IL with CF3SO3H in C4 alkylation,
and anion (e.g., [(HO3SC4)C1im][HSO4]). The alkylation alkylate quality was obtained similar to an imidazolium-based
using ILs with inherent acidity in either the cation or the anion IL system (Table 6, compare entry 40 to 35). This study
resulted in a very low butene conversion as well as poor further proves that the properties and catalytic activity of the
alkylate quality (Table 6, entries 3, 8, 21, and 22). In contrast, binary system of IL−acid mixture can be easily adjusted by
the ILs that had Brönsted acidity in both the cation and the varying either the cation or anion structure or concentration of
anion provided better alkylate quality even though the the IL in the system. However, these types of perfluorinated
conversions were still low (Table 6, entry 17). The conclusion anions are hydrolytically unstable and could decompose to release
was the acidity of neat ILs was not enough to catalyze C4 HF gas.93
alkylation to match the activity of H2SO4 or CF3SO3H. Wang et al.83 studied several with and without sulfonic-
Furthermore, the Brönsted acidic ILs were mixed with either functionalized IL combinations with CF3SO3H at different
H2SO4 or CF3SO3H at different ratios to tune the acidity of the volume ratios (Table 6, entries 41−46). Increasing the volume
IL-based acid system and were investigated in C4 alkylation. ratio of IL to acid (from 1:1 to 1:3) in the [(HO3SC4)Py]-
Upon increasing the concentration of the strong acid in IL, the [BF4]−CF3SO3H system enhanced the C8 selectivity from
activities of the IL−acid binary mixtures increased. These 31.8% to 70.6% (RON from 84.4 to 93.1) (Table 6, compare
binary mixtures showed a better performance than either the entry 42 to 41). At a 1:1 ratio of IL to acid, the alkylate
neat ILs or the pure acids. This is particularly true for the qualities were lower even if the structures of the ions were
binary mixture of IL with CF3SO3H, which exhibited high changed (e.g., [(HO3SC4)Py][CF3SO3] or [(HO3SC4)C1im]-
butene conversion as well as C8 selectivity (Table 6, entries [CF3SO3]), indicating that the acidities of the catalyst systems
13−16 and 26−28). This enhanced alkylate quality could be were not enough to catalyze the reaction (Table 6, entries 43
due to the synergetic effect of IL and CF3SO3H. It is and 44). However, the [(HO3SC4)C1im][CF3SO3]−CF3SO3H
interesting to note that ILs with longer alkyl chains, such as (1:3 vol ratio) catalyst system achieved the best quality of
[C8C1im][HSO4] (compared to [C4C1im][HSO4]), were alkylate (C8 selectivity 81.1% with RON 95.3). After a small
found to have better C8 selectivity, which could be due to, modification in the cation to [(HO3SC4)C4im]+ with the
for example, higher isobutane solubility and changes in surface [BF4]− anion and CF3SO3H, the quality of the alkylate
tension. The recyclability of the binary mixture of [C4C1im]- decreased (Table 6, entry 46). It is interesting to note that the
[HSO4] with H2SO4 or CF3SO3H was also superior to the combination of a simple IL such as [C4C1im][BF4] or
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Figure 7. Recycling study comparison of [C4C1im][SbF6]−H2SO4 (left) and [NA11−12][SbF6]−H2SO4 (right) (0.5 wt % IL/surfactant) vs
H2SO4.84,85
[C6C1im][BF4] with CF3SO3H (at 1:3 vol ratio) exhibited a increased (TMPs from 73.3 to 80.1) (Table 6, entries 63−66).
similar quality of alkylate in C4 alkylation to that of However, by further increasing the concentration of [NA11−12]-
[(HO3SC4)C1im][CF3SO3]−CF3SO3H (Table 6, compare [SbF6] from 0.5 to 1.0 wt %, the TMP was decreased from 80.1
entries 47 and 48 to 45). to 79.2 (Table 6, entries 66−68). Among the alkyl chain length
Huang et al.84 investigated trace amounts (0.5 wt %) of ILs variation in [NA11‑n][SbF6] (where n = 4,8,12,16), the
(imidazolium/ammonium cation with [SbF 6 ]− /[PF6 ]− / [NA11−12][SbF6] system was found to be the most efficient
[BF4]−/[CF3SO3]−) and H2SO4 to enhance the quality of catalyst, which could be due to the higher isobutane solubility
alkylate for C4 alkylation. Among these ILs, [C4C1im][SbF6]− or a change in surface tension. Furthermore, the recyclabilities
H2SO4 gave the best alkylate quality (Table 6, compare entry of [NA11−12][SbF6]-H2SO4 (0.5 wt % IL) and H2SO4 were
50 to entries 51−57). Furthermore, the recyclabilities of studied up to 60 times (Figure 7, right). The [NA11−12][SbF6]-
[C4C1im][SbF6]-H2SO4 and H2SO4 were studied up to 65 H2SO4 binary catalyst was recycled up to 58 times, with the
times (Figure 7, left). The [C4C1im][SbF6]-H2SO4 (0.5% IL) desirable alkylate quality. However, H2SO4 could only be
catalyst was recycled up to 52 times, with the desirable alkylate reused up to 28 times before its activity decreased, in good
quality. H2SO4 could be reused up to 28 times before its agreement with the study reported by Huang et al.84
activity decreased. The good performance of the [C4C1im]- Zhao et al.86 investigated a series of quaternary ammonium
[SbF6]−H2SO4 (0.5 wt % IL) system was attributed to and phosphonium surfactants as an additive to enhance the
maintaining the acid strength of the catalyst and the slow catalytic performance of H2SO4 for C4 alkylation. Ammonium-
formation of the acid-soluble oil. based surfactants showed much better catalytic activity than
Zhang et al.59 investigated the role of fluoride-containing ILs the phosphonium-based surfactants (Table 6, compare entries
(0.5 wt % [C4C1im][PF6] or 0.66 wt % [C4C1im][SbF6]) and 76−79 to entry 80). The enhanced catalytic activity using a
H2SO4 in C4 alkylation, focusing on the IL−acid reaction surfactant−H2SO4-based catalyst system may be due to the
mechanisms on the molecular level. Both binary systems good dispersion of the hydrocarbon in the acid and increased
produced enhanced alkylate qualities compared to every single hydrocarbon solubility.
component in the system. The enhanced activity using the 5.3.3. Effect of Hydroxy-Functionalized Cations. Cui et
binary system was due to either the release of HF and new al.87 developed several hydroxy-functionalized ammonium-
anion species (e.g., [PF 6 ‑ x ‑ 2 y (HSO 4 ) x (SO 4 ) y ] − or based ILs and combined them with CF3SO3H acid at different
[SbF6‑x‑2y(HSO4)x(SO4)y]−, discussed in Section 4), or HF vol % in C4 alkylation (Table 6, entries 86−94). All of the IL−
increased the concentration of hydrogen protons and CF3SO3H systems exhibited high catalytic activity (both
promoted the rate of hydrogen transfer. At the same time, conversion and alkylate qualities). Furthermore, compared
new anion species accelerated the dissociation of H2SO4. with the [HSO4]−-containing IL system, the [CF3SO3]−-
Meanwhile, the anion complex with the iso-octyl carbenium containing IL systems showed lower selectivity of TMPs, in
ion in the catalytic process could reduce the ASO generation. accordance with our previous study (Table 6, compare entry
On the basis of the control experiment, HF was removed from 92 to 91 and entry 94 to 93).36 The anion [CF3SO3]− is a
the binary system (called as “after HF release from binary weakly coordinating ion, and the carbocation stability in this
mixture system”) and used in C4 alkylation. Alkylate qualities environment is poor,94 which likely is the reason for the low
were decreased when compared with experiments using the alkylate quality.
binary system before HF release (Table 6, compare entry 60 to In addition to the reaction experiments, this group
59 and entry 62 to 61). investigated the corrosion rates of steels in the [HN222]-
5.3.2. Effect of Hydrophobic Cations with Perfluorinated [CF3SO3][CF3SO3H]2 IL system (prepared by mixing of
Anions. Wang et al.85 investigated a series of adamantane- [HN222][CF3SO3] and CF3SO3H at a 1:2 molar ratio) and
based surfactant salts coupled with H2SO4 in C4 alkylation. compared results with CF3SO3H and H2SO4 (Supporting
With increasing concentration of surfactant [NA11−12][SbF6] Information, Table S1).95 The corrosion rates of three different
from 0 to 0.5 wt % in H2SO4, the alkylate qualities were steels (e.g., carbon steel, 304 stainless steel, and 316 stainless
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Scheme 4. Chloroaluminate ILs Impregnated (top) and Grafted (bottom) on Solid Support78
steel) in an IL−acid system were significantly lower than in 200 system produced a higher quality of alkylate (Table 6,
both acids (e.g., CF3SO3H or H2SO4). These results conclude compare entry 110 to entries 111 and 112).
that IL such as [HN222][CF3SO3] exhibited good anticorrosive 5.4. Immobilized/Supported Ionic Liquids. All liquid IL
properties. Corrosion and equipment compatibility is often catalysts or IL/acid mixtures require considerable mixing to
overlooked in the literature and requires more studies in the enhance the mass transfer rates by increasing surface area. To
future. overcome this problem, the immobilization of ILs on a solid
5.3.4. Small Amount of Base in Acid (In Situ IL and Acid support is considered as a promising strategy.97 The very short
Mixture). Development of additives for the H2SO4-based C4 diffusion distances in the supported IL homogeneous film
alkylation process has attracted the interest of academics as avoids mass transfer limitations and warrants an efficient
well as industrial researchers since the process was introduced utilization of minimum volumes of IL. Acidic ILs can be
to produce a higher quality of alkylate. Caprolactam forms a supported in pretreated silica-based support materials to access
stable sulfate by reacting with H2SO4 and may improve the the acidic sites on the supported IL phase (SILP).98 ILs were
solubility of isobutane in H2SO4.96 Therefore, Li et al.88 used a supported into solid materials using two different methods: (1)
small amount of caprolactam as an additive in the H2SO4- impregnation (noncovalent bonding) and (2) grafting
based C4 alkylation process. It was believed that caprolactam (covalent bonding) the cation on the surface of the solid.
can also form an in situ IL ([Caprolactam][HSO4]) after Impregnation can be performed by “incipient wetness”; i.e., the
reacting with H2SO4 in the C4 alkylation process. This IL is added to the support until the mixture has the appearance
approach is similar to the approach of IL−H2SO4 binary of a dry powder. However, grafting of the IL on a solid support
systems (IL is a [HSO4]−-containing protic IL). Increasing the provides a covalent binding of the IL to the solid support.
Among these approaches, the grafting of IL on solid supports is
amount of caprolactam from 0 to 1.0 wt % in H2SO4, increased
reported to be more effective.97
the alkylate qualities (C8 selectivity from 78.5% to 88.1%)
Kumar et al.78 prepared immobilized AlCl3-based ILs using
(Table 6, entries 95−97 and 100−101). However, further
both approaches. The chloroaluminate IL [C4C1im][Al2Cl7]
increasing caprolactam from 1 to 3 wt % decreased the TMPs
was loaded on silica supports by an impregnation approach
from 80.1% to 79.2% (Table 6, entries 97−99). (called impregnated catalyst A). In this approach, an [Al2Cl7]−
Zhang et al.89 investigated heterocyclic basic compounds anion from IL bonded to the silanol hydroxyl group on the
such as pyridine and thiophene as an additive (1 wt %) in silica surface and released HCl (Scheme 4, top). To maintain
H2SO4-based C4 alkylation. Interestingly, after using the the [Al2Cl7]− anion in the supported IL, a grafting (or
thiophene−H2SO4 system in C4 alkylation, the alkylate quality functionalized) approach was used and prepared an [Al2Cl7]−
was significantly enhanced (Table 6, compare entries 104−105 anion-containing IL on solid supports like MCM-41 (i.e.,
to 102). This could be due to the in situ formation of 2- grafted catalyst B) (Scheme 4, bottom). These catalysts
thiophene sulfonic acid (after reacting thiophene with H2SO4) prepared from the impregnated and grafted approach were
and could further act as an efficient additive for the reaction; investigated in C4 alkylation and confirmed that the catalyst
however, in the case of the pyridine−H2SO4 system, the prepared from the grafted approach is more efficient (Table 5,
activity was similar to that of pure H2SO4 (compare entry 103 compare entry 31 to 30). The low activity in the impregnated
to 102). catalyst could be assigned to bonding between the active anion
Yu et al.90 investigated the acidic deep eutectic solvent of the IL and the silanol hydroxyl group on the silica surface
(DES) system, consisting of CF3SO3H and taurine/alanine/ (Scheme 4, top). It should be noted that these solid-supported
choline chloride, in polyethylene glycol (PEG-200) as the ILs found better catalytic activity than both zeolite H-beta (Si/
catalysts for C4 alkylation. These DES systems produced Al = 14) and Nafion−silica nanocomposite catalysts but lower
significantly higher alkylate qualities compared with the than the corresponding neat ILs.
corresponding individual components in the systems (e.g., Bui et al.54 used Dowex resin (sulfonic group-functionalized
CF3SO3H, taurine, PEG-200, and [CF3SO3H]3[Tau]). Among resin) as the solid support (similar to impregnated catalyst
the investigated DES systems, the [CF3SO3H]3[Tau]/PEG- approach)/additive for Lewis acidic IL [C8C1im][Br]−AlCl3
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
Table 7. Comparison of Alkylation Technologies28

Technology Comparison
H2SO4 HF Ionic Liquids (ISOALKY)
Isobutane/olefin molar 7−15 10 7−15
(I/O) ratio
Feed moisture Not critical <10 ppm <1 ppm
requirement
Reaction temp (°C) 0−15 35 0−100
Pressure (psi) 30−80 200 30−200
Alkylate quality (RON) 95−96 95 94−99
Conjunct-polymer 1−1.5 ∼0.5 0.3−0.5
formation rate, wt %
olefin (%)
Handling of conjunct Incineration Incineration Converted to naphtha and LPG
polymer
Catalyst makeup rate, lb ∼400× base, off-plot regeneration ∼2 × base, online regen base, online regen
IL/bbl alkylate
Safety and environmental Large H2SO4 required, handling the large quantities Large toxic HF required, volatile HF Small IL required, nonvolatile
impact of spent H2SO4, SOx emission during requires engineering control and special catalyst, reduction of caustic
regeneration PPE solution waste
in C4 alkylation. As compared to the neat IL, the impregnated 6. SAFETY HAZARDS

IL on resin produced a significantly higher alkylate quality As discussed in previous sections, oil refineries use either
(TMP selectivity increased from 21.3 to 53.0 wt %) (Table 5, anhydrous HF- or H2SO4-based technologies for alkylate
compare entries 35−37 with entry 34). This enhanced activity gasoline production. However, several industrial accidents have
could be due to the presence of Brönsted−Lewis bifunctional occurred in HF-based refineries from 1986 to 2019 resulting in
acidic sites in the system. the release of hazardous emissions of HF.99 The most recent
5.4.1. IL/Polymer−HF Complex. Olah et al.80 developed accident occurred on June 21, 2019, at a refinery near
HF-based complexes (ionic solid/liquid) for C4 alkylation Philadelphia, PA. Multiple explosions in the alkylation area
(Table 6, entries 81−85). The threshold temperature of HF released over 1500 kg of HF, which could have resulted in a
release was referred to as the temperature at which the catastrophic HF release effecting millions of people.100
complex lost more than 1 wt %. As expected, the threshold Compared to HF, H2SO4-based conventional alkylation
temperature of volatility increased with the increasing molar technology is safer and considered the most common
ratio of the base (e.g., pyridine or polyamine) to HF. In this technology. However, the usage and handling of large qualities
report, C4 alkylation was carried out at the threshold of spent H2SO4 (>50% in the process) are one of the long-
temperature and there was likely HF released from the standing environmental concerns. To overcome these limi-
complex. Still, this study proves that the amine−HF complex tations, various classes of ILs will be developed and
could significantly reduce the HF volatility and provide a more commercialized for C4 alkylation; however, there are still
convenient catalyst for C4 alkylation. some concerns that need to be addressed. For example,
5.5. Comparison of Large-Scale Alkylation Technol- moisture-sensitive ILs (e.g., chloroaluminate-based ILs) need
ogies. Chevron28 compared key features of conventional to be handled in an inert atmosphere. In IL catalysts where
alkylation technologies with their ISOALKY technology using HCl is added, such as the Chevron ISOALKY, the system still
ILs in a recently published book chapter, and this is has some vapor pressure (although much lower than HF or
summarized in Table 7. pure HCl), and precautions must still be taken. In the case of
The H2SO4 alkylation technology typically operates at less perfluorinated anion-based IL when combined with H2SO4,
than 15 °C with cooling, while the HF alkylation technology some of the anions are hydrolytically unstable and could
operates at about 35 °C with cooling water. However, the decompose to release HF.
ISOALKY technology has a potential operating window from 0
to 100 °C, but actual economic operating conditions are most 7. CONCLUSIONS
likely in a much narrower range. Chevron indicates that the Petrochemical alkylation processes require strong acidic
ISOALKY technology can produce a higher quality of alkylates conditions and currently use either large quantities of H2SO4
than other alkylation technologies by operating at 0 °C. To or volatile anhydrous HF as the catalysts. Next-generation
reduce the capital cost, the unit can be designed to operate at catalysts for alkylation chemistry will be based on ILs due to
35 °C with cooling water similar to HF alkylation technology. their ionic speciation (tunable Lewis and/or Brönsted acidic
The ISOALKY technology requires catalyst regeneration properties) and extremely low vapor pressure. In addition, ILs
similar to all conventional techniques that remove the acid- have the added advantage of fine tuning their acidic properties
soluble oils and regenerates the acidity. This is performed and wide liquid range by controlling solid/liquid acid
online and onsite with the regeneration products acceptable to concentration. In the present review, we have discussed the
be sent into a naphtha stream at a refinery. Additional speciation and mass transfer properties of ILs and their effects
advantages with respect to process safety include (1) a on the alkylation reaction, compared the authors’ inves-
reduction in acid catalyst inventory, (2) elimination of some tigations with regard to chemical speciation, and presented
emissions and waste caustic solutions, and (3) reduced levels examples of how the tunability of these IL materials is used to
of special PPE. overcome current process drawbacks.
Ind. Eng. Chem. Res. 2020, 59, 15811−15838
■
pubs.acs.org/IECR Review
Many different anionic and/or cationic acidic species AUTHOR INFORMATION

containing ILs have been evaluated for alkylation reaction Corresponding Author
and are discussed by the type of IL which includes (1) metal- Mark B. Shiflett − Department of Chemical and Petroleum
based Lewis acidic ILs, (2) metal-based Brönsted−Lewis acidic Engineering and Center for Environmentally Beneficial
ILs, (3) nonmetal-based Brö nsted acidic ILs, and (4) Catalysis, University of Kansas, Lawrence, Kansas 66045,
immobilized/supported ILs. However, most authors report United States; orcid.org/0000-0002-8934-6192;
the IL composition (not species) or assumed the speciation, Email: mark.b.shiflett@ku.edu
ignoring all the components of the catalytic mixture that might
influence the speciation. A deeper understanding of the Authors
speciation can lead to the erudite design of the IL catalyst. Rajkumar Kore − Department of Chemical and Petroleum
Also, several classes of IL catalysts are viscous, which can Engineering and Center for Environmentally Beneficial
reduce mass transport for the isobutane alkylation reaction Catalysis, University of Kansas, Lawrence, Kansas 66045,
even with high mixing. The connection between IL mass United States; orcid.org/0000-0002-3361-1188
transfer properties and catalytic activity in alkylation is rarely Aaron M. Scurto − Department of Chemical and Petroleum
discussed. ILs in combination with strong acids/additives/ Engineering and Center for Environmentally Beneficial
promoters produced enhanced activity (even compared with Catalysis, University of Kansas, Lawrence, Kansas 66045,
the H2SO4 process) due to their ionic speciation, but a few United States; orcid.org/0000-0001-7214-1871
concerns still need to be addressed. For example, chloroalu- Complete contact information is available at:
minate ILs are sensitive to moisture, and the ILs can deactivate https://pubs.acs.org/10.1021/acs.iecr.0c03418
releasing HCl gas as a result of the hydrolysis. During the
chloroaluminate IL-catalyzed alkylation, some solids form, and Notes
the acidity of IL will decrease, resulting in decreased activity of The authors declare no competing financial interest.
■
the recycled IL. In the case of nonmetal-based ILs (with
Brönsted acidic functional groups like −SO3H and [HSO4]−), ABBREVIATIONS
their acidity is usually too low to efficiently catalyze C4
alkylation. However, Brönsted acidic ILs used with strong BPD = Barrels per day
acids do produce a high quality alkylate. Some problems DES = Deep eutectic solvent
related to the use of strong acids, corrosion of equipment, IL = Ionic liquid
environmental concerns, and high operating costs in catalyst LCCs = Liquid coordination complexes
recycling are still not yet resolved. In addition, these ILs can be C4 alkylation = Isobutane/alkene alkylation
expensive. The high viscosity of ILs is another problem for TMPs = Trimethylpentanes
mass transfer limitations, particularly at low reaction temper- DMHs = Dimethylhexanes
atures. RONs = Research octane numbers
In the near future, new insights into the molecular structure I/O ratio = Ratio of isobutane (I) to olefins (O)
and dynamics of IL catalysts will provide more precise control t min = Time minutes
over their properties and open new opportunities for the P = Pressure
applications of this novel class of materials. There still remain Conv. = Conversion
many interesting combinations of ILs (speciation) that can Sel. = Selectivity
lead to new catalysts for C4 alkylation technology. One way to wt % = Weight percent
increase the acidity of nonmetal-containing ILs can be to ref = References
increase the number of acidic sites in ILs that could easily L = Ligand or base
catalyze C4 alkylation. Also, the introduction of electron- NMA = methyl acetamide
withdrawing groups into the ILs that could increase their DMA = N,N-dimethylacetamide
acidity. The cost of ILs can be reduced by designing new NMF = N-methyl formamide
approaches for IL synthesis (e.g., efficient scale-up technolo- NMR = Nuclear magnetic resonance spectroscopy
gies and lower cost starting materials) and also by considering IR = Infrared spectroscopy
natural materials (e,g., biomass-based compounds). To ESI-MS = Electrospray ionization mass spectroscopy
commercialize the IL-based C4 alkylation process, much H2SO4 = Sulfuric acid
fundamental work still needs to be completed for ILs, such HF = Hydrofluoric acid or hydrogen fluoride
as physicochemical properties, phase equilibrium thermody- CF3SO3H = Trifluoromethanesulfonic acid or triflic acid
namics, ionic speciation, and acidity. In addition, new reactor HCl = Hydrochloric acid
and separator designs should be explored to take advantage of AlCl3 = Aluminum chloride
the unique properties of IL catalysts. Material compatibility GaCl3 = Gallium chloride
FeCl3 = Ferric chloride
must be determined before any scale-up can occur.
■
CuCl = Cuprous chloride
ZnCl2 = Zinc chloride
ASSOCIATED CONTENT NiCl2 = Nickel chloride
*
sı Supporting Information SnCl4 = Stannic chloride
The Supporting Information is available free of charge at Cu(CF3SO3)2 = Copper(II) salt of trifluoromethanesulfonic
acid
■
https://pubs.acs.org/doi/10.1021/acs.iecr.0c03418.
Corrosion rates of steels in different catalyst systems CATIONS
(Table S1) (PDF) [CnC1im]+ = 1-Alkyl-3-methylimidazolium
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Revisión de La Tecnología de Alquilación de Isobutano Utilizando Catalizadores Iónicos Basados en Líquidos - Dónde Nos Encontramos - 2020

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Review of Isobutane Alkylation Technology Using Ionic Liquid-

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ABSTRACT: Conventional strong liquid acids such as H2SO4 and

liquid (IL) catalyst technologies oﬀer potential advantages over

1. INTRODUCTION that accumulate in the catalyst pores. Once this carbonaceous

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c03418

Scheme 1. Strong Acid (H2SO4/HF)-Catalyzed Mechanism for C4 Alkylation Reaction

Scheme 2. IL-Catalyzed Mechanisms for C4 Alkylation Reaction48,49

becomes basic or neutral, and the dominant anion is [MCl4]−.

CuO/ZnO/ × n.d. × × n.d. × × × ×

Ind. Eng. Chem. Res. 2020, 59, 15811−15838

C4 alkylation reaction, but rarely have they studied the eﬀect of

Eﬀect of Cations on Chloroaluminate-Based ILs

18 [P444−5][Al2Cl7] None n.d. 65 25 − 11.1:1 3.4 100 87.0 − 25.4 98.4 50

Effect of Additives on Chlorogallate-Based ILs

Effect of Organic Additives on Chloroaluminate-Based ILs

Figure 6. Overall ISOALKY technology process.28

Ind. Eng. Chem. Res. 2020, 59, 15811−15838

31 Graphted [SiC3C1im][Al2Cl7] on n.d. n.d. 80 270 110:1 − 97.0 59.7 − − − 78

Ind. Eng. Chem. Res. 2020, 59, 15811−15838

Effect of Perfluorinated Anion-based ILs

Effect of hydrophobic Cations with Perfluorinated Anions

Effect of Hydroxy-Functionalized Cations

Table 7. Comparison of Alkylation Technologies28

in C4 alkylation. As compared to the neat IL, the impregnated 6. SAFETY HAZARDS

Many diﬀerent anionic and/or cationic acidic species AUTHOR INFORMATION

[C4C1im]+ = 1-Butyl-3-methylimidazolium (2) Albright, L. F. Alkylations Industrial. In Encyclopedia of Catalysis;

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