X

Journal of Molecular Liquids 224 (2016) 177 –188

Contents lists available at ScienceDirectX

Journal of Molecular Liquids

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

Review

Ionic liquids as alternatives of surfactants in enhanced oil recovery—A state-

of-the-art review
Achinta Bera , Hadi Belhaj

Petroleum Engineering Department, The Petroleum Institute, Abu Dhabi, P.O. Box – 2533, United Arab Emirates
sound alternatives of surfactants in en-hanced oil
recovery. Available research works have already
marked them as “green chemicals” for a downstream
petroleum refinery. But again several issues should
article info abstract be considered to use this specific term for ionic
liquids as many of them are toxic and non-
Article history: Generally, biodegradable.
surfactants are
used to be The present review provides an overview of
Received 23 June 2016
considered as available works on ionic liquids and their
effective effectiveness in enhanced oil recovery. A thorough
Received in revised form 26 September 2016 Accepted 27 September candidates in discussion has been provided on the selection of
2016 chemical ionic liquids that is a very crucial issue for the
enhanced oil effectiveness of an ionic liquid in oil recovery
recovery due to methods. Laboratory works mainly focused on the
Available online 29 September 2016 their high-level charac-terization and their applications in interfacial
performances of tension reduction, wettability alteration and core
interfacial flooding experi-ments for additional oil recovery,
Keywords:
tension were documented in this review, although few in
reduction and numbers. Available literature indicates the
Ionic liquids wettability effectiveness of ionic liquids in the reduction of
alteration. After interfacial tension, additional oil recovery in core
a few laboratory flooding experiments and wettability alteration of
Surfactants experiments, a oil-wet rock surfaces. The future challenge of newly
chemical synthe-sized chemicals like active ionic liquids for
Chemical enhanced oil recovery namely “ionic oil recovery has also been discussed. It is believed
liquids” has that the present re-view will provide a platform for
immensely the new researchers to get an overview of the
Interfacial tension attracted the applications of surface active ionic liquids in
attention of the chemical enhanced oil recovery techniques. The
researchers for information provided in this critical review paper
Wettability alteration fur-ther will help to explore the topic deeply and make the
characterization progress of work smoothly.
Ionic liquid microemulsions of the candidate,
before taking a
decision about © 2016 Elsevier B.V. All rights reserved.
Ionic liquid microemulsions and . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
liquids phase behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
in . . . . . . . . . . . . . . . . . 184
hydroca . . . . . . . . . . . . . . . . .
rbon . . .
recover 182 8.3.
y and 6. Adsorption . . . . . . . . . . . . . . . . . . . . . .
Contents processi Advantages of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ng . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 185
. . . . . . . . . . . . . . . . . . . . . . 9.
. . . . . . . Mechanism and oil recovery performances of ionic
1. liquids . . . . . . . . . . . . . . . . . . . . . . . . .
Introduction . . . . . . . . . . . . . . . . . . . . . 182
. . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . Limitations of ionic liquids. . . 185
178 . . . . . . . . . . . . . . . . . . . . . . 10.
. . . . . . . . . . . . . . . . . . . . . . Future challenges of EOR by ionic
179 . . . . . . . . . . . . . . . . . liquids. . . . . . . . . . . . . . . . . . . . . . . . .
1.1. 4. . . . . . . . . . . . . . . . . . . . . . . . . . .
Background of ionic liquids . . . . . . . . Applica 182 186
. . . . . . . . . . . . . . . . . . . . . . . tions of 8. 11.
. . . . . . . . . . . . . . . . . . . . . ionic Influenced factors by ionic Conclusions . . . . . . . . . . . . . . . . . . . . . .
178 liquids liquids in EOR methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
in CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . .
- EOR . . . . . . . . . . . . . . . . . . 186
1.2. . . . . . . .
Aims, motivation and novelty of this . . . . .
183
review . . . . . . . . . . . . . . . . . . . . . . . . Corresponding author.
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . 8.1.
178 . . . . .
. . . . .
Interfacial tension reduction . .E-mail address: achintachm@gmail.com (A. Bera). X
2. . . . . . . . . . . . . . . . . .
Surfactants in EOR methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
. . . . http://dx.doi.org/10.1016/j.molliq.2016.09.105 0167-
179 179
3. 5. 8.2. 7322/© 2016 Elsevier B.V. All rights reserved. X
Ionic Wettability alteration. . . . . .
178
A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188

Acknowledgements
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
187
References. . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
187

Table 1 as follows:X much attention in scientific

community like chemists,
biolo-gist, and other related
works even in upstream and
downstream petro-leum
1. Introduction Though often considered as,
engineering. In general, ionic
whether the ionic liquids can
liquids are considered as
be used as green chemicals in
Due to frequent fluctuations of oil price, the oil industries are molten salts even when it was
downstream petroleum
forced to seek cost-effective enhanced oil recovery (EOR) first reported in 1914 or
operations is questionable.
methods by inexpen-sive chemicals. Commonly surfactants are before Walden [12].
Therefore, it is important to
used to decrease interfacial tension (IFT) between oil and water
know the specific properties However, initially, ionic
phases and alter the wettability of reservoir rock surface for
that are neces-sary for a liquids were used as a
improving oil recovery up to 60–70% original oil in place
chemical to be a green one in propellant in warfare
(OOIP) [1–4]. Hence, surfactant flooding for EOR attracts the industrial application. The specifically-ethylammonium
attention of petroleum engineers and researchers for ample main features of green nitrate. After that, the
efficien-cy to extract the trapped oil from the reservoir after chemistry/chemicals were significant proper-ties of ionic
conventional water flooding. But due to the high cost and documented by Anastas and liquids are determined
environmental issues, sometimes surfactants are not considered Warner [11] as follows:X gradually and they have been
as prospective chemicals for chemical en-hanced oil recovery inter-ests of researchers for
(CEOR) methods. Recently surface active polymeric materials more applications. Although
are considered as potential candidates for improving oil re-covery 1. The waste chemicals there are no hard and fast
due to the dual role (IFT reduction and viscosity increase) in should be recycled rules proposed, they are
EOR methods [5,6]. The production costs of these materials are considered to be ionic salts
having a melting point up to
expen-sive and they are not environmentally viable. Extensive
100 °C. Ionic liquids have
research works are continued to reduce the costs of chemicals and
some unique properties which
their environ-mental impacts in CEOR techniques. New cost-
make them favorable in the
effective, as well as envi-ronmental friendly surface active Maximum materials should
application of many industrial
chemicals, are desirable for oil recovery. Recently more be incorporated in preparation
as well as research works.
attentions have been waged to surface active ionic liquids to of the chemicals
Due to several attractive
explore their effective participations in CEOR projects as sound
properties of ionic liq-uids
alternatives of surfactants. But it has been seen from an exper-
The chemicals should have they have different
imental study that non-surface active ionic liquids can recover a
fewer hazards applications including: (1)
signif-icant amount of additional oil due to their ionic nature and
solvent extraction;X
aromaticity [7]. Non-surface active ionic liquids also proved the
Should have less toxic
ability to recover a significant amount of oil due to their ionic
properties
nature and aromaticity [7]. Therefore, other ionic liquids should (2) chemical analysis; (3)
dye-synthesized solar cells;
similarly be tested in near future research works to get a better
Should be user-friendly (4) oil shale pro-cessing; (5)
idea about other classes of ionic liquids al-though most of the
separation of petrochemicals
research works are in progress.X products; (6) electrochemis-
Should be energy efficient
try solvent; (7) materials
chemistry; (8) biocatalysts;
The raw materials used in (9) chemical and biochemical
synthesis should be renewable transformation; and (10)
nuclear based separation.
1.1. Background of ionic liquids
The chemicals should have
fewer derivatives Conventionally available
In 1961, a serious exclusive conversation with molten inorganic
ionic liquids can be classified
salts was held at the “Faraday Society Discussion” meeting on the
into mainly two categories
topic enti-tled “The Structure and Properties of Ionic Melts” in Should be good catalytic
attending the anions and
Liverpool [8]. Later on 1970 Bockris and Reddy [9] described agents cations. Borate, dicyanamide,
the natures of ionic liquids in their Modern Electrochemistry halide, bis
book to avoid the “molten salt” term. Ionic liquids are organic Degradable and (trifluoromethylsulfonyl)
salts that exist in a liquid state at room temper-ature below 100 environmental friendly imide, nonaflate, phosphate,
°C with poorly adjusted ions which have unique and promising sul-fate, sulfonate,
properties. Again Johnson [10] defined the modern ionic liq-uids Should be able to analyze thiocyanate, and
tricyanomethide are the
as the volatile organic solvents with low vapor pressure and mod- pollution in real time for
anions present in some ionic
erate specific conductivity. The modern ionic liquids mainly have prevention
liquids. Ammoniums,
properties of organic salt with quite large cations and anions. The
guanidiniums, imidazoles,
freez-ing point of the ionic liquid is preferably b100 °C and also
Should be suitable for safer morpholines, phosphoniums,
should be in a liquid state below 200 °C. The thermal stability of
chemistry works for accident piperidines, pyridiniums,
the ionic liquid is usu-ally high and workable viscosity is
prevention pyrrolidines, and sulfones are
normally N100 cP. The dielectric con-stant of this type of ionic
the cations present in the
liquid is usually b30 and polarity should be moderate with the
others. Depending on the an-
excellent catalytic property. Apart from these signif-icant Some classes of ionic liquids
ions and cations of the ionic
properties, some categories of modern ionic liquids are environ- have been found to fulfill all
liquids their properties vary
mentally friendly to be used for different purposes. All the above- these criteria and are claimed
and their effec-tiveness are
stated properties of modern ionic liquids are well documented in to be green chemicals. So, altered accordingly.
ionic liquids have attracted
 Polarity
Moderate
A salt Specific conductivity
Cation and or anion quite large Usually b10 mScm-1, “Good”
1.2. Aims, motivation and novelty of this review Molar conductivity
2 −1
b10 Scm mol
Electrochemical window
Different chemicals like surfactants, alkali, polymer, and organic N2 V, even 4.5 V, except for
Freezing point
sol-vent are generally used in chemical EOR methods. Preferably below 100 °C Brønsted acidic systems
Surfactants are Liquidus range Solvent and/or catalyst
Often N200 °C Excellent for many organic reactions
Thermal stability Vapor pressure
Table 1 Usually high Usually negligible
Viscosity
Normally b100 cP, workable
X
Properties of modern ionic liquids (adopted from [10]). Dielectric constant
Implied b30
A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188
179

considered as prospective mechanisms in surfactant

candidates in the upgrading EOR and thus readers will be
mainly considered for EOR to reduce IFT
of heavy oil by cracking the able to find a relationship
followed by wettability alter-ation to
large chain asphaltenes in between surfactants and ionic
increase the capillary number. Alkali is used
downstream petro-leum liquids applications in EOR.
to alter wettability of rock surface. Polymers
In this section, mainly the
are used to increase the viscosity of injected industry [17,18]. Ionic
activities of different
water to improve the sweep efficiency. A liquids have different
surfactants that are
combination of three may be considered potential uses in downstream
responsible for additional oil
sometime to get better results by influencing oil operation like a refinery,
recovery will be discussed,
all the driving parameters in CEOR. In the heavy crude, and tar
for an outline overview of
same way, ionic liquids can also be consid- upgrading with high-
surfactant EOR methods.
ered as surface active agents like surfactants efficiency [19–23].
in COER to reduce IFT, alter wettability and
Depending on some extreme
little increase in viscosity (some cases) of Surfactants are generally
environmental friendly
injected fluid. known as amphiphilic organic
properties ionic liquids can be
compounds composed of
actively used in crude
hydrophobic and hydrophilic
More recently many ionic liquids which transportation and oil-water
groups, with both oil soluble
might also be known as green separation. Other important
and water soluble parts which
chemicals/solvents strongly attract the most relevant topics for ionic
make them amphiphilic in
researchers for EOR pur-poses because of liquids are fuel (gasoline,
nature. They can
their unique properties such as high thermal diesel) desulfurization and
accommodate themselves at
stability over a wide temperature range, aliphatic/aromatic separation
the oil-water interface to
nonflammability, and solubility in many for downstream processing
reduce the IFT between oil
organic and inorganic compounds. Different and cur-rently several
and water. It is noticed that
types of eutectic sol-vent based ionic liquids research works are an
the water-hating part (hy-
can be prepared by the combination of zinc ongoing stage to progress the
drophobic) may extend out of
chloride and amides and diols which are field [24–28].X the bulk water phase into the
viscous in nature. These ionic liquids have
air or the oil phase while
metal containing anions and cations and
water-loving part
their physical properties are similar to other The present review paper has
(hydrophilic) likes to stay in
ionic liquids [13]. Deep Eutectic Solvents been formulated to gather the water phase accordingly.
current scenario of available
(DES) based ammonium and phosphonium
research works on ionic
associated ionic liquids ions are used for the
liquids for EOR. There are a Generally, four types of
measurement of their surface tension at a
few laboratory experiments surfactants, including anionic,
different tem-perature. Experimental results
available up to date on cationic, non-ionic and
imply that surface tensions of the sol-vents
applications of ionic liquids zwitterionic, were tested in
increase with an increase in temperature in EOR. In this review, we different laboratory
[14], and other properties such as ionic will provide a plausible experiments for their
nature and aromaticity of some ionic liquids understanding of the applications in enhanced oil
can also help to increase oil recovery. In this mechanism of ionic liquids production [29–33].
regard, ionic liquids can be used in during oil recovery. It is a
Depending on the headgroup
conventional water flooding to enhance oil fundamental study to
charges of surfactants, the
recovery from carbonate reservoir [7]. overlook on the matter that
surfactants have been se-
ionic liquids are really more
Researchers have started to think about the lected for the application in
cost-effective and less
ionic liquids-EOR by these particular ionic different types of the
hazardous alternatives of
liquid candidates as a poten-tial alternative reservoir. Generally, anionic
surfactants. The advantages
to traditional surfactants and other organic surfactants are preferred to be
of ionic liquids over
solvents. It is very important to take it an used in sandstone reservoirs
surfactants in EOR are
account of the enhanced properties of the due to the same surface
discussed in this review. We
chemicals when they have been produced charges of rock and
expect this review will open a
for any EOR application par-ticularly in surfactant. Cationic surfac-
door for the new researchers
high saline and high-temperature reservoir tants, however, are used in
to get a clearer idea for a
conditions.X carbonate reservoirs due to
further study of ionic liquids
same surface charges of
in oil recovery methods.
cationic surfactant and
The mechanism of surfactant flooding for carbonate rock. Nonionic
EOR consists of IFT reduc-tion and 2. Surfactants in EOR surfactants can be used in
wettability alteration due to their surface methods both cases, depending on the
active properties. In the same way, ionic effectiveness of trapped oil
liquids (modified by adding alkyl chain) are recovery, after secondary
As we are targeting to
also considered as surface active agents for water flooding. Zwitterionic
conduct a review on ionic
EOR due to their effectiveness to lower IFT surfactants are used but the
liquids as alterna-tives of
and micelle formation property. A few availability of this surfactant
surfactants in EOR, it is
laboratory research works have already is rare and production of
necessary to provide a brief
shown that the ionic liquids can reduce IFT these surfactants is also
description
even in high temperature and high salinity expensive. Several
conditions [15,16].X application-oriented re-search
about surfactant EOR in order works are on the laboratory
to get a basic idea of the scale. The selection of
Apart from the upstream oil recovery methods. The presented surfactant for different
methods, ionic liquids are also used in section on surfactant EOR is reservoirs is a crucial issue
downstream oil refineries. It has been only meant to provide a very since the rock surface
noticed now that ionic liq-uids can be cur-sory concept of different adsorption of the surfactant
makes the oil recovery process that all types of ionic liquids re-cent works on ionic liquids
economically unfeasible.X are not useful for oil recovery in oil recovery
application. All the ionic experiments.X
liquids listed in Table 2 do
not have surface active
4. Applications of ionic
3. Ionic liquids in hydrocarbon recovery nature, but somehow they are
and processing tested in the laboratory to liquids in CO2 - EOR
screening test their properties
(what properties). The results Nowadays ionic liquids are
Ionic liquids based on pyridinium,
of the studies reflect a considered as exciting
pyrrolidinium, piperidinium, triazolium,
negligible reduction of IFT in candidates of or-ganic
ammonium and phosphonium are being
some cases. The complex-ity compounds with potential
explored and uti-lized towards the
in ionic liquids should be efficiency to overcome the
applications of several engineering fields studied properly for EOR
associated problems of CO2-
[34]. Several ionic liquids have been tested application through
in the laboratory for uses in hydrocarbon laboratory screening test and EOR by CO2 capturing
extraction and the processing of heavy phase behavior. Uniquely de- technology. Gas flooding in
crude oil. It is shown in the liter-ature that signed ionic liquids are only EOR, especially in shale oil
the aggregation behavior of an ionic liquid applicable for the particular recovery, is a critical issue.
like dialkylimida-zolium is close to that of a purpose of oil recovery. In Thus, EOR by CO2 flooding
cationic surfactant (alkyltrime- this section ( Table 2) we is the interest of researchers
thylammonium salts), though ionic liquids as it has potential ability to
will present the list of ionic
have a better ability to self-organize, re-cover additional oil from
liquids that have been used in
especially as it concerns long-range the pore throat after
different laboratory
ordering [35]. They were selected experiments in EOR methods. secondary recovery. It is
depending on their abilities of oil recovery This description will help to
and heavy crude dis-solution. It is essential accumulate the overview of
180 A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188

Table 2

Some selected ionic liquids in laboratory experiments.

Ionic liquids
Purpose of use in experiments/brief description
References

Tetra-alkyl ammonium sulfate (Ammoeng 102); Quaternary ammonium

All these ionic liquids were screened for application in EOR methods. Among
[36] X
chloride (Ammoeng 110); Quaternary ammonium acetate
these ionic liquids, Tetra-alkyl ammonium sulfate acts as the most effective one

(poly[oxy(methyl-1,2-ethandiyl)]-
to reduce IFT and alter wettability. Most of them are water soluble except

alpha-(diethyl-hydroxyethylammonio)ethyl] -acetate) (Ammoeng 111);

Ammoeng 111 and Ammoeng 130. The main drawback of water insoluble ionic

(Poly[oxy(methyl-1,2-ethandiyl)]- alpha-(diethylhydroxyethylammonio)
liquids is that it is difficult to measure the IFT. It can be stated that water soluble

ethyl]-dihydrogenphosphate) (Ammoeng 112); Quaternary ammonium

ionic liquids should be chosen for application in oil recovery as IFT reduction is

sulfate (Ammoeng 120); 1-Octadecanaminium,N,N-dimethyl-Noctadecyl-,

one of the major issues. To reduce IFT the ionic liquids must be soluble in water

chloride (1:1) (Ammoeng 130); 1-Ethyl-3-methylimidazolium dicyanamide

and stay at the oil-water interface so that they can be absorbed in the interface

(IL25); 1-Ethyl-3-hydroxymethylpyridinium ethylsulfate (IL34);

to work properly in IFT reduction.

Tri-n-butylmethylphosphonium methylsulfate (IL37)

1-Butyl-3-methyl imidazolium chloride; 1-butyl-3- methylimidazolium

These ionic liquids were used to study their abilities in the dissolution of heavy
[37] X
bromide; 1-hexyl-3-methylimidazolium bromide;
crude oil. The IFT between ionic liquids and crude oil were measured and it was

1-octyl-3-ethylimidazolium chloride
found that these ionic liquids are able to reduce the IFT between oil-water

interfaces. So, imidazolium ionic liquids with halide anions (such as chloride and

bromide) are effective in crude oil dissolution. They are effective in IFT

reduction; hence, these types of ionic liquids are always preferable for oil

recovery experiments due to high-level surface activities.

1-Ethyl-3-methyl imidazolium tetrafluoroborate ([Emim]BF4)

This ionic liquid was used to conduct an experiment for extracting bitumen from
[38] X
oil sands at ambient conditions. The experimental results of bottle tests show
that the bitumen recovery is highly dependent on the volume ratio of ethyl

acetate to n-heptane. The addition of ionic liquids with ethyl acetate and

n-heptane mixture (3:6) enhances the bitumen recovery up to 10% (from 83 to

93% at the ethyl acetate to n-heptane ratio of 3:6). It is important to note that

−
[BF4] can produce HF in presence of water. Thus, special precautions should be

taken during working with these types of ionic liquids, otherwise one should

avoid these ionic liquids in laboratory experimental purposes where HF is

expected. This is also applicable for other ionic liquids that contain halogen

− − − −
anions like [AlCl4] , [PF6] , [CF3SO3] or [(CF3SO2)2N] ).

1-Ethyl-2,3-dimethylimidazolium tetrafluoroborate;
These ionic liquids were used to study the wettability alteration of carbonate
[39] X
1-Ethyl-3-methylimidazolium tetrafluoroborate;
rocks by the contact angle method. The results indicated that the ionic liquids

1-Butyl-3-methylimidazolium tetrafluoroborate;
are effective to alter the wettability of carbonate rocks from oil wet to water wet

1-Butyl-2,3-dimethyl-imidazolium tetrafluoroborate
state. In this case, it is important to notice the ionic natures of the ions of ionic

liquids. Since carbonate rocks are positively charged in nature, it is preferred to

choose cationic ionic liquids to reduce the rock surface adsorption of chemicals.

The rock surface adsorption of ionic liquids is thus suggested for further study.

Trihexyl(tetradecyl)phosphonium chloride
This ionic liquid is used to study phase behavior of the oil-brine-ionic liquid
[40] X
system for characterization to use in EOR method. In general, phase behavior

study targets consists surfactant, oil, brine, and cosurfactants. But it is very much

interesting to see that phase behavior study with ionic liquid does not need any

cosurfactants. The experimental result says that this ionic liquid has the
capability to form a triphasic system in a wide range of reservoir temperature. It

is well known that surfactant-oil-brine system can form three-phase

microemulsion system which acquires ultra-low IFT. Accordingly, phase

behavior of ionic liquid-oil-brine system should be studied for further

clarification of their properties. The microemulsion formed by ionic liquids in

the oil-water system is also important in oil recovery. More research works on

this topic should be conducted to further and better understand the phase

behavior of ionic liquid microemulsion systems.

1-Butyl-2,3,-dimethylimidazolium tetrafluoroborate (BMMIM BF4);

These two ionic liquids were again used to study the wettability alteration of
[41] X
1-butyl-3-methylimidazolium tetrafluoroborate (BMIM BF4)
carbonate rocks. It was found that the ionic liquids are able to alter the

wettability of rock samples effectively. Tetrafluroborate imidazolium ionic

liquids can be considered as a good candidate for wettability alteration agents.

The concentration of ionic liquids is a controlling factor as well.

Diethylammonium sulfate; Triethylammonium acetate; Triethyl ammonium

These six synthesized ionic liquids were used to measure the IFT between crude
[42] X
phosphate; Triethylammonium sulfate; Tripropylammonium sulfate;
oil and ionic liquid solutions. It was found that the ionic liquids are active to

3-hydroxypropylammonium trifluoroacetate
reduce IFT. Core flooding experiments were also conducted with ionic

liquid/surfactant/polymer/salt mixtures. Experimental results show promising

results and it is believed that the mixed slug is very effective to recover oil. There

is a huge scope of working on the interaction between ionic liquids and

polymer/surfactant in the presence of salt. For future study, it is recommended

to conduct different experiments on a design project to understand the

interactions among the chemicals and their effects on the viscosity of the

polymer. This study will help to understand the behavior of ionic liquids under a

mixing condition with surfactant/polymer/salt.

Butyrolactam formate; Butyrolactam acetate; Butyrolactam hexanoate;

These ionic liquids were used to measure the surface tension as well as IFT. It has
[43]X
Caprolactam formate; Caprolactam acetate; Caprolactam acetate;
been found that all the ionic liquids are able to reduce the surface tension of

Caprolactam hexanoate; Propylammonium formate; Propylammonium

water as well as IFT between crude oil and water. However, the IFT and surface

acetate; 3-hydroxypropylammonium formate; 3-hydroxypropylammonium

tension values are not big enough for application purpose. So, further

acetate; 3-hydroxypropylammonium trifluoroacetate

improvement of the properties of the ionic liquids is required.

Tributylmethylphosphonium dodecylsulfate ([P4441][DS], surface active ionic

This ionic liquid was synthesized based on SDS surfactant. The new synthesized
X
[44]
liquid)
ionic liquid can be used easily as it is not too much viscous up to 200 K

temperature. [P4441][DS] surface active ionic liquid can reduce IFT up to 0.08

−1
mNm which is desirable in CEOR. From the experimental results, it can be

−2 −1
stated that this ionic liquid is effective in EOR methods as it can achieve the IFT reduction in the range of 10 mNm . Compared to other studies it has been

A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188

181
Table 2 (continued)

Ionic liquids
Purpose of use in experiments/brief description
References

noticed that this synthesized ionic liquid is capable of reducing IFT in desired

range. One conclusion can be drawn from this study that proper synthesis of the

−4 −1
ionic liquid can produce ultra-low IFT (10 mNm ) in microemulsion

systems which are also achieved by few surfactant systems at present.

Imidazolium-based ionic liquids (CnmimBr, n = 6, 8, 10, 12, 14 and 16)
This series of surface active ionic liquids were synthesized in the present work.
[45] X
They are used for EOR application with a combination of the copolymer.

Copolymer/C8mimBr complex can reduce IFT better than water/C 8mimBr

system under the conditions of high temperature and salinity. The reduced IFT is

not too low to be considered for proper EOR method. More active ionic liquids

need to be developed for EOR application. In this study, the interesting part is

that the combination of ionic liquid and copolymer. It should be clarified the

proper reason for the higher reduction of IFT in the case of the ionic liquid and

copolymer mixture than water/C8mimBr system. A separate study on the

interaction of ionic liquids and polymer is necessary in order to understand the

phenomena occurring during the mixing process.

New chemical compound [Et3NH]Cl/1.5 AlCl3 (X = 0.6) like ionic liquid

A new chemical compound [Et3NH]Cl/1.5 AlCl3 (X = 0.6) modified with CuCl,

[46] X
was developed for enhancing the recovery of the free imbibition and core

flooding mechanisms for naturally fractured reservoirs. It was found that this

ionic liquid compound significantly reduces oil viscosity, molecular weight and

alters wettability to a desirable state. This chemical compound has the capability

of reducing the IFT and contact angle. The solution of proposed new chemical

−1
and brine (NaCl) with water can decrease the IFT from 1.1 mNm to 0.044

−1
mNm . This new chemical compound is capable of reducing the IFT into a

favored range in EOR method. Since NaCl addition to an ionic liquid system
helps reduce the IFT due to a synergistic effect, the effect of brine concentration

in ionic liquid solution on the IFT reduction must be studied properly to find the

optimal salinity, which is very important in EOR.

Chloride-based Deep Eutectic Solvent (DES) (ionic liquid analogue)

These solvents were used in core flooding experiment and wettability alteration
[47] X
purpose. It was reported that the solvents in low concentration are also effective

to recover heavy oil by keeping the capillary number high. Since ionic liquid

analogue is working effectively in EOR, other chemicals may be derived in this

path as well. A series of DES chemicals should be used for screening of their

effectiveness in EOR.

1-Alkyl-3-methylimidazolium chloride, [Cnmim][Cl], n = 6, 7 and 8

These three ionic liquids are used for IFT measurement between toluene-water
[48] X
interfaces. The IFTs are relevant in the presence of electrolytes than one in

−2
salt-free condition. For instance, with typical concentration of 3.00 × 10 mol

−3 −1
dm for [C6mim][Cl], the IFT value is 27.4 mNm whereas it reaches to 15.3

−1
and 14.3 mNm corresponding to 44% and 48% reductions in the IFT with KCl

−3
and NaCl (each with a concentration of 0.50 mol dm ), respectively. The ionic

liquids used in this study are not much effective in the reduction of IFT for EOR

purpose. Synergism is observed in this study. It can be stated from this study

that all ionic liquids are not highly capable of reducing IFT, even combined with

salt.

1-(1-alkyl)-3-methylimidazolium chlorides with alkyl chains containing 10, 12,

Surface activities of these surface active ionic liquids were investigated in this
[49] X
and 14 carbons
work and micellization properties studied extensively. These prepared ionic

liquids are highly polar, thermally and chemically stable with low melting point,

and negligible vapor pressure. So these ionic liquids can be used for different

purposes. The thermodynamic study of ionic liquids is important for the stability

of micelles, which is another important aspect in micellar flooding of EOR

application.

1-Alkyl-3-methylimidazolium ibuprofenate (n ibuprofenate anion and

The surface activities of [CnMIm][Ibu] ionic liquids were investigated and
[50]X
1-alkyl-3-methylimidazolium [CnMIm] + (n = 4, 6, 8) cations), [CnMIm][Cl]
compared to other ionic liquids like [CnMIm][Cl] and [Na][Ibu]. This study

and [Na][Ibu]
provides the information of the comparison between [CnMIm][Ibu] and

[CnMIm][Cl]. In the case of [CnMIm][Cl], only long chain alkyl compound shows

surface activity whereas all the compounds with different chain lengths show surface activity. As a variation of alkyl chain length of ionic liquid influences the surface activity, therefore, it is
necessary to undergo further investigation in this topic.
can be further used for EOR method, will be chemical reaction then again
which can be recycled byX the CO2 can be separated from ionic
liquids and can be reinjected into the
important to capture the produced CO2 during production and neces-sary for reservoir through another cycle. As a
sequestration. Ionic liquids have been proved to be effective to capture CO2, huge amount of ionic liq-uids are
required for field application, it is
hence it is believed that they can be utilized to reduce CO2 emission in the capturing the emitted CO2 in ionic
necessary to have a look on the
liquids and the rest injected into res-
environment [51–55]. One limitation of ionic liquids is that they restrict the synthesis of cost-effective ionic
ervoirs. It can be considered to inject
capacity of CO2 capture and sequestration. Addi-tionally, ionic liquids can liquids for CO2 capture. Presently re-
a mixture of ionic liquids and CO2
solubilize aromatics and light hydrocarbons if they are used in the CO2-EOR searchers are highly involved in
into the reservoir after the first cycle
improving the properties of the ionic
method. Hence, it is high time to think about the possible uses of ionic liquids in production, and the next injected
liquids to make them more suitable
CO2-EOR in a different way for uses of ionic liquids in near future technology. solution will act as a surface active for particular applications. Accord-
agent. Depending on the properties of
Ionic liquids can be used to separate the CO2 from produced oil. If the ionic ing to the needs, the ionic liquids can
the ionic liquids, if it is possible to
liquids can be successfully used in this type of project, then greenhouse gas be modified or synthesized by
develop some ionic liquids which can
emission can be easily reduced, which will help make the oil production opera- changing the ions (cations and
dissolve CO2 physically and there anions) and aliphatic chain as well.
tion an environmentally friendly process. The dissolved CO2 in ionic liq-uids
182 A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188
changes phase from Winsor I advantages over organic
to Winsor II through W III surfactants as doc-umented
5. Ionic liquid microemulsions and
with in-creasing salinity of bellow [72,73]:X
phase behavior
the system. Temperature has
also effect on the phase
In general, three types of microemulsions behavior of microemulsion The melting points or glass
are well known and Schulman et al. [59] system. Similarly, in the case transition temperature of
of ionic liquid microemulsion ionic liquids are below 100
proposed the term “microemulsion”. The
systems phase change occurs °C which makes them very
microemulsions are thermodynamically
with increasing user-friendly for different
stable isotropic, a transparent mixture of
temperature.X applications.
water (brine), oil and surfactant
Extraordinary thermal and
(cosurfactants), in which ei-ther water or oil
chemical stability in wide
or both may remain dispersed and the
liquid ranges of some ionic
droplet sizes are greater than micelles [56–
The stability of ionic liquid liquids [74,75]. X
58]. These are water-in-oil, oil-in-water, and
microemulsions is very
bicontinuous. Different types of
important for their
microemulsions can be prepared by varying Ionic liquids are adjustable
applications in harsh
the concentration of any one the phase in molecules with the change of
condition of the reservoir.
the microemulsion systems. Variation of numbers of cations and
Although it is ac-ceptable that
salinity can produce different types of anions combination. As a
microemulsions are stable,
microemulsion systems. Generally, result, effective ionic liquids
but further investigation is
changing salinity from low to high that are venerable needs of
necessary to ascertain the
concentration microemulsion system EOR chemicals can be
stability of ionic liquid
undergoes a phase change from Winsor type prepared for appli-cation
microemulsion for the
I to Winsor type II through Winsor type III
application in different [76,77]. X
as shown in Fig. 1. The conventional oil- conditions. Several research
water-surfactant microemulsion system has works on ionic liquid
been developed to apply for the purposes of microemulsions are reported Some ionic liquids based on
food technology, drug delivery, and oil in the literature [65–70]. cations or anions have a
recovery. To monitor the properties of relatively higher viscosity
Almost all the available
microemulsions sometimes it is necessary that surfactant solution,
literature discuss on
to regulate the salinity of the system. Some which is favorable in a
characterization and different
studies showed the preparation of ionic change of mobility ratio
properties of ionic liquid
liquids/oil microemulsions with a
microemulsions. It is [78]. X
combination of nonionic surfactant/ionic
liquids/cyclohexane. The formation of the apparent that severalX
microemulsion and its core structure was
Ionic liquids are cost-
deter-mined by light scattering and small-
effective and commercially
angle neutron scattering (SANS) [60–
available [79]. X
62].X
During micellar flooding,
cosurfactants are used with
surfactants. Co-surfactants
It is important to know the phase behavior
are medium chain alcohols
of ionic liquid microemulsion systems. An
which are volatile in nature
interesting study on the phase behavior of
and pose an environmental
ionic liquid microemulsion was presented
risk. But ionic liquids have
by Logo et al. [63]. They stat-ed that strong cohe-sive forces which
microemulsions composed of ionic liquids enable them to form stable
form three phases and remain in equilibrium micelles without the need of
with upper and lower phase. It was reported additional cosurfactants
from other studies that hydrodynamic
diameter of ionic liquid-water [80,44]. X
microemulsion depends on the
concentration of the ionic liquid, not on Fig. 1. Ionic liquid microemulsion
They are usually non-
water content. On the other hand, the size phase changes with salinity.
flammable and have a wide
and morphology of ionic liquid droplet
range of solubility and
depend on water content and diameter of kinds of research on
microemulsion droplet is water content surfactant microemulsion miscibility [81–83]. X
dependent. Along with the unique properties systems are available and
of ionic liquids, the formation of ionic they have an impact on oil Some ionic liquids are less
liquid-oil microemulsion can be recovery by regulating their toxic according to the criteria
spontaneous by incorporation of
properties [58,71]. It is of the Glob-
hydrocarbon domains. In another work,
necessary to study the effect
Rodríguez-Escontrela et al. [64] conducted of the ionic liquid
ally Harmonized System
the phase behavior study of surface active microemulsion in oil
(GHS) or Classification
ionic liquid in oil and water mixture. Effect
recovery.X Labelling and Pack-aging
of sa-linity on phase behavior was
(CLP) regulation based on
examined in their work. It has been found
their noncorrosive properties
that three phase microemulsion is formed 6. Advantages of ionic
with a variation of salinity. It is well liquids and recyclability [84]. X
understood from this study that
microemulsions formed by ionic liquids
Ionic liquids have many Due to all the reasons
mentioned above, ionic liquids have been recover till 90% yield of
con-sidered as a potential solvent in a extra-heavy oil from
7. Limitations of ionic
petroleum refinery. Ionic liquids can have Canadian tar sands and could
liquids
successful applications not only in refinery be recycled till five times
but also in the recovery of bitumen from oil without noticeable loss of
sands. A Large amount of water and huge efficiency. Surface-active Ionic liquids have several
energy consumption occurred during the ionic liq-uids are very advantages in EOR
recovery of bitumen from oil sands. effective in dehydrating light applications and they have
Problems associated with crude oil oil, heavy and ultra-heavy good impacts in industrial
production and surface transporta-tion to crude oils. Microwave applications too. Again ionic
the terminal are mainly SARA precipitation, irradiation significantly liquids have some typical
the high viscosity of crude. Heavy and increases the efficiency of the serious issues when they
extra-heavy crude oil productions from process. Besides these consist of halogen-contain-
reservoirs and transport to terminals are applications, recently it has −
ing anions like [AlCl4] ,
considerably hampered by several prob- been explored that surface- − − −
lems related to oil production, precipitation active ionic liquids have [PF6] , [BF4] , [CF3SO3] or
−
of oil-water emulsion for-mation, and [(CF3SO2)2N] ) which cross
advanced uses in EOR [63].
the limit of greenness. HF
corrosion of pipelines. Painter et al. [22,23]A com-parison between ionic
and HCl are produced during
showed that several problems related to liquids and surfactants for
deg-radation of ionic liquids
heavy oil and extra heavy oil production their applications in oil
that consist of Cl and F
can be minimized by using ionic liquids. recovery has been provided in
+
halides. So, we should take
Even the ionic liquids like [Bmim] Table 3.X care of the properties of these
− + −
[CF3SO3] and [Bmmim] [BF4] could ionic liquids during synthesis.
It is
A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188
183

questionable. here that such ionic liquids

Table 3 (some of them are stated in
a long time.
Table 2) must be avoided in
Comparison between ionic liquids and surfactants in any research purpose for
oil recovery purpose. Toxicity
Some ionic liquids are less toxic appli-cation in CEOR as
Surfactants are considerably anions of the ionic liquids are
Properties not stable in the pres-ence of
Ionic liquids
Surfactants and environmentally friendly for
water and producing HF and
hazardous in nature. HCl in an autocatalytic
hydrolysis process. Another
limitation is impurities of
using in different applications as
ionic liquids. Impurities of
ionic liquids can render their
IFT effectiveness. Hence,
Some surface active ionic liquids
They can reduce IFT up to reported in the different literature
preparation of ionic liquids is
very crucial to protect the
mixing of impurity. It is
−2
can reduce IFT up to 10 mN/m. important to highlight here
−4 −3
10 –10 mN/m to show about the hazardous natures
[72,85].X of ionic liquids. As it is
it is necessary to enhance the mentioned in several kinds of
their effectiveness in EOR Dissolution literature that some ionic
Ionic liquids can dissolve even liquids can be considered as
Surfactants cannot dissolve green chemicals but again
surface activity of ionic liquids for Power
applications. some are highly hazardous.
gases like H2, CO, and CO2. They During selection and working
these gases.
with ionic liquids proper
application in EOR.
caution should be taken to
can be used even under
avoid any accident.X
Viscosity
The viscosity of some ionic liquids
In aqueous solution, they
supercritical CO2. So they may be
can be manipulated by variations 8. Influenced factors by
cannot produce higher ionic liquids in EOR
methods
in branching and higher viscosity considered in water alternating
viscosity. Ionic liquids can be used as a
potential candidate in EOR
can be expected. methods to influence the IFT,
gas flooding replacing water.
wettability, and adsorption. In
Stability
this section, we will dis-cuss
Some ionic liquids are stable over a the effect of ionic liquids in
Stability of surfactants at high IFT reduction, wettability
alteration, and adsorption.
long temperature range and can be
There are very few articles
temperature is always available on this topics. With
the help of these articles we
also important to mention will try to explain the effects
stored without decomposition for
of ionic liquids on the above-mentioned Hezave et al. [88,89] study, Rodríguez-Escontrela
factors and how can we regulate the et al. [44] conducted phase
reported similar re-sults
properties of ionic liquids to monitor the
regarding the surface behavior and IFT
factors. The main challenge is to modify the
activities of ionic liquids. measurement of n-dodecane-
structures of ionic liquids as well as
Ionic liquids can better work brine-
properties so that they will be effective for
in saline water due to trihexyltetradecylphosphoniu
oil recovery purpose.
tolerance power of high mbis(2,4,4-trimethylpentyl)
salinity envi-ronment. Mainly phosphinate microemulsion
8.1. Interfacial tension reduction when cationic ionic liquids system. The produce
are used in saline water, microemulsion and oil phase
negatively charged ions show IFT 0.02 mNm-1 which
As most of the surfactants are used in
neutralize the positive is quite desirable IFT in EOR.
chemical EOR methods to re-duce IFT for a
charges of cationic ionic For more reduction of IFT
desirable increase of capillary number, −4 −3 −1
liquids, and as a result, (~10 –10 mNm ), more
therefore, alterna-tive chemicals should
accumulation of ionic liquids screening of microemulsion
have also surface active properties. Some
molecules at the oil-water sys-tem is necessary. As a
surface active ionic liquids have similar
interface become easier to primary screening test of the
surface active properties as surfactants and
reduce the IFT. But it is in ionic liquids in EOR
are thus considered to be good candidates
con-trary to discuss the application lots of
for EOR applications. Some surface active
efficiency of the ionic liquids experimental studies are
ionic liquids are used to investigate their
to reduce the IFT be-tween needed. Since the prop-erties
surface ac-tivities by measuring the IFT
oil-water interfaces. As ionic of ionic liquids can be altered
between oil and ionic liquid solution.
liquids have unique by alternating the anions and
Benzagouta et al. [86] measured IFT properties in other cat-ions of ionic liquids, it is
between one Saudi reservoir oil and several applications and new in oil expected that new group of
ionic liquid solutions. They also compared recovery experiments as ionic liquids will be
the reduction of IFT with one nonionic alternatives of surfactants, developed for achieving
surfactant Triton-X and reported that ionic therefore, some authors have ultra-low IFT between oil-
liquid (Tetraalkylammonium sulfate) is taken this opportunity to water systems. In this
more active to reduce IFT than the sur- publish huge numbers of circumstance, it is strongly
factant. Later Bin-Dahbag et al. [87] literature on uses of ionic recommended to investigate
liquids in oil recov-ery. If we the en-hancement of surface
studied all those series of ionic liq-uids as
see properly, then it will be properties of ionic liquids.
listed in Table 3 to screen their surface clear that ionic liquids can
activities as well as ability to alter 0 Sakthivel et al. [43] ex-
only re-duce IFT up to 10 –
wettability of reservoir rock surface. The −1 tensively studied effects of
10 mN/m (in special cases ring size, alkyl chain length,
tested ionicX −2 −1
concentrations of ionic
10 mNm ) which is not
required IFT in CEOR by liquids and the nature of
liquids should be water soluble for cation and anions on surface
surfactant active agents [15].
measurement of IFT between oil and water tension and IFTs. The results
Another in-teresting study on of the surface tension and IFT
and for reduction of IFT between two
IFT investigation by surface measurements show the
phases. It can be sug-gested that the phase
active ionic liquid was made reduction of values but not
behavior of ionic liquid-water-oil system
by Rodríguez-Escontrela et desirable. The IFT between
should be conducted along with IFT
measurement as phase behavior is a crucial al. [90]. They synthesized oil and water phases is
screening criteria for the selection of ionic imidazolium-based surface expected to be reduced below
−1
liquids or surfactants in CEOR methods. active ionic liquids combined 1 mNm after addi-tion of
The measurement of IFT at different brine with an ace-tate counter ion surface active agents. But the
concentrations is important for finding out for application in EOR. The present study showed the
the optimum salinity of a system. Only experimental results on IFT reduc-tion of IFT above 1
lower and higher salinity test for IFT is not measurements between crude −1
mNm which is not a
enough for screening criteria. A series of oil and the surface active
desirable value in CEOR. It is
brine concentration should be used to ionic liquid show the
very important for selection
measure the IFT to cap-ture the optimum reduction of IFT in the range
of chemicals in the
salinity of oil-brine-ionic liquid system. As of 2–3 mNm−1 which is not
application of oil re-covery.
the critical micelle concentration (CMC) of in fact promising value in
Synergism of surfactant and
the surfactant or ionic liquid is affected, EOR. The combination with salt mixture is well known in
therefore, the effect of brine concentration salt/alkali lowers the IFT up
IFT re-duction. In a similar
on CMC is also important for screening −1 −1
to 10 mNm range. As a way, ionic liquids also show
study of the ionic liquid. Structural variation
result the efficiency of ionic synergistic effect with salt in
influences the re-duction of IFT between oil
the reduction of IFT and
and ionic liquid solution. The present study liquid to reduce IFT alone is
surface tension. The study
reported that ionic liquids with longer alkyl questionable. Properly
showed that with increasing
chain length of an ionic liq-uids' cation tend designed surface ac-tive ionic
NaCl concentration surface
to increase the capability of reducing IFT liquids are necessary for
due to high surface activity. Smit et al. and application in EOR. For tension and IFT decreaseX
further improvement of the
184 A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188

for EOR applications:X moderate oil-wet state. The

decrease of contact angle
even at 200,000 ppm concentration. But it is
from 110° to 70° in the
very interesting to know the optimum salt
presence of ionic liquids
concentration at which lowest IFT or
implies the effectiveness of
surface tension can be found. They further Surface activity improvement
their uses in oil recovery.
investigated the conductivity behaviors of of ionic liquids to reduce IFT
During wettability alteration,
all ionic liquids to acquire an idea about the
there must be a mechanism of
critical aggregation concen-trations of ionic
Stability of ionic liquids in change of oil-wet state to
liquids. The used ionic liquids showed in
harsh conditions of reservoirs water-wet state. Generally,
the aggrega-tion concentrations below 1000
interactions between oil, rock,
ppm. Hezave et al. [15,16,89,91] also and ionic liquid play the
studied the effects of ionic liquids on oil- major role in wettability
water IFT reduction. The work conducted in Stability in high salinity alteration pro-cess. It would
these articles is based on imidazolium and water environment in be an interesting study if
pyridinium based ionic liquids. They found reservoir conditions some experiments can be per-
that ionic liquids can reduce IFT b1 mN/m. formed in micromodel
These works show some better efficiency of devices with ionic liquids and
Low cost production of ionic
ionic liquids in the reduction of IFT in oil to mimic the sandstone
liquids for economic
different concentrations of NaCl. It may be reservoir as polysilicon
feasibility
stat-ed that imidazolium and pyridinium microfluidic devices. For
based ionic liquids are suitable candidates further test-ing of the
for IFT reduction in EOR. Again the same 8.2. Wettability alteration effectiveness of ionic liquids,
story can be repeat-ed here for the optimum Mohammed and Babadagli
salt concentration of the ionic liquid and
Due to the surface active [41] similarly studied the
salt mixture system which is most important
nature of ionic liquids, they wettability alteration by ionic
part of EOR chemical screen-ing for the
can also alter wettability of liquids for oil-wet limestone
application. Further study on optimum
reservoir rocks. Limited and water-wet sandstone
salinity should be conducted on ionic liquid
research works have been samples. It was found that
systems in the measurement of IFT between
con-ducted on wettability ionic liq-uids can effectively
oil and water. In addition, core flooding
alteration by ionic liquids for alter wettability of oil-wet
results show promising recov-ery by the
EOR. Recently Bin-Dahbag limestone and sandstone
ionic liquid in these works. Fig. 2 shows compared to other chemicals
et al. [86] studied the
the effect of NaCl con-centration variation like surfactants. Imidazolium
wettability alteration of Berea
on IFT reduction between crude oil and ionic liquids were used in this
sandstone samples by ionic
ionic liquids at different concentrations. study and it is confirmed that
liquids in addition to brine.
Other studies also showed that ionic liquids ionic liquids also show
Different concentrations of
are able to reduce IFT but its efficiency is maximum oil recovery rate as
ionic liquids were used and a
still questionable [43,92,93]. In spite of well as ultimate recovery at
decreasing trend of the
an optimum concentration in
this, there is still a lot of scopes to improve contact angle with a variation
the range of 0.5–1.0 wt%.
the ionic liquid devel-opment fields for of concentration was found,
further applications in oil recovery methods.which indicates the favor-able This study encouragesX
The fol-lowings are recommended to change of wettability towards
improve the field of ionic liquids research water-wet state from

Fig. 2. Effect of NaCl concentration on the IFT

reduction at the different ionic liquid
concentrations: a) 1250 ppm, b) 2500 and 5000
ppm. (Reproduced from [15] with

permission). X
A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188
185

chance of improvement of oil studied the influences of ionic

researchers to conduct further experiments
using ionic liquids, on car-bonate reservoir,
heavy oil recovery. The Alberta heavy oil
reservoirs re-covery using chemical
methods is a challenging job. Thermal
methods are extensively used for these
types of reservoirs. Enhanced hot solvent
injection methods for heavy oil recovery are
very important issues. If ionic liquids can be
used in these heavy oil reservoirs during
thermal in-jection then there may be a
production. Again this is a
proposing and future thought
of a project that can be im-
plemented in Alberta heavy
oil reservoir depending on the
project cost and oil price.
Furthermore, the active and
high temperature stable ionic
liquids are necessary to
implement the idea in thermal
oil recovery. Cao et al. [39]
liquids on contact angle
behav-ior on oil-wet
carbonate rock. They found
that ionic liquids are effective
to alter the rock wettability
towards oil-wet state by
reducing the oil-water contact
angle. Fig. 3 shows that
ionic liquids can change the
con-tact angle along with the
same path of other wettability
alteration chemicals. As ionic liquids have
different charges, they have different at-
traction and repulsion with rock surfaces.
Ionic liquids-cations are more favorable to
be used in carbonate reservoirs whereas
ionic liquids-an-ions are more suitable in a
sandstone reservoir. Mohsenzadeh et al.
[47] also measured the contact angle
between crude oil and analogue of ionic
liquids (Deep Eutectic Solvents). It was
found that ionic liquid analogues are
effective to change the wettability of the
rock by changing contact angle values. The surfaces. The adsorption
concentration of the applied chemical on
wet-tability alteration is crucial for oil
recovery. The present study showed that
low concentration ~ 5 vol% has low effect different types of reservoir
on wettability alteration. Again 25 vol% has rocks during the chemical
the minor effect on wettability alteration. injection in EOR methods. A
For this type of solvent, higher
concentration may be required for the
expected change in wettability controlled by Bin-Dahbag et al. [87]
the nature of the ionic liquid ana-logue. As
the solvent is an analogue of the ionic
liquid, therefore, it can-not work in low
concentration. This observation again
proves that alteration of anions and cations
can noticeably change the ionic liquid
properties as well as their effectiveness. So,
the proper design of ionic liquid for
application in EOR is utmost interests to the
researchers. Al-though the applications of
ionic liquids in EOR are under research in
lab-oratory scale, it is expected they will
occupy the alternative positions of
surfactants in EOR applications.X
8.3. Adsorption
Adsorption of the chemical in EOR hinders adsorption of ionic liquid on
the economic feasibility of the process. So, reservoir rock. In this case,
it is necessary to consider the adsorption
capability of a chemical in EOR method. tures of ionic liquids which
Depending on the charges of ionic liquids it will offer a probable
is possible to adsorb onto the rock surface. (feasible) solution for the
But it is also apparent that different ionic problem. Sometimes it is also
liquids have different adsorption capabilitiesimportant to monitor the pH
onto
Fig. 3. Effects of test solution phase
change on the contact angle of
Grossmont carbonate. (Reproduced
from [39] with permission.)X
different types of rock
properties of ionic liquids
make them undergo for
adsorption preferences for
Few experimental works are
available in the literature.
studied the adsorption of
Ammoeng 102 ionic
solutions (ionic liquids-
anionic) onto kaolinite clays
(positively surface charges).
It was found that
considerable adsorption takes
place onto kaolinite sur-face
at high salinity rather than
low salinity. Therefore,
salinity has a strong effect on
the ionic liquid adsorption
onto the rock surface. If
adsorption takes place
maximum at high salinity,
then ionic liquids can-not
work properly under high
salinity reservoir
environment. Therefore,
alternative paths should be
followed to overcome high
we can think about the struc-
of the solution to reduce
adsorption onto the rock
surface. Based on the ionic
liquids nature and rock
surface charge pH can be
monitored to find out the best
solution to reduce adsorption.
In another work Hezave et al.
[89] reported that adsorption
can be controlled by
regulating the brine salinity.
It was noticed from the
experimental study that
adsorp-tion of ionic liquids is
low in the presence of
formation brine and oil. The
proposed mechanism behind
this phenomenon is the
hindrance of ionic liquid
movement towards to rock
surface due to the coverage of
pore surface by oil and
formation brine. As a result, it
follows the mass transfer
phenomenon which leads to
the diffusion of ionic liquids
into oil and formation brine
phases followed by
partitioning. This partitioning
of ionic liquids can ease the
formation of the
microemulsion. Once the
microemulsion is formed, the
IFT of the sys-tems is
reduced and oil mobilizes
easily. As ionic liquids have
ionic heads, therefore, the
adsorption can be controlled
to select the right ionic
liquids for a particular
reservoir. Criticism is coming
into the dis-cussion regarding
the adsorption of ionic liquids
onto the rock surface.
Surfactant adsorption is an
influencing factor for oil
recovery from high-salinity
and high-temperature
reservoirs [48,94–97]. It is
neces-sary to control ionic
liquids adsorption onto
reservoir rock as adsorption
also hampers micellization.
More studies are required to
understand the fundamental
of adsorption behaviors of
ionic liquids onto reservoir
rock surface during fluid
injection in EOR method.X
9. Mechanism and oil
recovery performances of
ionic liquids
As of now, there is no well-
established fundamental
mechanism of oil recovery by
ionic liquids. The proposed
mechanism of ionic liquid in
oil recovery can be stated as
the addition of ionic liquids
to the oil phase there may be
an attraction at the interface
of crude oil and water or
crude oil-rock surface (when
rock, crude oil, and ionic
liquids are present together)
due to the chargeable
interaction of heteroatom of
crude oil-ionic liquid and
rock surface. Due to this
interaction among them, the
reduction of IFT takes place
and consequently helping the
oil to get mobilized easily
through pore throats.
Some core flooding
laboratory experiments are
discussed here to show the
effective performances of
ionic liquids on oil recovery.
As discussed early, depending
on ionic liquids' chain length,
they have dif-ferent effects on
interfacial properties as well
as oil recovery. Recently
Sakthivel et al. [42] reported that long recovery by ionic liquid then microemulsion, although
the Bansal, Shah, O′ Connell some literature says that
chain ionic liquids are more effec-tive than
(BSO) equation for cosurfactant is not necessary
short chain ionic liquids in oil recovery
representing microemulsion for the preparation of ionic
process. In this circum-stance, there is a
systems may be applied here liquids microemulsion. This
correlation between water solubilization
after proper investigation. In sub-ject should be clarified
capacity of microemulsions formed by any
general, cosurfactants are again, with a better
surface active agent and alkyl chain length
required for the formation of understanding of theX
of the surface active agent. If we consider
a transparent, high effective
the formation of the microemulsion in oil
186 A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188
mechanism and perfor- From the point of view of the
mances, it is believed that upstream petroleum oper-
spontaneous formation of ionic liquids
there are many open scopes ation, the main challenge is to
microemulsions for application on EOR.
to focus on the modify the structures of ionic
They studied a series of ionic liquids with
liquids to make them
different chain length and found an order of
effective in CEOR. Another
oil recovery as 3-hydroxypropylammonium
challenging factor is to
trifluoroacetate N tripropylammonium
synthe-size cost-effective
sulfate N triethylammonium sulfate N
ionic liquids for applications
diethylammonium sulfate. They extensively
in CEOR purpose. There are
studied the oil re-covery by a different
several available surfactants
combination of ionic liquids, polymer, and
that are active in reducing
surfac-tants for comparison of different
IFT as well as changing the
slugs. The main mechanism of oil recovery
reservoir rock surface
by different (various) types of ionic liquids
wettability, but expensive and
depends on their chain length. The EOR
cannot work properly under
with increasing alkyl chain length of ionic
high-temperature and high-
liquids can be described based on higher
salinity reser-voir conditions.
van der Waals force of attraction with crude
So, cost-effective, high-
oil [42,88,93].X salinity resistant and
thermally stable ionic liquids
are highly demandable for
Mohsenzadeh et al. [47] studied the oil EOR purpose.
recovery performances by deep eutectic
solvents (DES), which are analogues of
The viscosity of the injected
ionic liquids. It is reported that oil recovery
fluid in EOR, by chemical
is maximum at an optimum concentration
injection, is an important
and even higher oil recovery was observed
matter. The modification of
with increasing concentra-tion of DES.
the viscosity of the injected
Therefore, it is confirmed that low
fluid is necessary to enhance
concentration of DES can effectively
the sweep efficiency.
recover the high amount of oil. Again Bin-
Recently, surface active
Dahbag et al. [87] conducted core flooding polymers have attracted the
experiments with ionic liquids and report-ed attentions of upstream
improved ultimate oil recovery of 60–70% petroleum re-searchers due to
in secondary mode at ini-tial oil saturation. the combined effects of these
Another core flooding study was provided polymers in IFT reduction as
by Pereira et al. [7] and typical oil recovery well as increasing the
Fig. 4. Additional oil recovery viscosity of the injected fluid.
profile by ionic liquids, brine and petrostep (AOR) by different flooding agents
So, depending on the present
chemical is shown in Fig. 4. They reported at 40 °C with: (▲) [C2mim][OTs]
(2 wt% ionic liquid); (●) brine scenario, it can be targeted as
that the injection of a 2 wt% ionic liquids solution (2 wt%); (■) Petrostep (0.15 a future challenge to synthe-
solution can produce a twofold increase of size of such ionic liquids
wt%). (Reproduced from [7] with
oil re-covery than a brine solution alone. which have both surface
From the present discussion, it is clear that permission.)X active and viscous properties.
ionic liquids can act as potentially injected
fluid in chemical EOR methods. Now more
Different studies already
experiments are required to make the final study of ionic liquid
proved that ionic liquids are
decision about the efficiency of ionic liquids application in oil recovery.
in oil recovery as a sound alternative agent Further visual observa-tion of potential can-didates for CO2
in harsh reservoir condition. Recently oil recovery process by ionic capturing and sequestration.
liquid should be investigated It is important to take care of
Joonaki et al. [46] studied the core flooding to get a better understanding the issue for making suitable
experiments with a newly synthesized of the mechanism and ionic liquids that can work
surface active ionic liquid to investigate the process. under reser-voir condition to
oil recovery performances of this candidate. the enhance oil recovery as
Surprising results were seen in the case of
this new chemical: If the chemical is used 10. Future challenges of well as reduce the CO2
from the beginning of the oil recovery, the EOR by ionic liquids emission. It is a great
production is ~26% OOIP and if it is challenge for the oil industry
applied after water flooding, then it can to use a chemical that can
Applications of ionic liquids
recover 10% OOIP. In this case, it may be in the oil recovery method enhance the oil recovery as
stated that during these two processes have just been started, to well as reduce the CO2
countercurrent and concurrent flow is examine their effectiveness emission to make the process
working in a different way. When ionic through some experimental environmentally friendly. In
liquid is used from the beginning then works. A few laboratory thermal oil recovery, CO2
countercurrent flow acts as a major factor, studies have shown some emission is a major problem.
therefore, oil recovery is high. On the other promising results in IFT Researchers and petroleum
hand when the ionic liquid is applied after reduction, wettability engineers are always looking
water flooding then concurrent flow is alteration, adsorption study, for a solution to reduce CO2
dominant over other flow and as a re-sult and oil recovery. More
emission in Alberta heavy oil
low recovery occurs.X experimental works,
recovery by thermal method.
however, are necessary, in
It might be thought that ionic
order to take a proper
liquids can help to offer a
decision about the major
solution in near future with
From the above discussion on oil recovery application parts of ionic improved technol-ogy by
liquids in EOR methods.
injecting ionic liquids during thermal surface. Current research methods as alternatives.
method to capture the pro-duced CO2 and works, to find out suitable
effective ionic liquids for
store for future use in CO2 EOR method. As EOR application in reservoir From the reported laboratory
it is considered that ionic liquids are results, it is again confirmed
conditions, are still in
capable of capturing CO2, we can expect progress. Depending on their that ionic liquids can act as
potential chemicals in EOR
something exceptional target with ionic properties and flex-ible
techniques. They can be
liquids in near future although the capability structures, it is assumed that
synthesized in different ways
is limited. ionic liquids are promising
to alter their structures and
chemical agents in EOR
the synthe-sized ionic liquids
method. It is believed that
11. Conclusions have different active
ionic liquids, in most of the
properties, which will help to
cases, follow the same
work in oil recovery even at
In this article, an overview of the current mechanism path of surfactant
harsh conditions of
research activities on ionic liquids and their in EOR. The unique
reservoirs. Because of these
applications in EOR has been documented properties of ionic liquids
unique properties of ionic
with differ-ent aspects such as IFT would help them to occupy
liquids deems to be positive
reduction, wettability alteration, additional the places of other chemicals
and more
oil recovery and adsorption on the rock like surfactants in EOR
A. Bera, H. Belhaj / Journal of Molecular Liquids 224 (2016) 177–188
187

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