Accepted Manuscript

Title: Study on evaluating potential of Imidazolium ionic

liquids as a surfactant in Enhanced Oil Recovery

Author: Shilpa K. Nandwani Naved I. Malek V.N. Lad

Mousumi Chakraborty Smita Gupta

PII: S0927-7757(16)31080-9
DOI: http://dx.doi.org/doi:10.1016/j.colsurfa.2016.12.037
Reference: COLSUA 21244

To appear in: Colloids and Surfaces A: Physicochem. Eng. Aspects

Received date: 28-10-2016

Revised date: 17-12-2016
Accepted date: 21-12-2016

Please cite this article as: Shilpa K.Nandwani, Naved I.Malek, V.N.Lad, Mousumi
Chakraborty, Smita Gupta, Study on evaluating potential of Imidazolium ionic liquids
as a surfactant in Enhanced Oil Recovery, Colloids and Surfaces A: Physicochemical
and Engineering Aspects http://dx.doi.org/10.1016/j.colsurfa.2016.12.037

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Study on evaluating potential of Imidazolium ionic liquids as a surfactant in Enhanced
Oil Recovery

Shilpa K. Nandwania, Naved I. Malekb, V. N. Lada, Mousumi Chakrabortya,*, Smita Guptaa,*

a
Department of Chemical Engineering, bDepartment of Applied Chemistry
Sardar Vallabhbhai National Institute of Technology Surat – 395 007, Gujarat, India

* Corresponding authors. Tel.: +912612201610; fax: +91 261 2227334 (Mousumi

Chakraborty), Tel.: +912612201717; fax: +91 261 2227334 (Smita Gupta).
E-mail addresses: mch@ched.svnit.ac.in (Mousumi Chakraborty), g.smita@ched.svnit.ac.in
(Smita Gupta)

GRAPHICAL ABSTRACT

1
Highlights

 Potential of the ionic liquid, C16mimBr, in reducing interfacial tension between oil
and aqueous system was studied.
 C16mimBr was found to have higher potential than conventional cationic surfactant,
CTAB, by significantly reducing IFT even under harsh reservoir conditions.
 Improved oil recovery rates when using C16mimBr as surfactants in a CEOR process
were attributed to the formation of oil in water emulsions.
 Occurrence of emulsions was confirmed by performing video microscopy of fluid
flowing through microchannels, modeled as porous structures present in the core.

Abstract

Enhanced oil recovery is a tertiary method for recovering oil trapped in porous rock of the
reservoir. This oil becomes trapped in porous media because of capillary forces. The
reduction of these forces by surfactants is an important aspect of enhanced oil recovery. The
development of ionic liquid -based surfactants has gained significant interest in their use as
cationic surfactants in analytical methods and separations. In the current study, functionality
of long chain imidazolium ionic liquids as surfactants have been investigated by measuring,
dynamic interfacial tension of water/ oil system and their ability to reduce IFT under harsh
conditions of salinity and temperature. In the present study, an advantage of 1-hexadecyl-3-
methyl imidazolium bromide (C16mimBr) over traditional cationic surfactant (CTAB) has
been highlighted. The efficiency of both (C16mimBr & CTAB) in recovering additional oil
when used in an EOR process has been found out by conducting lab-scale core flooding
experiments. Also, small Poly (dimethylsiloxane), (PDMS) microchannels have been
prepared and moduled as oil filled porous structures in the reservoir. Microscopic images of
surfactant solutions flowing through these channels have been recorded to find out whether
they form emulsions while flowing. The experiments revealed that C16mimBr is more
efficient in reducing interfacial tension between water/ oil system and thus recovering more
entrapped oil than traditional cationic surfactant CTAB. The results obtained here reflect high
interfacial activity, high oil solubility due to the formation of emulsions and stability under
harsh reservoir conditions for the IL in consideration.

Keywords: Interfacial tension, Surfactant flooding, Imidazolium ionic liquids, Emulsion.

2
___________________________________________________________________________
1. Introduction

The percentage of oil remaining in a reservoir varies from field to field. However many
field case studies have reported that after primary and secondary-oil recovery processes about
50 to 80% of original oil in place (OOIP) would be still left behind as residual oil trapped in
the pores of the reservoir rock [1-4]. The percentage of residual oil left behind depends
largely on the type of hydrocarbons (light oil, heavy oil or tar sands). Enhanced oil recovery
(EOR) is a propitious method for recovering significant amount of this residual oil. EOR is
oil recovery by the injection of materials not normally present in the reservoir viz., gases or
chemicals and/or thermal energy. Thermal, miscible, and chemical enhanced oil recoveries
(CEOR) are three main types of EOR techniques. Crude oil prices and cost effectiveness are
the two main factors governing EOR processes. The majority of EOR processes used today
were first intoduced in the early 1970’s when the oil prices were high and the interest
gradually declined in the late 1980s when the oil price dropped [5].

Chemical EOR methods popularized in the 1980’s, most of them in sandstone reservoirs.
Chemical methods involve process wherein a chemical formulation capable enough in
reducing mobility ratio and/or increasing capillary number is injected in the reservoir as
displacing fluid. The different chemicals usually employed are polymers, surfactants, low
salinity water and alkalines. The most renowned ones among the chemical EOR methods are
polymer flooding followed by microemulsion-polymer flooding and alkaline-surfactant-
polymer flooding [5]. Therefore and despite the volatility of oil prices, chemical EOR is fast
gaining attention due to its well-deserved option for almost complete oil field extraction.
Recent developments in chemical EOR, especially in the field of surfactant flooding, have
made even further developments making the processes comparatively safer, cleaner and more
cost efficient.

Surfactants are considered as good candidates for EOR since years because they can
significantly lower the interfacial tensions and alter wetting properties [4]. Surfactant
flooding systems are basically classified into, low-surfactant concentration systems and high-
surfactant concentration systems. At low-surfactant concentration (0.1 - 0.2 wt %), system
appears to be a two phase system, whereas at high surfactant concentration systems (around
4-8 wt % surfactant concentration) a middle phase microemulsion exists in equilibrium with
excess oil and brine [6]. One of the main challenges in chemical EOR by surfactant flooding

3
is the loss of surfactant due to adsorption on formation rocks and adsorption of such toxic
substances on the reservoir rock. In addition high cost of surfactants makes the entire process
uneconomical. In light of these serious drawbacks there are some additional issues regarding
the functionality of conventional surfactants being used in an EOR process. Most of the ionic
as well as nonionic surfactants loose stability at high salinity. It is thus clear that vast amount
of work needs to be done in the area of designing specific surfactants which are able to
tolerate harsh reservoir conditions, adsorb less on the reservoir rock and are less toxic, thus
optimizing the entire process [7].
Petroleum industry is among one of the energy suppliers to the world and in the last
decades it has shown profound interest towards transforming into a more clean and “green
industry” around the world. Ionic liquids are substances that consist of ions having weak
bonds amongst themselves. Most of the ionic liquids have melting points below 100⁰C
however some of them are in a liquid state at room temperature. Ionic liquids are receiving
importance due to a number of characteristics they own, namely an extremely low vapor
pressure, low melting temperatures, wide liquid temperature range, good chemical and
thermal stabilities and the ability of being doctored for a specific application by switching
ions or designing specific functionalities in their structures [8]. The amphiphilic nature of
ionic liquids and their ability to self organize in solutions opens additional perspectives for
applications in chemical synthesis, catalysis, electrochemistry, extraction and
chromatography, in the synthesis of polymer materials, nanomaterials etc [9]. For their
versatility and properties, it is found from literature that ionic liquids have vast potential for
different application in petroleum industry such as to inhibit the deposition of asphaltenes and
paraffins [10], in crude oil dehydration and desalting [11], refining [12], as well as catalysts
and solvents for petrochemical processes [13, 14]. Ionic liquids can also replace organic
surfactant in breaking water/oil emulsions in oil refining process [15]. Micelle formation of
ionic liquid solution enables them to act as emulsifying agents and make them capable
enough to solubilise and disperse otherwise non-compatible materials like oil.

More recently, ionic liquids have received interests as a green alternative to conventional
emulsifying agents for EOR purposes. Many researchers have reported that ionic liquids are
capable of decreasing interfacial tension between crude oil and formation water. Also they
are more effective in high saline formation brine even at very low concentration of 100 ppm
and have minor adsorption in the rock surface [7, 16-23]. In a recent study, Iago Rodriguez et
al. [22], reported about the interfacial properties of the ionic liquid, 1-dodecyl-3-methyl

4
imidazolium acetate (C12mimOAc) for enhanced oil recovery. The effect of different
variables, namely the concentration of ionic liquid, electrolytes (NaCl) and alkalis (NaOH,
Na2CO3), and temperature had been analyzed. They found significant lowering of interfacial
tension and stability of ionic liquid under harsh reservoir conditions [22]. Most of the efforts
on evaluating ionic liquids as suitable alternatives of traditional surfactants in EOR process
focus on the imidazolium family of ionic liquids. Imidazolium ionic liquids behave like
typical cationic surfactants in that their aggregation behaviour is similar to that of
alkyltrimethylammonium salts (CnTAX) [9].

Based on these findings, in the present work surface activity of some long chain
imidazoliums, 1-alkyl-3-methylimidazolium bromides (CnmimBr (n = 12, 14, 16)) has been
investigated. The imidazolium ionic liquid which reduces the interfacial tension (IFT)
between oil and surfactant solution the most, was then chosen for further study viz.,
C16mimBr. The dynamic interfacial tensions between aqueous solution of the C16mimBr and
paraffin liquid light oil (henceforth mentioned as oil), under harsh reservoir conditions has
been evaluated. On this basis, efficiency of C16mimBr in recovering residual oil has been
examined by carrying out lab-scale core flooding experiments. Although much research has
been done in the past few years where scientists have tried to evaluate the amphiphilic
character of different ionic liquids and its application in oil recovery, it is rare that a direct
comparison of surface active ionic liquids had been made with traditional surfactants. Hence
in the present study, the potential of C16mimBr to act like a surfactant in an EOR process was
evaluated and was then compared with a traditional cationic surfactant, Cetyl
trimethylammonium bromide (CTAB) for the first time for enhanced oil recovery. Further,
to confirm formation of emulsions different surfactant solutions were flooded through small
Poly(dimethylsiloxane) PDMS microchannels already containing oil. These microchannels
have been moduled as oil filled porous structures in the reservoir.

2. Experimental

2.1 Materials used

Paraffin liquid light oil (Finar Chemicals) was used as the oil phase. Sodium chloride
(99%), Cetyl trimethylammonium bromide (CTAB) (99%) was purchased from Sigma-
Aldrich (India). Three long-chain imidazolium-based ionic liquids, 1-alkyl-3-
methylimidazolium bromides, C12mimBr, C14mimBr and C16mimBr, were prepared and
purified as mentioned elsewhere [24]. Aqueous solutions of the ionic liquids were prepared

5
by weighing on an analytical balance in degassed Millipore-grade water. Sand (50 mesh size)
used in the sand pack column was purchased from Sunrise Glass Factory, India. Iso-propanol
(Finar Chemicals Ltd.,India) was used as micro-channel swelling agent.

2.2 Experimental technique

2.2.1 Interfacial/ surface tension measurements:

In the present study interfacial tension (both static and dynamic) between oil phase and
brine phase was measured using a KRUSS-T9 Tensiometer (Germany), (Du-Nuoy ring
method) under atmospheric pressure. The platinum ring was cleaned and flame-dried before
each measurement. In all cases, more than three successive measurements were carried out.

2.2.2 Droplet size distribution analysis and stability of microemulsion

Different ratios of oil and surfactant solutions were homogenized using an IKA
ULTRA-TURRAX T-25 homogenizer for 5 mins at a speed of 6500 rpm. A sample of the
microemulsion phase was then extracted using a micro-pipette. Emulsion size distribution
measurements were performed using laser diffraction method of Zetasizer Ver. 6.00 (Malvern
Instruments Ltd., Worcestershire, UK). The physical stability of the blends was analyzed on
scanning the sample by light rays of 880 nm wavelength using Turbiscan classic MA 2000
(Formulaction, France). All the experiments were conducted at 298 K.

2.2.3 Sand pack column assays

Two types of vertical sand pack columns were used to perform the EOR tests in this
work. The large scale setup was an acrylic column vertically placed (FIG. 1). The dimensions
of both the setups are given in TABLE 1.

2.2.4 Method of preparing microchannels

PDMS Sylgard 184 (containing silicon elastomer and curing agent, Dow Corning,
Midland, USA) was used for the fabrication of the microchannels as per the method
elaborated in detail by YueFei et al. [25], Ralekar (S. Ralekar, M. Tech. Dissertation, Sardar
Vallabhbhai National Institute of Technology-Surat, India, 2015) and Lad and Ralekar [26].
Conceptually, the silicon elastomer base and curing agent were mixed in the ratio 10:1,
followed by pouring the mixture in the moulds. Moulds were also prepared by using small

6
aluminum containers, wires, micropipette tips, sealing agent (Resibond-SL330, Bondtite,
India) as detailed therein [26]. Curing at 65˚C, followed by de-moulding and swelling in iso-
propyl alcohol as per the protocol [26] resulted in the microchannels of 384 µm diameter.

The microchannel was fed at constant flow rates through accurately controlled pumping
using a syringe pump NE-4000 (New Era Pump Systems Inc., USA). Firstly, oil was flown
in the channel at a constant flow rate of 0.5ml/min, following which different surfactant
solutions (yellow coloured due to addition of methyl orange dye) were passed through the
micro-channel at the same flow rate. An inverted microscope Nikon Eclipse TS100 (Japan)
equipped with a microscopic camera DS-Fi2 (Nikon, Japan) was used to observe formation of
emulsion inside miniature channels. Microscopic images were analysed by NIS element
documentation 4.3 microscope (Nikon, Japan) supported software (FIG. 2).

3. Results and discussions

3.1 Aggregation in water

First, the aggregation behaviour of three ionic liquids, CnmimBr (n = 12, 14, 16) in
water was evaluated by means of surface tension (Ɣ). Surface tension was measured for
different concentrations at 298 K and results are presented in FIG. 3.

At very low surfactant concentrations, the dissolved surfactant molecules are dispersed
as monomers. When surfactant quantity increased to a critical concentration called the critical
micelle concentration (CMC) the molecules starts to aggregate and forms micelles. After
CMC of the surfactant in an aqueous solution is reached there is no appreciable change in the
surface tension and it almost remains constant [27]. For each ionic liquid, the surface tension
progressively decreased with the increase in the ionic liquid concentration up to a plateau
region, above which a nearly constant value (Ɣ CMC) was obtained. Absence of a minimum
around the breakpoint confirms the high purities of these long-chain imidazolium ionic
liquids.

From the surface tension plot, other important parameters, i.e., the effectiveness of
surface tension reduction, ΠCMC and the surface excess concentration of surfactant at
saturation, Γmax were calculated. The values obtained for all these properties are presented in
TABLE 2 together with literature values [28, 29] for the same ionic liquids.

7
 From TABLE 2, it is evident that the CMC values decrease in the order C12mimBr
>C14mimBr >C16mimBr, which is in accordance with the literature reported [28, 29]. A
reason for this is increase in hydrophobicity due to elongation of hydrocarbon chain, thus
favouring micelle formation. Thus a larger hydrophobic domain would result in a lower CMC
[29]. When compared with traditional cationic surfactants having the same hydrocarbon chain
length the CMC values for [Cnmim]X salts are lower than for CnTAX with the same n value
[28,30], for e.g. CTAB had a CMC of 0.89mM [31] compared to 0.57mM of C16mimBr
presented in this work. A lower CMC of imidazolium ionic liquids as compared to
conventional cationic surfactants of the same chain length implies that the less polar methyl
imidazolium head group makes micelle formation energetically more favourable. From the
above study it is observed that C16mimBr is superior to, or at least comparable to, traditional
cationic surfactant CTAB in their capability for micelle formation.

3.2 Effect of Ionic Liquid on Interfacial tension (IFT) in paraffin oil /water and paraffin
oil /brine solution systems

The effect of ionic liquid concentration on the IFT between ionic liquid solution in
distilled water/brine water and paraffin oil were investigated (FIG.4).The results revealed that
the measured IFT for C12mimBr, C14mimBr and C16mimBr decreased from 43.97 mN/m to
9.1mN/m, 7.2 mN/m and 4.7 mN/m respectively as the concentration of ionic liquid
increased in distilled water and above the CMC, no decrease in IFT was observed (Figure
inset). It was also observed that there is a sharp reduction in CMC, around 500 ppm for
C14mimBr and around 250 ppm for C16mimBr. It means, as the length of the alkyl chain
increased the capability of the ionic liquid to reduce the IFT increased. This might be due to
strong adsorption at the interface of surfactants with higher alkyl chain length. As a
consequence, even a small amount of surfactant arriving at the interface causes a large
decrease in the IFT. Heazve et al. [20] in their work also observed a similar behaviour and
thus concluded that as the length of the chain increases the capability of the ionic liquid to
reduce the IFT increases, longer tails are more effective at low concentrations; that is, less
surfactant is needed to achieve the same IFT.

The salinity of the displacing fluid has a strong influence on the oil/aqueous systems
interfacial tension. For this reason, various experiments were carried out for 1-Alkyl-3-
methylimidazolium bromides ((CnmimBr) with n = 12, 14, 16) at a constant NaCl
concentration (3 wt %), FIG. 4.

8
 The results revealed that under same operating conditions the measured IFT for
C12mimBr decreased slightly from 9.1 mN/m (distilled water) to 8.7 mN/m (brine water), 7.2
mN/m (distilled water) to 5.9 mN/m (brine water) for C14mimBr, while the IFT for C16mimBr
experienced significant reduction from 4.7 mN/m (distilled water) to 3.9 mN/m (brine water).
From FIG. 4 it is clear that the presence of ion not only increased the strength of ionic liquid
to reduce the IFT but also lowered the CMC for all the three ionic liquids. It is worth
mentioning that CMC of C16mimBr reduced from 250 ppm to about 100 ppm. Similar results
were obtained by Heazve et al [20], as they measured the IFT between crude oil and four
different ionic liquid solutions, C12mimCl, C8mimCl, C12PyCl and C8PyCl in the presence
and absence of salinity.

The effect of change in concentration of C16mimBr on IFT between oil and brine
solution (varying salinity from 0 ppm to 30000ppm ~ 3 wt %) was studied. It was observed
that as the salinity increased the counter-ions (Cl-) available for neutralizing the charge of
surfaces increased and decreased CMC. It was found that at 3 wt %salinity, the CMC had
reduced to about 100 ppm. Hence further studies were limited to C16mimBr and a traditional
cationic surfactant having the same hydrocarbon chain length CTAB.

3.3 Comparison of C16mimBr with CTAB in reducing IFT under high salinity conditions.

Anionic surfactants have a negative headgroup and get less adsorbed on the sandstone
rocks (surface charge of sand being negative). Hence are most widely used in chemical EOR
processes. However, anionic surfactants cannot render ultralow interfacial tension under high
salinity conditions. In a recent study Zhao et al [32], observed such antagonism between
inorganic salt and Dodec-MNS surfactant (anionic). Cationic surfactants have a positive
headgroup and get strongly adsorbed in sandstone rocks. They are generally not used in
sandstone reservoirs, but can be used in carbonate rocks for recovering residual trapped in the
reservoir. In recent investigation, it has been proved that cationic surfactants like CTAB
performed better than anionic surfactants in altering the wettability of the carbonate rock to a
more water wet [33]. As mentioned earlier, imidazolium ionic liquids behave like typical
cationic surfactants in that their aggregation behaviour is similar to that of
alkyltrimethylammonium salts. Hence when evaluating efficiency of C16mimBr in reducing
IFT, it was compared with a conventional cationic surfactant having the same hydrocarbon
chain length and same anion type Br, CTAB. The results obtained are shown in FIG. 5.

9
As seen in FIG. 5, C16mimBr was found to be more efficient in reducing interfacial tension
(3.8mN/m) between oil and surfactant solution systems under high salinity conditions. From
FIG. 5 it is seen that CTAB showed a larger IFT (7.7mN/m) under same salinity conditions.
Thus, the obtained results suggest C16mimBr as a novel candidate for the chemical EOR
processes dealing with the harsh conditions of salinity.

3.4 The Dynamic Interfacial Tension (DIFT)

Once the displacing fluid is injected in the reservoir, the two immiscible fluids generate
a new interface. However the equilibrium interfacial tension is not instantly reached.
Equilibrium interfacial tension is reached only after the surfactant molecules from the
displacing fluid diffuse to the newly generated interfacial layer, get adsorbed and further
orient themselves. These steps are characterized by dynamic interfacial tension (DIFT).

In this stage, the effect of NaCl concentrations (0.2- 3 wt %) on the DIFT of the IL/ oil
system were evaluated at a constant concentration of the C16mimBr (0.01 wt %). FIG. 6
shows that as NaCl concentration in the IL solution increased the DIFT reduced. It was seen
that for the IL solution, the DIFT reaches its equilibrium value in less than 15 mins even
under high salinity conditions.

Zhao et al. [32] reported that with increasing inorganic salt mass concentration, the time
required for the anionic surfactants DIFT to reach the ultimate value increases. It was
observed that IFT between oil and IL solution almost remained constant with time at a given
brine concentration (0.5 wt % NaCl-3.5 wt% NaCl). Nevertheless, the profiles of the dynamic
interfacial tension were different for different salinities. Equilibrium interfacial tension
stabilized around 7.54 mN/m, when NaCl concentration was set to 0.2 – 0.5 wt %, and
stabilized around 6.08- 5.84 mN/ m for NaCl concentrations in the mentioned range 1.5–3.5
wt %. A similar behaviour was reported, wherein increasing NaCl concentration decreased
the interfacial tension, however showed a limiting effect as above for 1-dodecyl pyridinium
chloride and 1-dodecyl-3-methylimidazolium acetate at much higher NaCl concentrations
[20, 22].

In order to test the effect of temperature on the DIFT between oil and IL soution,
aqueous solutions of the surfactant ILs were prepared in brine (3wt % NaCl) and a series of
experiments were carried out at four different temperatures. The results obtained are shown in

10
FIG. 6 (inset). It is seen that an increase in temperature led to increase in DIFT. An
explanation to this behaviour might be that as the temperature increases viscosity of oil
decreases. The resistance to mass transfer and surfactant diffusion in the oil phase lowers and
above the phase inversion temperature (PIT) emulsion inversion takes place. However, the
time required for the surfactant to reach equilibrium remains the same between temperatures
298 K-333 K. This behaviour with temperature was also found in literature for other ionic
liquids [18-23]. Heazve et al. [18] attributed this behaviour of imidazolium ionic liquids to
the cationic head which is more lipophilic than the cationic head of conventional surfactants.

3.5 Size Distribution of Emulsion Droplet and stability study

Lowering interfacial tension with surfactants leads to the formation of emulsions and
microemulsions. High oil solubilisation is one of the key characteristic of surfactant used in
enhanced oil recovery process. In other words, micelles in the aqueous phase should be able
to solubilise oil from the hydrocarbon phase, thus forming emulsions. In this section the size
of emulsion formed when the IL solution and oil are homogenized is determined using
dynamic light scattering technique.

The system under study being a low surfactant concentration system of surfactant
flooding, the concentration of C16mimBr was varied from 0.1 wt% - 0.5 wt% in brine (3 wt%
NaCl) solution.The reason behind selecting a range well above CMC was to overcome the
loss of surfactant due to adsorption on reservoir rock throughout the flooding process. It was
observed from Fig.7 that microemulsions have smaller size and narrow droplets size
distribution, which indicates stability of the emulsion [34]. The average diameter of dispersed
oil droplets formed with 0.3 wt % C16mimBr concentration was found to be 474.5 nm. Thus
for further study in core flooding experiments the concentration of C16mimBr and
concentration of NaCl was set to 0.3 wt% and 3 wt % respectively.

The stability of emulsion was then examined by scanning the sample in a turbiscan for
a period of 24 hours. The Transmission profile of the homogenised mixture is elucidated in
FIG.8. From FIG. 8 it was observed that the oil in water emulsion in the lower phase broke
down gradually with time and separated into water and oil phase after a period of 24 hrs. As
separation of phases took place gradually it indicates that emulsion droplets formed in
homogenized sample were large enough to be stable. However it took about 6 hrs for the
emulsion phase to destabilize, which would be enough for the IL solution to sweep along

11
with it some amount of solubilised oil. This solubilised oil would then separate out into an oil
bank.

3.6 Core flooding experiment

The core flooding experiments were carried out at room temperature. A schematic
representation of the sand packed columns is shown in FIG. 1. Pore volume (PV cm3) of sand
column was calculated by measuring the volume of water required to saturate the column
[17]. The porosity (%) of the column was calculated as

PV
𝑃orosity (%) = (1)
Bulk Volume of the sand column

In the second step, paraffin liquid light oil was injected into the column, until there was
no more water coming out from the downstream. Original oil in place (OOIP, cm3) was then
calculated from volume of oil retained in the column. Initial oil saturation (Soi %) and initial
water saturation (Swi %) were calculated as follows respectively [12] :

𝑂𝑂𝐼𝑃
𝑆𝑜𝑖 (%) = × 100 (2)
𝑃𝑉

𝑆𝑤𝑖 (%) = 100 − 𝑆𝑜𝑖 (3)

The sand pack column was then sealed with a parafilm and allowed to stand for 24 hrs.
After 24 hrs, the sand column was waterflooded until there was no more oil in the effluent
stream. The amount of oil recovered after water flooding (ORWF, cm3) was determined
volumetrically. The residual oil saturation (Sor, %) was then calculated as follows:

The residual oil was then subjected to EOR processes. The column was then flooded
with surfactant solutions. The effluent was collected in graduated test tubes (25 cm3). All the
fractions recovered correspond to the oil recovered after surfactant flooding (ORSF, cm3). All
the results represent average of two independent experiments. The EOR (%) was calculated
as follows:

𝑂𝑅𝑆𝐹
𝐸𝑂𝑅 (%) = [(𝑂𝑂𝐼𝑃−𝑂𝑅𝑊𝐹)] × 100 (4)

3.6.1 Effect of different surfactant solutions on oil recovery efficiency

The effect of IL concentration on the oil recovery efficiency was investigated by

performing three different core flooding tests with gradual increase in volume of IL

12
containing water (pore volume).It is observed that with an increase in the IL concentration
from 0.1 to 0.3 wt %, oil recovery improved from 58.75 to 73.25%. These results could be
attributed to the IFT reduction, wettabilty alteration and the coacervation process. In the next
step, five EOR assays were performed in the small scale setup, using 3 wt % NaCl solution
without any surfactant, 0.3 wt % C16mimBr aqueous solution, 0.3 wt % C16mimBr in 3 wt%
brine solution, 0.3 wt % CTAB aqueous solution and 0.3wt% CTAB in 3 wt% brine solution.
The results obtained are reported in TABLE 3 and FIG. 9.

The sand pack column in the small setup had a PV in the range of 32 – 34 cm3and the OOIP
was between 17 – 24 cm3. Water –flooding with pure water removed about 60- 75 % of the
oil entrapped in the column thus leaving behind only 25- 40% of the initial oil in place. After
the secondary water – flooding step, tertiary EOR processes were performed as described
above. It was found that in all the assays, after injecting about 4 PV of slug no more oil
recovered. As seen from the TABLE 3, surfactant slug containing 0.3 wt % C16mimBr in 3
wt% brine solution recovered the maximum percentage of oil, 71.83%, trapped in the sand
packed column after secondary water flooding process.
FIG. 9 represents the oil recovery as a function of the volume of surfactant slug
injected. Percentage oil recovered when a surfactant slug prepared in brine water was injected
through the column was found to be larger than the oil recovered when the same surfactant
slug prepared in distilled water was injected. This improvement might be attributed to more
to additional decrease in IFT in the presence of NaCl as shown in FIG. 9. The IL solution was
found to be more efficient in recovering oil (both in distilled water and brine) when compared
with the traditional cationic surfactant CTAB. With oil recovery of 71.83 % the IL solution
prepared in brine was found to be the most efficient in an EOR process.

To investigate the effect of configuration of the sand pack column, another set of core
flooding experiments were performed in a large scale setup, dimensions of which are
mentioned in TABLE 1. After packing the sand in the acrylic column tightly, the two ends
were sealed with a sieved cap. The fluids were injected into the column at the rate of 2.33
ml/min. For the sand packed in the large scale setup, the PV was approximately 44 cm3. The
OOIP (average of two readings) was 20 cm3. After secondary water flooding step, the
residual oil saturation (Sor), was found to be approximately 30 %. During the tertiary oil
recovery process, an IL slug having composition (0.3 wt% C16mimBr in 3 wt % NaCl
solution) was injected into the acrylic column. The oil recovered after the IL-EOR process in
a sand bed packed in the acrylic column, was 75.65 % of the residual oil trapped in the pores
of the bed after secondary water flooding process, which was almost the same as in the case
of small setup. The results are shown in FIG. 9. Similar results were reported in another study

13
where EOR process was carried out by alkaline flooding for Western Canadian heavy oil
recovery [35].

3.7 Recycling of surfactant slugs for CEOR

To test the ability of recycling of the surfactant slug as well as its adsorption on sand, a
series of experiments was carried out for the two surfactant (CTAB and C16mimBr) slugs on
three different sand-pack columns. In the first step, fresh surfactant slug (either 0.3 wt %
CTAB or 0.3 wt% C16mimBr in 3 wt % brine solution), Cycle1, was flooded into core 1.
Effluent produced at the end of the chemical flooding process from core 1, known as Cycle 2
was then flooded into core 2 during its tertiary oil recovery process. Again effluent collected
from core 2, known as Cycle 3, was flushed as a chemical slug into core 3 during the CEOR
stage of the latter one. The purpose of doing this was to evaluate the depletion in efficiency of
the chemical slug, in recovering oil from the pores which was further attributed to loss of
surfactant due to adsorption on sand particles in the reservoir. The results are shown in
FIG.10. It was observed that when a chemical slug of 3.5 PV and a composition, 0.3 wt%
C16mimBr in 3 wt % brine solution, was injected into core 1, the additional oil recovered was
73.33%. From FIG. 10 it is observed that the efficiency of recovering trapped oil, of Cycle 2
has dropped down to 37.5% in core 2. In core 3, however not a significant depletion in
efficiency was observed i.e. Cycle 3 when flooded in core 3 recovered about 32% of the
trapped oil. Similar results were obtained for CTAB; however the oil recovered from core 3
reduced drastically to about 8%.

From the above results it is evident that both the surfactants, (CTAB and C16mimBr),
get adsorbed on the negatively charged sand particles in the packed column. The reason
being, that both of them have a headgroup with cationic charge. From FIG. 10 it can be seen
that amount of surfactant adsorbed on sand in core 1 was larger as compared to adsorption of
surfactants on sand particles in core 2 and core 3 in case of both CTAB and C16mimBr. T. Gu
et al.[36] suggested that at low concentrations surfactant molecules adsorb in a linear fashion
whereas at higher concentration, the adsorption suddenly increases due to hemimicellization,
initiated by some adsorbed surfactant molecules on the surface. Thus it is clear that amount
of surfactant adsorbed on the sand particles depends strongly on its concentration in the
effluent stream. Thus the IL solution retains its efficiency as compared to CTAB and thus
can be reused to serve as a more economical alternative to the traditional cationic surfactant,
CTAB.

14
3.8 Fourier Transform Infrared (FTIR) Spectroscopy of light oil and oil recovered after
flooding with surfactants (C16mimBr and CTAB) in brine solution.
IR spectra of the Paraffin liquid light oil used in the present study were recorded
between 400 and 4000 cm-1. A typical IR spectrum of pure oil is shown in FIG. 11. It also
shows spectra of oil recovered after flooding with CTAB and C16mimBr in brine solution.
FTIR spectra shown in the FIG.11 suggests the newly developed peak between 1600 -
1700 cm-1, may be due to the interaction between the C-N- C of the surfactants (C16mimBr &
CTAB) and CH2 from the oil part. Here it is noteworthy to mention that the micelles of the
surfactants (concentration well above CMC, 0.3 wt %) have been injected into in the sand
packed column. As general observation, micelles are more hydrophobic than the monomers,
the hydrophobic-hydrophobic interaction between the micelles of the surfactants and oil is
expected and which are confirmed through the newly generated peak between 1600 -1700
cm-1. The spectrum of the IL treated oil (FIG. 11) gives almost the same peak as that of the
CTAB treated oil, but with an improved interaction. It is noted that two bands at 3432 and
3481 cm-1 are due to the asymmetric υ3 and symmetric υ1 stretching modes of water, where
the water interacts with the anion via H-bonding in a symmetric complex [37]. In case of
C16mimBr, these peaks are merged and present as the single broad band in the recovered oil
sample after interacting with C16mimBr. Hence it is clear that C16mimBr might be reacting
with the hydrocarbon (oil) inside the packed column and a stronger interaction is responsible
for the better oil recovery in case of IL than the other systems studied which is CTAB.

3.9 Flow of surfactants through microchannel

A high percentage of oil recovered in surfactant – based enhanced oil recovery is
attributed to the formation of emulsions [6]. Emulsions are formed due to decrease in
interfacial tension between the oil and surfactant slug. In the present study it had been
observed that use of IL as well as CTAB as a surfactant solution improved oil recovery, the
two being more efficient under high salinity conditions. From emulsion droplet size
distribution experiments (section 3.5); this behaviour might be attributed to formation of
emulsions. In order to have a deeper insight on the formation of emulsions, miniature
microchannels were prepared and modelled as oil filled porous structure in the reservoir.
Slugs were then passed though these PDMS microchannels at the rate of 0.5 ml/min with the
help of a syringe pump. The flow of the fluids was recorded to mark formation of emulsions
if any. FIG. 12 shows frames of the video captured.

15
 It was observed that when pure brine without any surfactant was flown inside the
channel, no emulsions were formed. FIG. 12 (a) displays frames when brine solution is
passed though the microchannels initially filled with oil. When a high salinity brine solution
with strong dipole moment is injected into the column, electrostatic attraction between the
negative charge of sand surface and the ionic groups causes an increase in the oil recovery.
Zhang et al. [38] also showed that on injecting saline water into the core, oil was recovered. J.
Periera[17] in his studies had also observed oil recovery when brine solution was injected
into sand packed column after secondary oil recovery. They have attributed this oil recovery
to electrostatic attractions between brine solution and the surface charge of the sand particles
[17].

When the IL solution containing 0.3 wt % C16mimBr in distilled water was flushed
into the channel a clear presence of o/w emulsions was observed. However these emulsions
coalesced and gradually disappeared (FIG. 12(b)). Oil drops in the emulsion prepared in the
absence of salt were discrete and spherical. However for an IL solution in brine ((0.3 wt %)
C16mimBr + (3 wt %) NaCl), number of o/w emulsions formed was larger than those formed
in the case of IL solution in distilled water. Also a large variation in the size of these
emulsions was observed, FIG.12(c). Similar behaviour of effect of NaCl on emulsion size
was also reported by Binks et al. [39], when studying the effect of salt concentration on oil-
in-water emulsions stabilized solely by nanocomposite microgel particles. They concluded
that addition of salt resulted in tight concealing of ionized groups and also increased the
degree of ionization of imidazolium groups on the surface of the particles [39]. From FIG. 12
(c) it was observed that degree of flocculation was negligible in brine solution. Thus we can
conclude that when chemical flooding with IL in brine solution, a high recovery might be
observed due to formation of large number of o/w emulsions. When a surfactant solution
containing 0.3 wt% CTAB in brine (3wt% NaCl) was passed through the oil filled
microchannels, a cluster of very small o/w emulsions were observed at the interface (FIG.
12(d)).

The reasons for a lower efficiency of CTAB in recovering oil as compared to

C16mimBr can be attributed to the following reasons:

 The imidazolium ionic liquids have a bulky heterocyclic ring as cationic portion;
however, CTAB possesses a smaller quaternary ammonium cation. This bulky structure gives

16
the IL more hydrophobicity and consequently more interfacial activity than conventional
cationic surfactants [28].
 It has been reported that the imidazolium cations are aromatic in nature and have a
sextet of π-electrons [40].This aromatic character of ILs acts as driving force for oil
solubility. It might be due to the π-π interactions between IL and oil that more amount of oil
is solubilised in the o/w emulsions formed.
 The FTIR spectra of the oil recovered after CEOR from the sand packed column
indicates a stronger interaction between C16mimBr and oil. B.Dong et al. [23], also observed
slightly higher micropolarity of the Stern layer for CnmimBr micelles than that for CnTAB
micelles owing to the bulkiness of the imidazolium head group. The author concluded that
due to this behaviour CnmimBr would serve for potential application of ILs in colloidal
systems [28].

4. Conclusion

The surface activity of 1-alkyl-3-methyl imidazolium bromide (CnmimBr), n = 12, 14,

16, was evaluated by means of surface tension. It was found that surface activity of the ionic
liquids improved with increase in alkyl chain length. In addition to a lower CMC, interfacial
tension between oil and C16mimBr solution were lower than those obtained when using
CTAB surfactant solution under high salinity conditions. This interfacial activity of
C16mimBr solution was found to sustain even at high temperature conditions unlike other
conventional surfactants.

Sand-packed columns were moduled as reservoir cores and the potential of the two
surfactants (CTAB and C16mimBr) in recovering additional oil in an EOR process were also
investigated. Chemical flooding with IL in brine solution extracted more oil trapped in the
reservoir when compared to CTAB solution with same composition. FTIR of the recovered
oil further pointed out a stronger interaction between C16mimBr and oil, thus validating its
increased efficiency. PDMS microchannels were moduled as oil filled pores in the reservoir.
Inside the pores, IL solutions solubilise oil by forming o/w emulsions. C16mimBr showed
promising results when the effluent from a surfactant flooding process was reused in the
CEOR process of another sand packed column.

Based on the obtained results it can be concluded that C16mimBr has characteristics
which make them a promising candidate for surfactants to be used in EOR processes.
However other screening criterion in selection of surfactants for EOR process are: ultralow

17
interfacial tension and low adsorption on reservoir rock. Thus in our ongoing research we are
formulating ionic liquid surfactant solution which pass this screening criteria.

Funding: This research did not receive any specific grant from funding agencies in the publc,
commercial, or not-for-profit sectors.

REFERENCES
[1] V.Pillai, J.R.Kanicky, D.O.Shah, Application of Microemulsion in Enhanced Oil
Recovery, in: P.Kumar, K.L.Mittal (Eds.), Handbook of MicroemulsionScience and
Technology, Marcel Dekker Inc., New York, 1999, pp. 743-754.

[2] D.W. Green, G.P. Willhite, Enhanced Oil Recovery, fourth ed., Henry L. Doherty
Memorial Fund of AIME, Society of Petroleum Engineers, 1998.

[3] J.J. Sheng, Surfactant-Polymer Flooding, in: J.J. Sheng (Ed.),Enhanced Oil Recovery –
Field Case Studies, Elsevier, 117-142

[4] L.L. Schramm, D.G. Marangoni, Surfactants and Their Solutions: Basic Principles, in:
L.L.Schramm (Ed.), Surfactants: fundamentals and applications in the petroleum industry,
Cambridge University Press, UK, 2000.

[5] V. Alvarado, E. Manrique, Enhanced oil recovery: An update review, Energies. 3 (2010)
1529–1575.

[6] D.O. Shah, Fundamental aspects of surfactant–polymer flooding process, Keynote paper
presented at the European Symposium on Enhanced Oil Recovery, Bournemouth, England,
1981.

[7] M.S. Benzagouta, I.M. AlNashef, W. Karnanda, K. Al-Khidir, Ionic liquids as novel
surfactants for potential use in enhanced oil recovery, Korean J. Chem. Eng. 30 (2013) 2108–
2117.

18
[8]P. Wasserscheid, T. Welton (Eds.), Ionic Liquids in Synthesis, second ed., Wiley-
VCH,Weinheim, 2002.

[9] N.A. Smirnova, E.A. Safonova, Ionic liquids as surfactants, Russ. J. Phys. Chem. A 84
(2010) 1695–1704.

[10] M. Boukherissa, F. Mutelet, A. Modarressi, A. Dicko, D. Dafri, M. Rogalski, Ionic

liquids as dispersants of petroleum asphaltenes, Energy Fuels 23 (2009) 2557–2564.

[11]R.C.B. Lemos, E.B. Da Silva, A. Dos Santos, R.C.L. Guimarães, B.M.S. Ferreira, R.A.
Guarnieri, C. Dariva, E. Franceschi, A.F. Santos, M. Fortuny, Demulsification of water-in-
crude oil emulsions using ionic liquids and microwave irradiation, Energy Fuels 24 (2010)
4439– 4444.

[12] X. Chen, S. Yuan, A.A. Abdeltawab, S.S. Al-Deyab, J. Zhang, L. Yu, G. Yu, Extractive
desulfurization and denitrogenation of fuels using functional acidic ionic liquids, Sep. Purif.
Technol. 133 (2014) 187–193.

[13] H. Olivier-Bourbigou, V. Lecocq, Ionic liquids as new solvents and catalysts for
petrochemical and refining processes, Sci. Technol. Catal. 145 (2003) 55–60.

[14] P. Painter, P. Williams, A. Lupinsky, Recovery of bitumen from Utah tar sands using
ionic liquids, Energy Fuels 24 (2010) 5081–5088.

[15] M.H. José-Alberto, A. Jorge, Current knowledge and potential applications ofionic
liquids in the petroleum industry, in: P.A. Kokorin (Ed.), Ionic liquids:applications and
perspectives,InTech, 2011, pp. 439–456.

[16] S. Lago, H. Rodríguez, M.K. Khoshkbarchi, A. Soto, A. Arce, Enhanced oil recovery
using the ionic liquid trihexyl(tetradecyl)phosphonium chloride: phase behaviour and
properties, RSC Adv. 2 (2012) 9392-9397.

[17] J.F.B. Pereira, R. Costa, N. Foios, J.A.P. Coutinho, Ionic liquid enhanced oil recovery in
sand-pack columns, Fuel 34 (2014) 196–200.

[18] A.Z. Hezave, S. Dorostkar, S. Ayatollahi, M. Nabipour, B. Hemmateenejad,

Investigating the effect of ionic liquid (1-dodecyl-3-methylimidazolium chloride ([C12mim]
[Cl])) on the water/oil interfacial tension as a novel surfactant, Colloids Surf., A421 (2013)
63–71.

19
[19] A.Z. Hezave, S. Dorostkar, S. Ayatollahi, M. Nabipour, B. Hemmateenejad, Dynamic
interfacial tension behavior between heavy crude oil and ionic liquid solution (1-dodecyl-3-
methylimidazolium chloride ([C12mim][Cl] + distilled or saline water/heavy crude oil)) as a
new surfactant, J. Mol. Liq.187 (2013) 83–89.

[20] A.Z.Hezave, S. Dorostkar, S. Ayatollahi, M. Nabipour, B. Hemmateenejad, Effect of

different families (imidazolium and pyridinium) of ionic liquids-based surfactants on
interfacial tension of water/crude oil system, Fluid Phase Equilib.360 (2013) 139–145.

[21] A.Z.Hezave, S. Dorostkar, S. Ayatollahi, M. Nabipour, B. Hemmateenejad, Mechanistic

Investigation on Dynamic Interfacial Tension Between Crude Oil and Ionic Liquid Using
Mass Transfer Concept, J. Dispers. Sci. Technol.35 (2014) 1483–1491.

[22] I. Rodríguez-Palmeiro, I. Rodríguez-Escontrela, O. Rodríguez, A. Arce, A. Soto,

Characterization and interfacial properties of thesurfactant ionic liquid 1-dodecyl-3-
methylimidazolium acetate for enhanced oil recovery, RSC Adv. 5 (2015) 37392–37398.

[23] M. Bin Dahbag, A. AlQuraishi, M. Benzagouta, Efficiency of ionic liquids for chemical
enhanced oil recovery, J. Pet. Explor. Prod. Technol. 5 (2015) 353–361.

[24] N.I. Malek, Z.S. Vaid, U.U. More, O.A. El Seoud, Ionic-liquid-based surfactants with
unsaturated head group: synthesis and micellar properties of 1-(n-alkyl)-3-vinylimidazolium
bromides, Colloid Polym. Sci. 293 (2015) 3213–3224.

[25] Y. Jia, J. Jiang, X. Ma, Y. Li, H. Huang, K. Cai, S. Cai, Y. Wu, PDMS microchannel
fabrication technique based on microwire-molding, Chin. Sci. Bull. 53 (2008) 3928–3936.

[26] V.N. Lad, Ralekar Swati, Controlled evacuation using the biocompatible and energy
efficient microfluidic ejector, Biomed. Microdevices 18 (2016) 96.

[27] M.J. Rosen (Ed.), Surfactants and Interfacial Phenomena, third ed., John Wiley & Sons,
New Jersey, USA, 2004.

[28] B. Dong, X. Zhao, L. Zheng, J. Zhang, N. Li, T. Inoue, Aggregation behavior of long-
chain imidazolium ionic liquids in aqueous solution: Micellization and characterization of
micelle microenvironment, Colloids Surf., A 317 (2008) 666–672.

[29] R. Vanyúr, L. Biczók, Z. Miskolczy, Micelle formation of 1-alkyl-3-methylimidazolium

bromide ionic liquids in aqueous solution, Colloids Surf., A 299 (2007) 256–261.

20
[30] J. Łuczak, J. Hupka, J. Thöming, C. Jungnickel, Self-organization of imidazolium ionic
liquids in aqueous solution, Colloids Surf., A 329 (2008) 125–133.

[31] V. Mosquera, J.M. del Río, D. Attwood, M. García, M.N. Jones, G. Prieto, M.J. Suarez,
F. Sarmiento, A Study of the Aggregation Behavior of Hexyltrimethylammonium Bromide in
Aqueous Solution., J. Colloid Interface Sci. 206 (1998) 66–76.

[32] Z. Zhao, C. Bi, W. Qiao, Z. Li, L. Cheng, Dynamic interfacial tension behavior of the
novel surfactant solutions and Daqing crude oil, Colloids Surf., A 294 (2007) 191–202.

[33] D.C. Standnes, T. Austad, Wettability alteration in chalk 2. Mechanism for wettability
alteration from oil-wet to water-wet using surfactants, J. Pet. Sci. Eng. 28 (2000) 123–143.

[34] E. Chrisman, V. Lima, P. Menechini, Asphaltenes – Problems and Solutions in E&P of

Brazilian Crude Oils, in: M. El-Sayed Abdel-Raouf (Eds.), Crude Oil Emulsions-
Composition Stability and Characterization, InTech, 2012, pp. 1-25.

[35] Q. Liu, M. Dong, S. Ma, Y. Tu, Surfactant enhanced alkaline flooding for Western
Canadian heavy oil recovery, Colloids Surf., A 293 (2007) 63–71.

[36] T. Gu, Z. Huang, Thermodynamics of Hemimicellization of Cetyltrimethylammonium

Bromide at the Silica Gel/ Water Interface, Colloids Surf. 40 (1989) 71–76.

[37] L. Cammarata, S.G. Kazarian, P. a. Salter, T. Welton, Molecular states of water in room
temperature ionic, Phys. Chem. Chem. Phys. 3 (2001) 5192–5200.

[38] Y. Zhang, N.R. Morrow, Comparison of Secondary and Tertiary Recovery with Change
in Injection Brine Composition for Crude Oil/ Sandstone Combinations, SPE/DOE Symp.
Improv. Oil Recover. (2006).

[39] B.P. Binks, R. Murakami, S.P. Armes, S. Fujii, Effects of pH and salt concentration on
oil-in-water emulsions stabilized solely by nanocomposite microgel particles, Langmuir 22
(2006) 2050–2057.

[40] T.M. Krygowski, W.P. Oziminski, C.A. Ramsden, Sigma- and pi- electron structure of
aza-azoles, J. Mol. Model. 17 (2011) 1427–1433.

21
 Inner bore

Acrylic column
d
Tight cap Sand bed
L
Sieve

FIG. 1: Schematic representation of sand pack columns.

22
FIG. 2: Schematic diagram of set-up of recording flow in microchannels; (i) syringe
pump NE-4000 holding syringe. (ii) Nikon eclipse microscope TS100 (iii) Desktop
showing microscopic image (iv) microchannel.

23
 FIG. 3: Surface tension of aqueous solutions of surfactant ionic liquids at 298 K
and atmospheric pressure.

24
FIG. 4: Effect of surfactant concentration on IFT between oil and brine water (3 wt%
NaCl).

25
FIG. 5: Comparison of C16mimBr with CTAB on the basis of reduction of IFT between
oil/distilled water system and oil/ brine water (3 wt% NaCl) system.

26
FIG. 6: Plot of interfacial tension and temperature against time between oil and IL
solution (C16mimBr (0.01 wt %)) under varying salinity conditions.

27
 40
35 0.1 wt%
30 0.2 wt%
0.3 wt%
25
Intensity (%)

0.4 wt%
20
0.5 wt%
15
10
5
0
200 700 1200
Size(d.nm)

FIG. 7: Influence of change in concentration of C16mimBr on the size of emulsion at

constant brine concentration (3 wt %) and a constant WOR (4:1).

28
FIG. 8: Transmission profile of homogenised oil and IL solution.

29
FIG. 9: Comparison of enhanced oil recovery by chemical flooding using different
surfactants and different setups.

30
FIG.10. Effect of recycling of surfactant slug on EOR

31
FIG.11: FTIR spectrum of pure oil and oil recovered after surfactant flooding.

32
(a) Sequence of frames after 3 wt% NaCl is passed through the channel filled with oil. The
images are displayed using 4 times magnification for a microchannel of 384 µm diameter.

(b) Sequence of frames after IL solution containing 0.3 wt % C16mimBr in distiiled water
is passed through the channel filled with oil. The images are displayed using 4 times
magnification for a microchannel of 384 µm diameter.

(c) Sequence of frames after IL solution containing 0.3 wt % C16mimBr in brine (3 wt %

NaCl), is passed through the channel filled with oil. The images are displayed using 4
times magnification for a microchannel of 384 µm diameter.

(d) Sequence of frames after surfactant solution, (0.3 wt %) CTAB + (3 wt %) NaCl, is

passed through the channel filled with oil. The images are displayed using 4 times
magnification for a microchannel of 384 µm diameter.

FIG.12: Flow of different chemical slugs through PDMS microchannels.

33
TABLE 1: Dimensions of the large scale as well as the small scale setup used in the core
flooding process.
Inner diameter (d), Length of packed
(cm) sand bed (L), (cm)
Large scale setup 2.9 22.3
Small scale setup 2.9 10.9

34
TABLE 2: Surface properties of C12mimBr, C14mimBr, and C16mimBr at 298 K.
Ionic CMC (mmol/L) ƔCMC (mN/m) П CMC (mN/m) Γmax (µmol/m²)
liquids This Ref Ref This Ref Ref This Ref Ref This Ref Ref
work (28) (29) work (28) (29) work (28) (29) work (28) (29)
C12mimBr 9.03 10.9 9.8 39.4 39.4 na 32.6 33.6 na 0.42 1.91 na

C14mimBr 2.43 2.8 2.5 39.2 39.2 na 32.8 33.8 na 1.37 1.96 na
C16mimBr 0.54 0.55 0.61 38.6 39.1 na 33.4 33.9 na 1.55 2.03 na

na – not available

35
TABLE 2: Oil recovery in sand pack columns after flooding with NaCl (3 wt %), IL
surfactant – C16mimBr, conventional cationic surfactant – CTAB.

CTAB C16mimBr
Specifications of sand NaCl CTAB C16mimBr (0.3 wt %) (0.3 wt %)
pack column (3 wt %) (0.3 wt %) (0.3 wt %) + NaCl + NaCl
(3 wt %) (3 wt %)
Pore volume (cm3) 33.15 32.6250 33.4050 33.55 33.67
Porosity (%) 40.78 40.135 41.0950 41.27 41.455
Original oil in place,
17.1 23.5 21.5 18 19.5
OOIP (cm3)
Initial oil saturation,
51.58 72.0250 64.355 53.65 57.93
Soi (%)
Initial water saturation,
48.42 27.9750 35.6450 46.35 42.07
Swi (%)
Residual oil saturation,
26.9 29.78 20.93 33.33 36.14
Sor (%)
EOR with 4PV injected
12.61 32.145 62.53 54.87 71.83
(%)

36