Journal of Molecular Liquids 306 (2020) 112843

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Journal of Molecular Liquids

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

Primary evaluation of a synthesized surfactant from waste chicken fat as

a renewable source for chemical slug injection into carbonate
oil reservoirs
Iman Nowrouzi a, Amir H. Mohammadi a,⁎, Abbas Khaksar Manshad b,c,⁎⁎
a
Discipline of Chemical Engineering, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa
b
Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology (PUT), Abadan, Iran
c
Department of Petroleum Engineering, Faculty of Engineering, Soran University, Kurdistan Region, Iraq

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

Article history: Oil and fat extracted from plant seeds and animal tissues, as renewable sources, are used to produce various sur-
Received 1 January 2020 factants. These surfactants can be used in diverse industries including petroleum industry. One of the most im-
Received in revised form 29 February 2020 portant applications of surfactants is the reduction of water-crude oil interfacial tension (IFT) during the
Accepted 3 March 2020
chemicals injection into oil reservoirs. In the current study, chicken skin fat was used as the primary substance
Available online 05 March 2020
for the synthesis of a surfactant. The surfactant was synthesized by the processes of esterification and
Keywords:
sulphonation and was characterized by Fourier-Transform Infrared Spectroscopy (FTIR) and its temperature sta-
Surfactant bility was studied using thermal gravimetric analysis (TGA). Pendant drop surface tension tests, spinning drop
Interfacial tension (IFT) IFT, contact angle, and chemical alkali-surfactant-polymer (ASP) slug injection at optimal salinity and optimal al-
Wettability alteration kali with polymer were used to measure the usage of surfactant in the process of enhanced oil recovery (EOR). In
ASP slug injection addition, the surfactant foamability with nitrogen was investigated by foam generation in a temperature-
Foamability controlled Ross-Miles foam generator. The emulsion stability formed by the surfactant was also tested by obser-
Emulsion vational experiments. According to the results, the reduction of IFT to a low value (4.3 × 10−2 mN/m) at critical
micelle concentration (CMC), altering the wettability of carbonate rock from oil-wet to water-wet and eventu-
ally, about 18% increase in oil recovery by flooding the chemical ASP slug were obtained.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction IFT of 2.123 × 10−2 mN/m at CMC and 2.037 × 10−3 mN/m at optimal
salinity using a soap-nut surfactant. The alteration in the wettability
Surfactant injection into oil reservoirs is an effective EOR method. of sandstone was obtained from hydrophobic to hydrophilic, and a
Surfactants with the main purpose of reducing water-oil IFT and 30% increase in oil recovery was resulted by injection of a small
overcoming capillary pressure are injected into the reservoirs. In ad- surfactant-polymer slug into a sandstone plug [2]. Kiani et al. studied
dition, these materials also affect other mechanisms such as wetta- a series of new anionic surfactants (iC18S (FO-180)) in the process of
bility alteration and forming emulsion and foam. Different types of EOR. Significant reductions in IFT and contact angle on the glass and a
surfactants have been investigated for their different applications recovery factor equivalent to 72% in the flooding process of surfac-
in EOR mechanisms. Saxena et al. investigated surfactants synthe- tant in the glass micromodel were resulted [3]. Tay et al. examined
sized with the base of Madhuca longifolia (Mahua) oil in EOR pro- Internal Ketone Sulfonates (IKS) as a new surfactant in the process
cesses. They obtained an IFT of 10−2 mN/m, an alteration in the of seawater injection. Reduced IFT at optimum salinity up to
wettability from hydrophobic to hydrophilic, and an increase of 3.5–4.0 mN/m, and a very high recovery factor were obtained in
20% in oil recovery factor by injection of a slug of surfactant- water injection [4]. Najimi et al. used the ionic liquids of [C8Py][Cl]
polymer into the sandstone plug [1]. They also obtained an optimum and [C18Py][Cl] as surfactants. They reported a reduction of 70% in
IFT values at high NaCl salinity using only 1000 ppm ionic liquids
[5]. Manshad et al. examined [C18Py][Cl], [C8Py][Cl], [C18mim][Cl],
⁎ Corresponding author. and [C 12mim][Cl] ionic liquids as surfactants in EOR processes. By
⁎⁎ Correspondence to: A. K. Manshad, Department of Petroleum Engineering, Abadan screening, they selected [C18mim][Cl] solution as more efficient ad-
Faculty of Petroleum Engineering, Petroleum University of Technology (PUT), Abadan,
Iran.
ditive and obtained a 13% increase in oil recovery by flooding in a
E-mail addresses: amir_h_mohammadi@yahoo.com (A.H. Mohammadi), carbonate plug [6]. Kumar and Mandal synthesized a family of zwit-
khaksar@put.ac.ir, akmanshad113@gmail.com (A.K. Manshad). terionic surfactants and investigated them in EOR. Surfactants were

https://doi.org/10.1016/j.molliq.2020.112843
0167-7322/© 2018 Elsevier B.V. All rights reserved.
2 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843

synthesized with carboxybetaine base and hydrophobic tail of 12, 14, use, some issues such as the desired performance in reducing IFT
16 and 18 carbons. Their results confirm a further reduction of IFT by and stability at reservoir conditions should be considered. Fats and
increasing carbon atoms in the hydrophobic part. Also, the injection oils extracted from plants and animal tissues have long been used
of a small slug of the surfactant, polymer, and alkali resulted in a 30% to prepare surfactants. In this study, extracted chicken waste fat as
increase in oil recovery [7]. Madani et al. synthesized and used a non- a renewable source, inexpensive, and available primary material
toxic and environmentally friendly amino acid-based surfactant. The was used to prepare surfactant. Characterization of the synthesized
reduction of IFT in their studies did not reach the ultra-low values, surfactant was performed by FTIR and TGA analyses. Surface tension,
but the alteration in wettability in both sandstone and carbonate interfacial tension, contact angle and flooding tests were used to
samples and the final oil recovery of 57.26% for the total secondary measure the application of surfactant in EOR. In addition, the com-
and tertiary flooding were achieved [8]. Pal et al., synthesized a Gem- patibility of injectable surfactant solution with formation water,
ini surfactant based on Sunflower oil and investigated its effects on foam behavior and emulsion stability are also demonstrated by sim-
EOR processes. They reduced the IFT to 10 −2–10 −3 mN/m [9]. Pal ple experiments.
et al. synthesized another surfactant based on coconut oil and exam-
ined its application in EOR. In addition to obtaining ultra-low IFT and 2. Experimental section
the change in quartz wettability to water-wet, they increased the oil
recovery factor by 20.05% [10]. Pillai et al. used ionic liquids as sur- 2.1. Materials
factants in EOR experiments. Their results confirm the application
of ionic liquids used at high temperatures and high salinity condi- The crude oil from Gachsaran oil-field in southwestern Iran with
tions, with a 32% oil recovery increase in flooding of chemical slug 3.7 mgKOH/g acidity and 87 cp viscosity and the information listed in
containing ionic liquids, polymer, and alkali in sandpack [11]. Table 1 and formation water with the information in Table 2 were
Rostami et al. used a Lysine Derivative Surfactant in EOR. They used. The used rock was the samples of the out-crop carbonate with
lowered the IFT of water-kerosene system by more than 40% and 39% calcite and 61% dolomite contents. Fig. 1 shows the SEM and XRD
also the carbonate rock wettability alteration from hydrophobic to analyses of the carbonate rock. Chicken skin fat was purchased from a
hydrophilic. Eventually, a 12% recovery was achieved in the flooding local store. This fat was extracted by chicken skin mincing and heating
of the surfactant in a carbonate plug [12]. Hussain et al. tested a new it. Usually, from every 100 g of the original tissue, 30 g of fat are pro-
family of quaternary ammonium Gemini surfactants and their appli- duced in this way and it is traditionally used to make soap and ointment
cation in EOR. Their results, confirm the temperature stability of the to prevent dry skin. The specifications of the fat included: a density of
surfactants and their good solubility in saline water show that by in- 0.962 g/cm3, an acidity of 16.8 mg KOH/g and a free fatty acid of
creasing the spacer length in the structure of Gemini surfactants, 0.58%. Polyethylene glycol 400 potassium hydroxide, diethyl ether, so-
CMC and surface tension decrease [13]. In addition, some researchers dium bicarbonate, chlorosulphonic acid, pyridine, sodium carbonate,
looked at the foaming behavior of surfactants in EOR studies. For ex- n-butanol, petroleum ether, partially hydrolyzed polyacrylamide
ample, Skauge et al. reviewed the effect of surfactant concentration (PHPA), and NaCl from Merck Co. (Germany) were purchased.
on the foamability. They showed that foam is also formed at very
low concentrations of surfactant (under CMC) but in-situ foam gen- 3. Method
eration in porous media, especially in oil-wet carbonate rocks, is very
difficult and complex [14]. Dongxing et al. reviewed the dynamic be- 3.1. Surfactant synthesis
havior of the foam formation in the entrance region of porous media.
They stated that foam could push more liquid into later parts of po- Surfactant synthesis from chicken skin fat was performed in two
rous media. They compared the efficiency of CO 2-foam and N2 - stages of Esterification and Sulphonation. For esterification, the fat was
foam and concluded that the N2-foam creates more liquid saturation initially combined with polyethylene glycol 400 plus 0.5% potassium
in the input section and lower recovery is achieved [15]. Janssen et al. hydroxide as a catalyst. The resulting mixture was stirred continuously
introduced Foam-Assisted Chemical Flooding as a new EOR method. for 30 min at 70 °C and then poured into the separation funnel to purify
They used two stable surfactants in salinity and reservoir tempera- the ethyl ester produced in the higher layer. Subsequently, the catalyst
tures for this purpose. They injected the surfactant slugs and then and extra polyethylene glycol were filtered. A solvent containing diethyl
produced in situ foam by nitrogen injection and compared it with ether and sodium bicarbonate was used to wash residual fatty acids. The
pre-generated foam. They found that the presence of crude oil final product of this stage was evaporated in a distillation device con-
weakens foam stability. In addition, pre-generated foam injection in- nected to the vacuum pump for 40 min to eliminate the moisture con-
creased the recovery factor by 13% compared to foam in-situ foam tent of the sample. At this stage, a viscous creamy liquid was obtained.
[16]. In addition to the benefits of using surfactants in the EOR, In the Sulphonation step, 5.40 g Chlorosulphonic acid was added along
there are challenges such as costs, sometimes environmental mis- with 30 ml pyridine in a round-bottom flask and the mixture was stirred
matches, inefficiencies, and instability at reservoir temperature and at 60 °C for 30 min to obtain a clear solution. The solution was quenched
salinity. The injection of surfactant with polymer and alkali as a with sodium carbonate and sodium bicarbonate saturation solution in a
low-volume slug is a way to reduce the amount of the material but separator funnel. A solution of n-butanol (50 ml) was used to remove
at the same time, the use of expensive surfactants as a slug also re- nonreactive organic matter. The aqueous layer containing the final
quires a lot of material in the field. Natural base surfactants have product was evaporated at 120 °C to separate water and pyridine. The
been considered in recent years due to their low prices but in their product was evaporated for 40 min in a distillation device connected

Table 1
Analysis of Gachsaran crude oil.

Component C1 C2 C3 iC4 nC4 iC5 nC5 C6 C7 C8 C9 C10 C11 C+

12 Total

Molar percent 0.00 0.08 0.73 0.72 2.22 1.10 1.10 8.66 9.32 6.60 7.14 5.36 5.01 51.96 100.00

Molecular weight = 247.

Molecular weight of C+ 12 = 380.
Specific gravity of C+
12 @ 15.55 °C = 0.9369.
Saturation pressure of reservoir fluid @ 60.6 °C = 14.04 MPa.
 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843 3

Table 2 The crude oil-surfactant solution IFT tests at different concentrations

Analysis of formation water sample. and then the effects of NaCl salinity and NaOH alkali on IFT at CMC were
Specie Conc. (ppm) studied by the spinning drop method at 75 °C to obtain optimum salin-
Cl− 39,050
ity and alkali. The SITE 100HS device manufactured by KRÜSS, Germany
SO2−
4 220 was used for this purpose. The ability to measure surface tension in the
HCO− 3 210 range of 0.0001–50 mN/m, and temperature variation up to 100 °C, are
Mg2+ 1700 the features of this device. One drop of oil is placed in a horizontal sy-
2+
Ca 3500
ringe filled with an aqueous solution and then the spin starts. A camera
Na+ 25,300
Fe+ 30 reports the droplet status to the device software at any time. The basis of
2
K+ 180 this device is to calculate the IFT by Eq. (2):
PH 7.50
TDS 74,000 !
D3
γ ¼ 0:521 Δρ ð2Þ
P2
to the vacuum pump and the final sodium ethyl ester sulfonate anionic
surfactant was obtained as a white powder. where D is the diameter of the droplet, P is the number of spins and Δρ is
the difference in the density of the oil phase and the aqueous phase.
3.2. FTIR and TGA analyses For the contact angle experiments, the thin sections were placed in
toluene for 1 day to clean them after cutting. The washed and dried sec-
The temperature stability and characterization of the surfactant tions were aged in crude oil for one month at 75 °C to obtain hydropho-
were studied by TGA and FTIR analyses. For FTIR analysis, a bit of surfac- bicity [20]. Finally, the contact angle experiments were performed in a
tant and KBr were used in combination. IR spectra were recorded on the surfactant solution at CMC and at a temperature of 75 °C over time.
Tensor 27 FT-IR Bruker spectroscopy. It has a spectrum of For contact angle experiments, the IFT400 was also used. In this exper-
370–7500 cm−1 and can analyze the liquid and solid samples. For iment, a section holder is closed at the top of the cell to hold a section in
TGA, 15 mg of the surfactant sample was heated in a Netzsch TG209 an aqueous medium. The oil drop is placed on the rock surface by the
F1 analyzer in an atmosphere of nitrogen at a rate of 10 °C/min and a needle. The camera reports the images of the system to the software
stream of the flow rate of 30 ml/min. and the software calculates the contact angle at any moment.

3.3. Surface tension, interfacial tension, and contact angle experiments 3.4. Compatibility, foamability, and emulsion stability tests

Surface tension tests of surfactant solutions were carried out at 75 °C The compatibility of the injectable fluid with formation water is a
and the amount of CMC was determined by IFT400 device. The basis of very important issue in chemical water injection methods. The incom-
the device is the pendant drop method. In the course of surface tension, patibility of the chemical solution with the formation water in the reser-
a drop of surfactant solution is hanged in an air environment. The cam- voir leads to sediment and damages the formation. To determine the
era transfers the images of the droplet to the computer momentarily compatibility and critical salinity of NaCl salt at concentrations of
and the software calculates the surface tension by Eq. (1). Other details 20,000, 30,000, 50,000, 70,000, 100,000, and 130,000 and
of this device are reported in our previous studies [17–19]. 160,000 ppm, as saline water was used. 10 ml of the optimum solution
of surfactant and 10 ml of each saline water were mixed in a test tube
and stored in an oven for 2 weeks at 75 °C. Subsequently, the contents
ΔρgD02
γ¼ ð1Þ of each tube were passed through filter paper. The filter paper was
H dried at 50 °C for one day and then the weight of the sediment was cal-
culated. In addition, similar steps were taken for formation water. For
where Δρ is the density difference (g/cm3), g represents the earth grav- foamability tests, N2-foam was prepared using nitrogen blowing in a
itational acceleration (cm/s2), D′ stands for the larger diameter (cm), surfactant solution at CMC and at 75 °C in a Ross-Miles foam generator
and H is a function of S = d/D, where d represents the smaller diameter capable of adjusting the temperature of the foam container. Fig. 2 shows
at a distance D from the top of the droplet. the schematic of the foam generator system. This device consists of a

Fig. 1. XRD (left) and SEM (right) analyses of the rock samples.
4 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843

Fig. 2. The schematic of the Ross-Miles foam generator with the ability to adjust the temperature of the foam container by hot water flow.

glass column graded as a foam casing with a height of 100 cm and a di- into the plug. The injection rate is adjustable. The output fluid from
ameter of 2 cm, below which is a metal grille for better gas flow and is the plug is collected and measured in a graduated container. The system
connected to the nitrogen source and above the foam outlet valve. A is housed in an oven for temperature regulation.
flow-meter controls the flow of nitrogen from the source to the foam
casing. The temperature of the foam container with hot water flows 4. Results and discussion
into the foam shell, which acts as a heat exchanger, is supplied by a
water bath. To prepare N2-foam, 40 ml of the optimum surfactant solu- 4.1. FTIR and TGA analyses
tion was poured into the foam container and nitrogen gas was blown
with different flow rates. In this way, the properties of N2-foam includ- The FTIR analysis is shown in Fig. 4. The sulphonation fat is con-
ing foam height and stability were investigated. firmed by peaks (a) at 622, (d) at 857 and (g) at 1161 cm−1, indicating
An emulsion stability test was performed for a surfactant solution at the stretching vibrations of the S_O, S\\O and S\\O bonds in the sulfo-
CMC. For this purpose, a solution of surfactant and crude oil was equally nate group, respectively. The overall correlation of peaks with functional
distributed by ultrasonic mixer UP400 manufactured by Hielscher groups derived from FTIR analysis is presented in Table 3. The tempera-
GmbH for 30 min at 400 W power. The emulsion was then poured ture stability of the surfactant is also confirmed according to the TGA
into a test tube and placed in an oven at 75 °C to observe the results. analysis shown in Fig. 5. A temperature peak starts at 25 °C and con-
tinues at about 140 °C. Weight loss after this peak reaches 15%. Consid-
3.5. Oil recovery by ASP flooding ering the evaporation of the sample moisture at this temperature peak,
the composition of the surfactant at reservoir temperatures is protected
Surfactant solution at CMC and optimum salinity and alkali and from degradation.
1000 ppm partially hydrolyzed polyacrylamide (PHPA) polymer was se-
lected as an optimum solution for measuring the recovery factor by the 4.2. Surface tension and interfacial tension
chemical ASP slug injection. The flooding tests were done with a
0.2 ml/min flow rate at a temperature of 75 °C. The ASP injection was Fig. 6 shows the results of the surface tension experiments. Surface
executed as 0.5 PV slug. As a result, after the secondary flooding with sa- tension decreases with a steep slope by increasing the concentration
line water, the ASP solution was injected at optimum concentrations to a CMC of 5500 ppm and then there is not much change in the decreas-
and then saline water was injected. The used flooding device is shown ing or increasing trends of surface tension. Amphiphilic molecules oc-
schematically in Fig. 3. A hydraulic fluid (distilled water) is pumped to cupy the solution surface due to their dual structure of hydrophobic-
the back of the piston in the cylinders and injects the selected fluid hydrophilic so that the hydrophilic head is dissolved in aqueous solution

Fig. 3. Schematic of the core-flooding device. 1: HPLC pump, 2: Barometer, 3: Valve, 4: Cylinder containing crude oil, 5: Cylinder containing brine, 6: Cylinder containing surfactant solution,
7: Core holder, 8: Fluid flow distributor, 9: plug, 10: Rubber blocker, 11: Oven, 12: Manual hydraulic pump, 13: Container collecting outlet fluid.
 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843 5

Fig. 4. FTIR analysis of the surfactant.

Fig. 5. TGA analysis of the surfactant.

and the hydrophobic head avoids it [21,22]. Fig. 7 shows the IFT values is further reduced. If the amount of injectable alkali is sufficient, it can
of surfactant solutions and crude oil, and Fig. 8 shows the effect of salin- form soap with all the acidic constituents of the oil [27]. Therefore, the
ity from NaCl salt. Fig. 9 shows the effect of NaOH alkali on IFT at CMC. A optimum amount of alkali is controlled by the number of acidic oil com-
similar trend with surface tension variations is observed in Fig. 7 for sur- ponents. In other words, the optimization of the IFT value at a specific
factant solutions and crude oil IFT. At 75 °C, the IFT value of the surfac- concentration can be attributed to the number of acidic oil components
tant concentration has an inverse relationship, and the rapid drop out in the presence of alkali.
of the IFT occurs to a specific concentration of CMC (4.3 × 10−2 mN/
m). Thus, IFT values at concentrations of 1500, 2500, 3500, 4500, 4.3. Contact angle
5500, 6500 and 7500 ppm were obtained 10.421, 7.813, 3.578, 0.974,
0.043, 0.063 and 0.060 mN/m, respectively. Different amounts of salinity Fig. 10 shows the average contact angle values as a graph. Accord-
also affect the IFT of surfactant solution at CMC and crude oil but there is ingly, the contact angle of the oil droplet and the cross-section with
an optimal concentration. According to Fig. 8, the values of IFT of surfac- the passage of time in the surfactant solution at 15, 30, 45, 60 and
tant at CMC and at salinity of 5000, 10,000, 15,000, 20,000, 30,000 and 120 min were obtained 139.21, 101.65, 73.15, 43.16 and 43.11°, respec-
40,000 ppm were achieved to 0.046, 0.044, 0.038, 0.042, 0.069 and tively. By comparing the magnitude of the contact angle and the initial
0.091 mN/m, respectively. By adding alkali, the IFT values are further re- angle, after 60 min, the wettability has altered from hydrophobic to hy-
duced. The IFT values at concentrations of 500, 1000, 1500, 2000, 2500, drophilic. In addition, the diagram of contact angle changes over time
3000, 4000 and 5000 ppm alkali, were obtained 0.042, 0.040, 0.037, shows that after 60 min there is little change in the contact angle so
0.030, 0.034, 0.041 and 0.045 mN/m, respectively (Fig. 9). The reason that only 3° of change is observed after 120 min. Therefore, 60 min
for the change in IFT by ions also depends on the adsorption of ions in can be considered as the equilibrium time. Contact angle variations
the interface due to the presence of polar components in the oil. In ad- over time are due to the time-varying mechanisms of the wettability al-
dition, at lower concentrations due to the effect of salt-in, lower IFT oc- teration and interactions of surfactant molecules and the surface of the
curs [23–25]. In the presence of alkali, the IFT is further reduced. It can rock. It is generally accepted that the absorption of surfactant molecules
be attributed to the ionization of carboxylic acid with alkali [26]. In ad- on the surface of the rock results in the wettability alteration of the
dition, the reactions of alkali and acidic components of the oil in the rocks. This absorption is due to electrostatic interactions between
water-oil interface further reduce IFT. The most important reaction of charged sites of the rock surface and charged head-groups of ionic sur-
alkali and acid is the production of in-situ soap in the interface. This factants [28]. Carbonate rock has a positive charge in the presence of
means that the amount of additional surfactant as a result of this reac- aqueous solution and anionic surfactant molecules are opposite to the
tion strengthens directly the formed layer in the interface and the IFT charge of the surface of the rock. This creates a gravitational force be-
tween the surfactant molecules and the carbonate surface, and
Table 3
Peak communication with functional groups in FTIR spectra of chicken skin fat surfactant.

Peak Wavenumber, cm−1 Functional group Vibration mode

a 622 \O
S\ Stretching
b 710 \
\CH_CH Bending
c 715 \
\CH_CH Bending
d 857 \O
S\ Stretching
e 963 CH\\CH Bending
f 1234 \
\CH Bending
g 1161 S_O Stretching
h 1234 C\\H (CH2) Bending
i 1371 C\\H (CH3) Bending
j 1451 C\\H (CH2) Bending
k 1736 C_O Stretching
l 2851 C\\H (\
\CH2) Stretching vibration
m 2924 C\\H (\
\CH2) Stretching vibration
n 2955 C\\H (CH3) Stretching vibration
o 3006 C_H Stretching
p 3477 \
\OH Stretching
Fig. 6. Surface tension graph of the surfactant solutions at 75 °C.
6 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843

Fig. 7. IFT curve of the surfactant solutions and crude oil at 75 °C. Fig. 10. The curve of contact angle of an oil droplet on the cross-section changes in the
presence of a solution of surfactant at CMC over time.

0.1
Interfacial tension, mN/m

0.09 value reaches an equilibrium value and then there is not much change
0.08 in the contact angle over time.
0.07
0.06 4.4. N2-foam characterization
0.05
0.04 It is accepted that aqueous solutions with low surface tension are
0.03 more suitable for foam generation [31–34]. The formation of foam by
0.02 surfactants is due to their hydrophilic-hydrophilic dual structure. A
0.01 water-film surrounding a gas bubble as the hydrophobic part enters
0 the bubble and the hydrophilic part enters the film and this arrange-
0 10000 20000 30000 40000 50000 ment makes the foam stable. This film of separating gas bubbles is
NaCl concentraton, ppm known as foam lamellae [35]. Fig. 11 shows the height chart of N2-
foam at different times. The height of the foam column was mea-
Fig. 8. Effect of salinity on the IFT of the surfactant solution at CMC and 75 °C.
sured when the foam column was filled (at this moment the gas
flow was cut off) and it was based on the interface of the
surfactant-foam solution. Based on Fig. 11, the height of the foam de-
ultimately the surfactant molecules are adsorbed on the surface. The ad- creases over time and reaches zero after 35 min. This time is known
sorption of surfactants creates a thin film on the surface of the rock, as half-life time foam, which is shown with t1/2 and as shown in
which has a wetting effect that has an opposite wettability to the origi- Fig. 11 for the surfactant at CMC is equal to 13 min. Foam decay de-
nal rock. However, the adsorption of surfactants alters the wettability if pends on the initial structure of the foam. The foam structure is de-
the orientation of the surfactant molecules is favorable. There is another termined by some parameters, such as gas flow rate and soluble
mechanism in wettability alteration by surfactant at CMC where the ori- impurities such as salts. The effects of gas flow rate and time on bub-
entation of molecules is regular and that is the formation of Hemi- ble size were evaluated qualitatively. Given the scale of the images
micelles. Hemi-Micelles are agglomerates of the surfactant molecules and the size of the bubbles, as shown in Fig. 12, the size of the bub-
that form at a specific concentration on the solid surface. The arrange- bles increases over time. Over time, the effects of the forces involved
ment of the molecules in the film consisting of Hemi-Micelles is ar- in the aqueous film, such as gravity, increase the tendency of the fluid
ranged in such a way that the heads of the surfactant molecules are to collapse at the bottom of the foam column. On the other hand, the
placed on a solid surface and their tails are upward. The orientation of internal force of the gas inside the bubble to the wall, due to both the
the molecules is also determined by intrinsic properties such as surfac- difference in the mass of gas and liquid and the movement of gas
tant type and surface charge of the rock [29,30]. After the surface is oc- molecules, makes the film of the thinner. As a result, the gas phase
cupied by adsorbed molecules and Hemi-micelles, the contact angle ratio increases so that some bubbles with an adjacent bubble

0.05
Interfacial tension, mN/m

0.045

0.04

0.035

0.03

0.025
0 1000 2000 3000 4000 5000 6000
NaOH concentration, ppm

Fig. 9. Effect of NaOH alkali on the IFT of the surfactant solution at CMC and 75 °C. Fig. 11. The curve of N2-foam height formed by surfactant at CMC over time.
 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843 7

Fig. 12. Time-effect on bubble size of N2-foam generated by the surfactant at CMC and optimum salinity and gas flow rate equal to 10 ml/s.

through the percolation of a liquid film form a larger bubble. Fig. 13 Fig. 16 shows the stability of the emulsion formed by the surfactant
shows the effect of different gas flow rates on the size of the bubbles solution at CMC and crude oil over time. The first phase separation and
in the N2-foam formed by the surfactant at CMC immediately after exit from the monophasic mode occurred after 5 days. After that, the
filling the column of foam. The bubble images in Fig. 13 clearly three phases of oil, water, and the middle are in the system. As time
show that with increasing gas flow rate the size of the bubbles in- goes on, the volume of the oil and water phase increases and the volume
creases. However, bubble enlargement means increasing the gas of the middle phase decreases accordingly. In these experiments, the
phase and decreasing the liquid phase in the foam system, which exact amount of phases cannot be determined, but the separation of
can change the foam stability. The images of Fig. 13 confirm the the three phases can be distinguished from one another. The acceptable
lower gas flow rate for a homogeneous-foam creation. However, stability of the emulsion is confirmed after 25 days of complete phase
due to the qualitative nature of the survey, it is not possible to deter- separation. The formation of emulsions by surfactants is very important
mine the exact rate according to them. Some references suggest the as one of the mechanisms to enhance oil recovery. The reduction of IFT
gas flow rate between 20 and 30 ml/s as the most suitable gas flow results in the formation of an emulsion on the front of the injection sur-
rate for homogeneous foam in terms of bubble size [35]. Increasing factant slug. The emulsion is formed when the oil and the injectable so-
the gas flow rate with increasing bubble size also increases foam vol- lution are adjacent to each other and are sufficiently combined in a
ume. Fig. 14 shows the effect of gas flow rate on the volume of N2- continuous phase. Emulsion breaks down large oil droplets and turns
foam produced by the surfactant at CMC over time. Based on them into smaller droplets, resulting in an increase in the oil-water
Fig. 14, as gas flow rate increases, less time is needed to fill foam col-
umns or to reach a constant volume. For gas flow rates of 10, 20, 30
and 50 ml/s, approximately 55, 40, 30 and 20 s are needed to fill
foam columns, respectively.

4.5. Compatibility and emulsion stability

Fig. 15 shows the results of experiments of compatibility with for-

mation water and saline water at different NaCl concentrations. Based
on the results, after 2 weeks of mixing the solution of surfactant with sa-
line samples at 75 °C, the surfactant compatibility with formation water
is confirmed because the sediment is not seen in the solution. With in-
creasing salinity of 20,000, 30,000, 50,000, 70,000 and 100,000 ppm,
the solution remains consistent. The sediment was observed for solu-
tions of 130,000 and 160,000 ppm, at 0.1417 and 0.2376 g, respectively.
This means that the surfactant for reservoirs with a salinity of less than
130,000 ppm is applicable and after this critical salinity, the formation of Fig. 14. Gas flow rate effect on the volume of N2-foam generated by surfactant at CMC over
time.
sediment occurs and pore plugging may occur in the reservoir.

Fig. 13. Effect of different gas flow rates on the size of the bubbles in the N2-foam generated by the surfactant at CMC immediately after filling the column of foam.
8 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843

Fig. 15. Compatibility of a solution of the surfactant at CMC with different salinity at 75 °C.

Fig. 16. Emulsion stability of a surfactant solution at CMC and crude oil over time.

interface. When the water-oil interface increases, the absorption of sur- 5. Conclusions and recommendations
factant molecules in the interface will increase and as a result, IFT is re-
duced further, which can have a positive effect on the capillary pressure An anionic surfactant from waste chicken fat as a renewable source
and production of oil [36,37]. was synthesized and its application in EOR was investigated. Based on
the tests and analyses, the following results were obtained:

4.6. ASP injection

Fig. 17 shows the oil recovery and the pressure drop in the flood ver-
sus injected fluid volume. The injection test was done in a carbonate
plug with a length of 7 cm, a diameter of 1.5in, an effective porosity of
18.4%, an effective pore volume of 14.67 cm3, an absolute permeability
of 5.39 md, initial water saturation of 16%, and an original oil in place
of 12.2 cm3. Secondary brine injection increased oil recovery by 44.7%.
An ASP injection of 0.5 PV was continued and the brine was injected
again. A final recovery factor of 62.5% was obtained which is 17.8% be-
longs to the tertiary injection. Oil recovery in brine is more like a sweep-
ing efficiency. However, some of it is linked to wettability alteration by
soluble ions but in the ASP injection, both mechanisms of IFT reduction
and wettability alteration increase the recovery of oil after brine injec-
tion. This is while the polymer plays an additional role in the injection
front and it pistonizes the injection front and prevents the production
of injectable fluid early through the fingering. Fig. 17. Oil recovery curve for injectable PV in the chemical ASP slug injection.
 I. Nowrouzi et al. / Journal of Molecular Liquids 306 (2020) 112843 9

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