Journal of Molecular Liquids 249 (2018) 73–82

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Journal of Molecular Liquids

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

Synthesis and physiochemical performance evaluation of novel

sulphobetaine zwitterionic surfactants from lignin for enhanced
oil recovery
Shuyan Chen a, Hongjuan Liu a, Hong Sun b, Xiang Yan a, Gehua Wang a, Yujie Zhou a,⁎, Jianan Zhang a,⁎
a
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China
b
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

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

Article history: Lignin sulphobetaine zwitterionic surfactants (LSBA) were successfully synthesized by a cost-effective three-step
Received 25 September 2017 route containing sulfonation, quaternization and alkylation reaction from renewable alkali lignin. The synthe-
Received in revised form 2 November 2017 sized surfactants were characterized by FT-IR, UV and 1H NMR analysis. The physicochemical properties of syn-
Accepted 2 November 2017
thesized surfactants had been tested to investigate the effectiveness of LSBA surfactants for enhanced oil recovery
Available online 06 November 2017
(EOR). The hydrophile lipophile balance (HLB) values of LSBA-1, LSBA-2 and LSBA-3 were 14, 11 and 10, respec-
Keywords:
tively. LSBA surfactants exhibited high surface activity with low surface tension and the critical micelle concen-
Zwitterionic surfactant tration (cmc) of LSBA-1, LSBA-2 and LSBA-3 were 4.36 × 10−4 mg/L, 4.45 × 10−4 mg/L and 1.04 × 10−3 mg/L,
Surface tension respectively. The dynamic interfacial tension (IFT) between the crude oil from Huabei and Xinjiang oilfields
Interfacial tension (China) and the LSBA solution was measured. Compared with Huabei crude oil, LSBA surfactants showed better
Synthesis interfacial activity on Xinjiang crude oil. LSBA surfactants reduced the IFT between Xinjiang crude oil and brine
Alkali lignin down to ultra-low (b10−3 mN/m) under weak alkaline conditions.
Enhanced oil recovery © 2017 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, more and more attention has been paid to surfactant
flooding recovery, which is one of the promising chemical methods for
enhanced oil recovery (EOR) [1–3]. Surfactants can not only decrease
the oil/water interfacial tension (IFT) but also improve the capillary
number, making the residual oil trapped in reservoir flow, thus the effi-
ciency of oil recovery can be improved greatly [4–6]. At the present
stage there are a lot of serious problems in surfactant flooding, such as
adsorption loss, large dosage and high cost, which obviously limit the
wide application of surfactants in EOR [7]. Therefore, the research and
development of high efficiency and low-cost oil-displacing surfactants
has become one of the major challenges for the scientific workers. The
production of eco-friendly green surfactants which make full use of nat-
ural renewable resources and the green chemical synthesis technology
are the hotspot and primary development direction for the current
oil-displacing surfactants [8,9].
As the second abundant renewable resource in the nature, lignin is a
kind of biopolymer composed by benzene propane monomer on earth
after cellulose [10–12], which is expected to play an important role in
⁎ Corresponding authors.
E-mail addresses: zhouyj@mail.tsinghua.edu.cn (Y. Zhou), zhangja@tsinghua.edu.cn
(J. Zhang).
the near future as a raw material for the production of bio-products.
Most industrial lignins are produced as a by-product during the paper
pulping process with a large volume of approximate 50 million tons
each year [13]. And the majority of them are burnt or drained directly
into rivers and lakes as waste, which not only cause the waste of re-
sources but also seriously pollute the environment [14,15]. In addition,
the molecular structure of lignin on the benzene ring and the side chains
contains a number of different functional groups, such as methoxyl
group (–OCH3), hydroxyl (–OH), carbonyl group (–CO–), alkyl and so
on, which can be modified through a variety of chemical reactions
[16–18]. The water solubility and interfacial activity of lignin will be af-
fected by the introduction of the hydrophilic and lipophilic groups [19,
20]. Therefore, the surfactants synthesized from the biodegradable
and low-cost lignin will be one of the most promising applications in
EOR.
Lignosulfonate is the first surface active component applied in sur-
factant flooding, but the industrial lignosulfonate has strong hydrophilic
groups without long-chain of lipophilic group, which leads to the inhibi-
tion of interfacial activity of lignosulfonate [21]. Therefore, the lignosul-
fonate cannot decrease the IFT to ultralow level (b 10− 3 mN/m)
between oil and water when used alone, it usually need to be
compounded with other main surfactants to form oil-displacing surfac-
tants with better interfacial performance [22,23]. In order to improve
the interfacial performance of the surfactants synthesized from lignin,

https://doi.org/10.1016/j.molliq.2017.11.021
0167-7322/© 2017 Elsevier B.V. All rights reserved.
74 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82
a wide range of synthesis techniques such as sulfonated, alkylation, ox-
idation, amination and carbonylation have been developed to alter the
molecular structure of alkali lignin [24–28]. However, most of these
methods can only improve the oil-soluble of lignin surfactants and
the existing lignin surfactants are in general relatively hydrophilic,
the modified lignin surfactants used alone still cannot decrease the
IFT of oil-water to ultralow level. Moreover, multiple steps, the
high modification cost and special equipments are also needed in
these techniques.
In the last decade zwitterionic surfactants have attracted the atten-
tion of researchers for their adaptability in EOR [29–31]. The superior
properties of zwitterionic surfactants, such as good biodegradability,
salt resistance, high temperature resistance, good water solubility and
enough lipophilicity and good synergistic effect with some nonionic
and anionic surfactants, which enable them to be effective on increasing
the oil recovery efficiency [32–34]. At present, there are many different
zwitterionic surfactants synthesized and the demand for this kind of
surfactant is increasing each year. However, the relatively high cost of
zwitterionic surfactants limits their large-scale application in EOR com-
pared to other types of surfactants. At present, the synthesis and per-
formance research of zwitterionic surfactants are the focus of
attention for researchers, and little attention has been paid to study
and synthesis of zwitterionic surfactants from low-cost and renew-
able lignin. Sulphobetaine and their derivatives are a class of zwitter-
ionic surfactants containing quaternary ammonium cation and
sulfonic acid anion, with excellent stability under acidic and alkaline
conditions.
In the present work, a new cost-efficient and high performance zwit-
terionic surfactants from alkali lignin as raw materials were successfully
synthesized by an economic pathway, in which a three-step procedure
was involved. First, the alkali lignin was selectively oxidized and
sulfonated with hydrogen peroxide and sodium sulfite to obtain the
product lignosulfonate. Second, (2, 3-epoxypropyl) alkyl dimethyl am-
monium chloride (ADAC) was prepared by the reaction of long
alkylchain dimethyl tertiary amine and epichlorohydrin. Last, this inter-
mediate ADAC was subsequently reacted with phenolic hydroxyl
groups of lignosulfonate to synthesize lignin sulphobetaine zwitterionic
surfactant (LSBA). Thus, both long alkylchain and amine functional
groups were introduced into the lignin molecules to improve the sur-
face activity and solubility of lignin surfactants. The structures of target
products LSBA were analyzed by FI-IR, UV and 1H NMR. The hydrophile
lipophile balance (HLB) experiments for LSBA surfactants were exam-
ined. The surface active and interfacial behavior of LSBA surfactants
were also evaluated by surface tension and interfacial tension measure-
ments, respectively.
2. Experimental procedures
2.1. Materials
Alkali lignin was provided by Shandong paper mills of China. Hydro-
gen peroxide (30 wt%), sodium sulfite, epichlorohydrin, sodium hydrox-
ide, sulfuric acid, hydrochloric acid, sodium carbonate, isopropanol and
acetone were purchased from Sinopharm Chemical Reagent Co., Ltd.,
Beijing, China. Decyldimethyl tert-amine, dodecyldimethyl tert-amine,
tetradecyldimethyl tert-amine, p-hydroxybenzoic acid, N, N-
dimethylformamide and tetra-n-butylammonium hydroxide were pur-
chased from Sigma Chemicals. All the chemicals were analytical pure
grade.
Partially hydrolysed polyacrylamide (HPAM, Mw = 1800 × 104) was
given from Beijing Hengju Chemical Group Co., Ltd., China. Two kinds of
dewatered and degassed crude oil were provided by Xinjiang and
Huabei oilfields, China. The density of crude oil from Xinjiang and
Huabei oilfields was 0.85 g/cm3 and 0.78 g/cm3, respectively. The ionic
composition of simulated brine from different oilfields was shown in
Table 1.
Table 1
Composition of simulated brine from Huabei and Xinjiang oilfields, China.
Oilfield Ca2+ Mg2+ Na+ K+ Cl− SO2−
4 CO2−
3 HCO−
3
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
Huabei 53.6 22.0 3900.7 32.2 4737.5 117.5 – 1925.9
Xinjiang 56.9 13.4 2085.0 – 2577.0 131.6 5.8 1156.9
2.2. Methods
2.2.1. Synthesis of oxidized sulfonated lignin
The quantitative lignin (40 g) dissolved with 300 mL deionized
water was added into a three-necked round-bottom flask equipped
with a stirrer. After the pH of solution being adjusted to 12 with sodium
hydroxide solution, 6 g hydrogen peroxide was added into the flask at
70 °C for 1 h with stirring. Then the sodium sulfite (8 g) was added
into the reactor and the reaction continued for 1 h at 180 °C. After the
reaction, the pH of resulting mixture was adjusted to 2 with dilute sul-
furic acid and the precipitation was separated by centrifuge. Thus, a
brown power of oxidized sulfonated lignin was obtained after drying
in a vacuum oven.
2.2.2. Synthesis of (2, 3-epoxypropyl) alkyl dimethyl ammonium chloride
The epichlorohydrin (9.25 g) and hydrochloric acid (4.38 g) were
added into a three-necked round-bottom flask and agitated at 25 °C
for 30 min, then decyldimethyl tert-amine (18.54 g) was added
dropwise in 20 min after the reaction temperature was went up to 40
°C. After that, the pH of the mixed solution was adjusted to 9 with sodi-
um hydroxide solution and the reaction continued for 2 h at 50 °C. Thus
the intermediate (2, 3-epoxypropyl) decyldimethyl ammonium chlo-
ride (ADAC-1) was obtained after cooling to room temperature.
By varying the carbon chain length of tertiary amine, the intermedi-
ates ADAC-2 and ADAC-3 were synthesized according to the above syn-
thetic pathway using the dodecyldimethyl tert-amine and the
tetradecyldimethyl tert-amine, respectively.
2.2.3. Synthesis of lignin sulphobetaine zwitterionic surfactant
In a 500 mL round-bottom flask, 25.4 g oxidized sulfonated lignin
which was dissolved in 200 mL acetone was added and the temperature
of the mixture was raised to 40 °C gradually. Then the pH of solution
was adjusted to 12 by adding sodium hydroxide and insulation for
30 min in order to fully dissolve the oxidized sulfonated lignin in ace-
tone. After that, the intermediate ADAC-1 (30.81 g) was added
dropwise into the flask with stirring after the reaction temperature in-
creased up to 50 °C and the reaction was carried out for 2.5 h at 50 °C.
After removing the solvents by rotary evaporator under reduced pres-
sure, the 200 mL isopropanol was added into the mixture and refluxed
at 70 °C for 3 h to filter off inorganic salts. Then the mixture was neutral-
ized by distilled water and dried in a vacuum oven at 60 °C for 20 h, a
light brown solid powder of lignin sulphobetaine zwitterionic surfac-
tant (LSBA-1) was obtained.
The products LSBA-2 and LSBA-3 were synthesized according to the
above synthetic method using the intermediates ADAC-2 and ADAC-3,
respectively.
2.2.4. Chemical analysis
Fourier transform infrared spectroscopy (FT-IR) (Thermo 6700,
USA) was employed to characterize the structures of alkali lignin and
synthesized LSBA surfactant by potassium bromide (KBr) pellet method
in the range of 500 cm−1 to 4000 cm−1 with a resolution of 4 cm−1. Ul-
traviolet spectrum (UV) measurements were performed in a Lambda
UV–Visible Spectrometer (Perkin-Elmer co., America). Element analyses
of alkali lignin and LSBA surfactant were carried out on the Vario ELL III
type element analyzer (Elementar Co., Germany). Nuclear magnetic res-
onance (NMR) spectroscopy was used to obtain the 1H NMR spectra of
 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82 75

100 point, mL; a is the theoretical titer of p-hydroxybenzoic acid in the sam-
ple, mL; c is the concentration of the titrant, mol/L; m is the quality of
sample, mg.
80
2.2.6. Surface tension measurement
Transmittance (%)

60 Surface tension of the samples was determined by a dynamic surface

-1
3430 cm -1 tensiometer QBZY-2 (CANY, China) at 25 ± 0.1 °C with the Wilhelmy
1462 cm
plate method. Before testing, aging time of 30 min was necessary for
40 each sample so that the liquid surfaces reach an equilibrium state.
Three measurements were performed for each sample and the average
value of equilibrium was recorded.
20
-1
2850 cm
-1 2.2.7. HLB measurements
1610 cm
The HLB values of LSBA surfactants were measured using a 100 mL
0
4000 3500 3000 2500 2000 1500 1000 500 cylinder with stopper by the emulsification method. First, the cotton-
seed oil (HLB = 6) and turpentine (HLB = 16) were used to prepare a
-1
wavenumber (cm ) series of standard oil samples, in which the HLB values were 7, 8, 9,
(a) 10, 11, 12, 13, 14, 15, and 16, respectively. Then 25 mL standard oil sam-
ples with different HLB value and 25 mL LSBA (0.4 wt%) solution were
100
added into the cylinder. After that, the cylinder was shaken drastically
-1
910 cm and laid aside until the two phases were separated. The separation
time of oil and water was recorded, and the HLB of tested sample was
80 1210 cm
-1 in keeping with the HLB value of standard oil owned the best emulsify-
ing effect.
Transmittance (%)

-1 2.2.8. IFT measurements

60 3430 cm
The dynamic IFT between synthesized LSBA surfactants in brine and
crude oil was conducted on the SVT20N spinning drop IFT apparatus
(Eastern-Dataphy, China) with the spinning drop technique. Crude oil
40 721 cm
-1 was from Huabei and Xinjiang oilfields of China and the measurements
were taken under the reservoirs temperature of Huabei and Xinjiang
-1 -1
2850 cm 1610 cm -1 oilfields, 54 °C and 28.7 °C, respectively. Each measurement lasted for
2926 cm
-1 1462 cm
1 h until the equilibrium value of IFT was obtained.
20
4000 3500 3000 2500 2000 1500 1000 500
-1 3. Results and discussion
wavenumber (cm )
(b) 3.1. FT-IR analysis

Fig. 1. FT-IR spectra of alkali lignin (a) and the synthesized surfactant LSBA (b). The FT-IR spectra of alkali lignin and synthesized surfactant LSBA
were depicted in Fig. 1. IR spectrum was made up of the adsorption
alkali lignin and synthesized surfactant LSBA using deuterated dimethyl peak which was consistent with the functional group of the sample.
sulfoxide (DMSO-d6) as solvent with the AVANCE III spectrometer And the peaks contributed to acknowledgement for the synthesis of
(500 MHz) (Bruker, France). the product after reaction. Compared with alkali lignin (Fig. 1(a)), the

2.2.5. Phenolic hydroxyl content determination

The non-aqueous potentiometric titration method [35] was used to 0.7
measure the content of phenolic hydroxyl groups in raw materials and 255 nm
the synthesized surfactants. A DDS-11A conductivity tester (Rex, China)
equipped with platinum black electrode was employed for these exper- 0.6 LSBA
iments. First, 350 mg sample and 50 mg p-hydroxybenzoic acid were 300 nm Alkali lignin
added to a 100 mL four-neck flat-bottom flask, then 2 mL distilled
0.5
water, 0.2 mL hydrochloric acid and 60 mL N, N-dimethylformamide sol-
Absorbance

vent were added sequentially into the flask with stirring for 5 min at 25
°C in nitrogen atmosphere. After that, the sample was titrated with tetra- 0.4
n-butylammonium hydroxide standard solution (0.05 mol/L). At the
same time the conductivity curve was recorded until two isoelectric
points appeared. According to the conductivity-titrant dosage curve, 0.3
the isoelectric points were determined by tangent extension method.
The phenolic hydroxyl content was calculated as follows:
0.2


Vz −Vy −a  c
½OH  ¼ ð1Þ 220 240 260 280 300 320 340 360 380 400
m
Wavelength (nm)
where, Vz is the dosage of titrant corresponding to the second isoelectric
point, mL; Vy is the dosage of titrant corresponding to the first isoelectric Fig. 2. UV spectra of alkali lignin and the synthesized surfactant LSBA.
76 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82

absorption band of O\\H in LSBA surfactant at 3430 cm−1 was weak- Table 2
ened due to the phenolic hydroxyl in the feedstock being involved in The determination of phenolic hydroxyl content.

the alkylation reaction (Fig. 1(b)). The peaks at 2926 cm− 1 and Sample Alkali Oxidized sulfonated LSBA-1 LSBA-2 LSBA-3
2850 cm−1 indicated the presence of C\\H stretching vibration in lignin lignin
\\CH2\\ and\\CH3 groups, the absorption band at these regions was Content of phenolic 0.2622 0.1933 0.1261 0.1159 0.1162
broadened because of the introduction of long alkylchain amine. The hydroxyl (mmol/g)
strong and wide absorption peaks at 1610 cm−1 and 1462 cm− 1 re-
vealed the presence of benzene ring in LSBA. The C\\N stretching vibra-
tion absorption seen at 1459 cm−1 in which the peaks were overlapped 3.2. UV analysis
with the peaks of benzene ring, the bending vibration absorption peak
and small absorption peak for C\\N appeared at 721 cm− 1 and The UV absorption spectra of alkali lignin and LSBA surfactant were
1000 cm−1 to 910 cm− 1, respectively. These peaks were consistent shown in Fig. 2. It could be seen that the characteristic absorption ap-
with the characteristic absorption peaks of the quaternary ammonium peared nearby 255 nm and 300 nm in the alkali lignin spectrum,
salt. In addition, the stretching vibration absorption of S_O groups at which was the typical absorption peak of alkali lignin [36]. For the
1370 cm−1 and 1210 cm−1 was present, revealing the introduction of LSBA spectrum, there was no obvious absorption peak except for the
sulfonate group to the alkali lignin molecule. weak absorption band and the UV absorption decreased to different

Fig. 3. 1H NMR spectra of alkali lignin (a) and the synthesized surfactant LSBA (b).
 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82 77

Table 3 70
The determination of nitrogen content.
LSBA-3
Sample Alkali lignin LSBA-1 LSBA-2 LSBA-3 LSBA-2
60
Nitrogen content (mmol/g) 0.3142 1.5357 1.6143 1.6753 LSBA-1

Surface tension (mN/m)

50
degrees. The absorption peak associated with the phenolic hydroxyl
group of alkali lignin disappeared nearby 255 nm and 300 nm in the
LSBA spectrum. As a result of comprehensive FT-IR spectra, it was 40
found that most of the phenolic hydroxyl groups in the alkali lignin
were consumed in the reaction. This proved that the phenolic hydroxyl
groups of alkali lignin had been etherified with the intermediates, indi- 30
cating that the quaternary ammonium groups were introduced to the
phenolic hydroxyl groups of the oxidized sulfonated lignin.
20
1
-4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5
3.3. H NMR analysis
Log c
The chemical shifts in 1H NMR spectra of alkali lignin and synthe-
sized LSBA surfactant were obtained as shown in Fig. 3. The 1H NMR Fig. 5. The plots of surface tension versus log C (concentration of surfactant in g/L) at 25 °C.

spectra could be used to confirm the molecule structure of compounds

because of each hydrogen element of the sample could produce a corre-
sponding absorption peak in the 1H NMR spectra. In Fig. 3(a) all the
peaks ranging from δ 0.5 to 0.95 ppm were related to the methyl proton
(CH3C–). The methylene proton (–CCH2C-) and methine proton (–
CCHR2) were shown at δ 1.0–1.3 ppm and δ 1.4 ppm, respectively. The
peak at δ 2.5 ppm was due to DMSO-d6. The intense peak centered at
δ 3.4 ppm was attributed to the methoxy protons (–OCH3). The peaks
appearing in the range of δ 6.0 to 7.5 ppm were due to the aromatic pro-
tons in alkali lignin. In LSBA surfactant, the peaks ranging from δ 0.6 to
1.4 ppm were obviously enhanced, which proved that the long
alkylchain lipophilic group containing a large number of methyl and
methylene groups was introduced after the alkylation reaction
(Fig. 3(b)). The methyl proton at (CH3N+) and the methylene proton
at (RCH2N+) for quaternary ammonium ion were shown ranging from
δ 3.0 to 4.0 ppm and they had partial overlap, which also confirmed
that the quaternary ammonium groups were introduced into the chem-
ical structure of LSBA surfactant. The peak at δ 4.3 ppm was due to the
proton of methylene group attached to the benzene ring and sulfonate
group, indicating the introduction of sulfonate group to the alkali lignin
molecule.

200 140
180
120
160
140 100
120 80
Time (min)

Time (min)

100
80 60

60 40
40
20
20
0 0
7 8 9 10 11 12 13 14 15 16 7 8 9 10 11 12 13 14 15 16
HLB value HLB value

(a) (b)
300

250

200
Time (min)

150

100

50

0
7 8 9 10 11 12 13 14 15 16
HLB value

(c)
Fig. 4. HLB values of the synthesized surfactants LSBA-1 (a), LSBA-2 (b) and LSBA-3 (c).
78 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82

Table 4 amine was introduced into the oxidized sulfonated lignin. Therefore
The calculated surface activity parameters of LSBA surfactants at 25 °C. the nitrogen content in the lignin sulphobetaine could be used as an in-
Sample LSBA-1 LSBA-2 LSBA-3 dicator of product yields. The nitrogen contents of alkali lignin, LSBA-1,
Ccmc (mg/L) 4.36 × 10−4 4.45 × 10−4 1.04 × 10−3
LSBA-2 and LSBA-3 were measured and the results were shown in
γcmc (mN/m) 30.29 25.97 27.87 Table 3. It was seen that the nitrogen contents of LSBA obtained after
Γmax (mol/cm2) 8.08 × 10−10 6.53 × 10−10 6.44 × 10−10 modification increased obviously compared to that of alkali lignin. The
Amin (nm2) 0.21 0.25 0.26 molecular weights of LSBA-1 and LSBA-2 were lower than that of
LSBA-3, but the nitrogen content of LSBA-3 was relatively higher com-
pared with the other two. This indicated that the yield of LSBA-3 was
3.4. Phenolic hydroxyl content measurement higher than that of LSBA-1 and LSBA-2.

The phenolic hydroxyl contents of alkali lignin, oxidized sulfonated 3.6. HLB measurement
lignin and synthesized surfactants LSBA were given in Table 2. It was
found that the phenolic hydroxyl content of oxidized sulfonated lignin HLB value is a crucial indicator which represents the hydrophilic or
was lower than that of alkali lignin. The benzene ring of alkali lignin un- lipophilic degree of surfactants to some extent. The stronger the hydro-
dergone a certain degree of damage after oxidation reaction and some of philicity of the surfactant, the higher the HLB value, and vice versa. And
the hydroxyl groups were oxidized, leading to a decrease of phenolic the HLB value is related to the interfacial properties of the surfactant [37,
hydroxyl content in oxidized sulfonated lignin. The phenolic hydroxyl 38]. The surfactant with more hydrophilic is not beneficial for the ad-
contents of LSBA-1, LSBA-2 and LSBA-3 were 0.1261 mmol/g, sorption of surfactant molecules on the gas/liquid interface, whereas
0.1159 mmol/g and 0.1162 mmol/g, respectively. It indicated that the surfactant with more lipophilic cannot be dissolved in water. Therefore,
phenolic hydroxyl groups of oxidized sulfonated lignin were involved the surfactants with suitable HLB values can be used in practical applica-
in the reaction with the intermediates ADAC in the subsequent chemical tions for EOR [39].
modification, resulting in a decline of the phenolic hydroxyl content in The HLB values for LSBA-1, LSBA-2 and LSBA-3 were measured and
the products. The slight difference of phenolic hydroxyl content the results were shown in Fig. 4. It could be seen that the HLB values
among LSBA-1, LSBA-2 and LSBA-3 was due to the errors of measured of LSBA-2 and LSBA-3 were 11 and 10, respectively. According to the re-
values caused by the different chain length of surfactants. lationship between HLB value and the physicochemical properties of
surfactant [40], the HLB values of LSBA-2 and LSBA-3 being in the
range of 8–13 indicated that they had good emulsification in O/W sys-
3.5. Nitrogen content measurement tem. The HLB value of LSBA-1 was 14, which was in the range of
12–15 and therefore exhibited good wetting performance. Although
The nitrogen content in the lignin sulphobetaine would be increased the lipophilic group of straight alkylchain was attached to the lignin
after alkylation reaction in which the long alkylchain dimethyl tertiary molecule, the amino acid in acidic conditions could produce ammonium

10 10
LSBA-1 (0.6 wt%) LSBA-2 (0.6 wt%)
LSBA-1 (0.4 wt%) LSBA-2 (0.4 wt%)
LSBA-1 (0.2 wt%) LSBA-2 (0.2 wt%)
Interfacial tension (mN/m)

LSBA-1 (0.1 wt%) 1 LSBA-2 (0.1 wt%)

Interfacial tension (mN/m)

0.1

0.1
0.01

0.01 1E-3
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)

(a) (b)
100
Interfacial tension (mN/m)

10

LSBA-3 (0.6 wt%)

0.1
LSBA-3 (0.4 wt%)
LSBA-3 (0.2wt%)
LSBA-3 (0.1 wt%)
0.01
0 10 20 30 40 50 60
Time (min)

(c)
Fig. 6. Concentration effects of LSBA-1 (a), LSBA-2 (b) and LSBA-3 (c) on the IFT between Huabei crude oil and brine at 54 °C.
 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82 79

salt because of the introduction of more hydrophilic amino and sulfonic As shown in Table 4, the cmc values of LSBA-1 and LSBA-2 were 4.36
acid groups at the same time. And the HLB value of LSBA-1 was higher × 10− 4 mg/L and 4.45 × 10−4 mg/L, which was smaller than that of
than that of the other two surfactants due to the introduction of shorter LSBA-3 (1.04 × 10−3 mg/L). This indicated that LSBA-1 and LSBA-2
alkyl carbon chains. were prone to forming micelles in solution compared to LSBA-3. The
minimum surface tension values of LSBA-1, LSBA-2 and LSBA-3 at cmc
3.7. Critical micelle concentration (cmc) and surface tension (γcmc) were 30.29 mN/m, 25.97 mN/m and 27.87 mN/m, respectively. The
LSBA surfactant molecules could aggregate to form micelles in solution
The surface tension measurements for the solutions were conducted at lower concentrations due to the introduction of long chain lipophilic
on the dynamic surface tensiometer at 25 °C and the results were shown groups, thus the surface activity of the modified lignin sulphobetaine
in Fig. 5. It could be seen that the surface tension gradually decreased surfactant was obviously improved. For LSBA-1, the value of surface ex-
and then tended to a stable region with the increase of LSBA concentra- cess concentration Γmax was slightly higher than that of LSBA-2 and
tion. The excessive surfactant molecules would form micelles in aque- LSBA-3 while the value of area per molecule Amin was lower than that
ous solutions when the break point appeared in the curves, and the of LSBA-2 and LSBA-3. It could be attributed to the proportion of hydro-
further increase of surfactant concentration had little impact on the sur- philic head group in LSBA-1 molecule was larger compared to that of
face tension of solution, and thus the surfactant tension remained al- LSBA-2 and LSBA-3. In addition, the zwitterionic surfactant with positive
most constant. charge would cause a smaller repulsion between the molecules, forming
The cmc values of LSBA-1, LSBA-2 and LSBA-3 were calculated from a closer surfactant adsorption layer at the air/water interface, and the
the break point of the curves for each sample as depicted in Fig. 5. The hydrophobic carbon chains of surfactant would be partially overlapped.
surface adsorption parameters including maximum surface excess con-
centration (Γmax) and area per molecule (Amin) were evaluated accord- 3.8. IFT measurements
ing to Gibbs adsorption equation. And the results were listed in Table 4.
It is well known that the ultralow IFT is an important indicator for
   
1 dγ 1 dγ the successful application of surfactant flooding in EOR. The IFT of oil/
Γ max ¼− ¼− ð2Þ water interface is strongly influenced by many factors, such as the
RT d lnC T 2:303RT d logC T
type and concentration of surfactants, the temperature of reservoir,
the salinity of liquid phase and the alkane carbon number in the crude
Amin ¼ ðΓ max NA Þ−1 ð3Þ oil [41,42]. In this work, the effects of surfactant LSBA concentration
on the IFT were first investigated at 54 °C between Huabei crude oil
where, Γmax is the maximum surface excess concentration, R is the gas and brine, without addition of any polymers, alkaline reagents and co-
constant, T is the temperature in Kelvin, γ is the surface tension, C is surfactants. The dynamic IFT between Huabei crude oil and brine con-
the surfactant concentration, Amin is the area per molecule and NA is taining lignin sulphobetaine (LSBA-1, LSBA-2 and LSBA-3) at the con-
the Avogadro constant. centration varying from 0.1 wt% to 0.6 wt% was illustrated in Fig. 6. As

1 1
LSBA-1 (0.4 wt%) LSBA-2 (0.4 wt%)
LSBA-1 (0.4 wt%)+Na2CO3(0.2 wt%) LSBA-2 (0.4 wt%)+Na2CO3(0.2 wt%)
LSBA-1 (0.4 wt%)+Na2CO3(0.4 wt%) LSBA-2 (0.4 wt%)+ Na2CO3(0.4 wt%)
0.1 LSBA-2 (0.4 wt%)+Na2CO3(0.8 wt%)
Interfacial tension (mN/m)

LSBA-1 (0.4 wt%)+Na2CO3(0.8 wt%)

Interfacial tension (mN/m)

0.1

0.01

0.01
1E-3
-3
IFT < 10 mN/m

1E-4 1E-3
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Time (min) Time (min)

(a) (b)
10

1
Interfacial tension (mN/m)

0.1

0.01 LSBA-3 (0.4 wt%)

LSBA-3 (0.4 wt%)+Na2CO3(0.2 wt%)
LSBA-3 (0.4 wt%)+Na2CO3(0.4 wt%)
LSBA-3 (0.4 wt%)+Na2CO3(0.8 wt%)
1E-3
0 10 20 30 40 50 60 70
Time (min)

(c)
Fig. 7. Effects of Na2CO3 concentration on the IFT between LSBA-1 (a), LSBA-2 (b), LSBA-3 (c) and Huabei crude oil at 54 °C.
80 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82

1 1
LSBA-1 (0.4 wt%)
LSBA-1 (0.4 wt%)+Na2CO3(0.2 wt%)
LSBA-1 (0.4 wt%)+Na2CO3(0.4 wt%)
0.1 LSBA-1 (0.4 wt%)+Na2CO3(0.8 wt%) 0.1
Interfacial tension (mN/m)

Interfacial tension (mN/m)

0.01 0.01

1E-3 -3
IFT < 10 mN/m 1E-3 -3
LSBA-2 (0.4 wt%)
IFT < 10 mN/m LSBA-2 (0.4 wt%)+Na2CO3(0.2 wt%)
LSBA-2 (0.4 wt%)+Na2CO3(0.4 wt%)
LSBA-2 (0.4 wt%)+Na2CO3(0.8 wt%)
1E-4 1E-4
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)

(a) (b)
1
LSBA-3 (0.4 wt%)
LSBA-3 (0.4 wt%)+Na2CO3(0.2 wt%)
LSBA-3 (0.4 wt%)+Na2CO3(0.4 wt%)
0.1 LSBA-3 (0.4 wt%)+Na2CO3(0.8 wt%)
Interfacialtension (mN/m)

0.01

1E-3 -3
IFT < 10 mN/m

1E-4
0 10 20 30 40 50 60
Time (min)

(c)
Fig. 8. Effects of Na2CO3 concentration on the IFT between LSBA-1 (a), LSBA-2 (b), LSBA-3 (c) and Xinjiang crude oil at 28.7 °C.

shown in Fig. 6(a), the IFT decreased to 10−2 mN/m within 20 min and In general, when the interactions of surfactant film at the oil/water
the equilibrium IFT was achieved when the LSBA-1 concentration was interface are balanced, the IFT of oil/water can be decreased to ultralow.
0.4 wt%. And the IFT was much lower than those used with other surfac- It is usually difficult to obtain ultralow IFT using a single surfactant alone
tant concentrations. Similar interfacial activity was found with LSBA-2 and alkali is occasionally added to the surfactant solution to reduce the
and LSBA-3, though the equilibrium IFT was 10−1 mN/m level for the IFT [43]. The influences of weak alkali sodium carbonate (Na2CO3) on
0.4 wt% LSBA-3. The results showed that the ability of surfactants on re- the IFT were investigated at 54 °C between Huabei crude oil and brine,
ducing IFT was related to the surfactant concentration, and however, IFT and the results were shown in Fig. 7. The surfactant with a fixed concen-
of water/oil could not be further decreased with higher surfactant con- tration of 0.4 wt% and the Na2CO3 concentrations ranging from 0.2 wt%
centration. The lowest IFT between Huabei crude oil and brine could be to 0.8 wt% were included in the chemical solution. It was seen that dy-
achieved with the appropriate surfactant concentration (0.4 wt%). namic IFT of LSBA-1/crude oil decreased after adding Na2CO3 into solu-
tion compared to that of LSBA-1 solely (Fig. 7(a)). And the IFT of LSBA-1/
1 crude oil decreased with increasing the Na2CO3 concentration. When
the concentration of Na2CO3 was 0.4 wt%, the equilibrium IFT of LSBA-
surfactant 1/crude oil could reach 10−3 mN/m in 10 min. The effects of Na2CO3
surfactant/polymer on the IFT of LSBA-2/crude oil and LSBA-3/crude oil were analogous to
0.1 that of LSBA-1/crude oil (Fig. 7(b) and Fig. 7(c)). In addition, the IFT be-
Interfacial tension (mN/m)

tween LSBA-1 and Huabei crude oil was much more stable and lower
than that of LSBA-2 and LSBA-3 under the same Na2CO3 concentration.
It had been recognized that the alkali could effectively reduce the IFT be-
0.01 tween oil and water due to synergistic effect between the substance
produced in situ by the reaction of acidic components in crude oil
with alkali and the surfactant in solution [44–46].
1E-3 -3 In order to further understand the influence of crude oil on the IFT,
IFT < 10 mN/m
the IFT measurements between Xinjiang crude oil and brine at 28.7 °C
were conducted under different Na2CO3 concentrations. As shown in
Fig. 8(a), the dynamic IFT of each system gradually decreased to the
1E-4 equilibrium value and held for the remaining time. The IFT of Xinjiang
0 10 20 30 40 50 60 crude oil/brine reduced as the increase of Na2CO3 concentration. And
Time (min) the ultra-low IFT was obtained for LSBA-1 with 0.8 wt% Na2CO3. This in-
terfacial behavior was similar to that of LSBA-2 and LSBA-3 in the pres-
Fig. 9. The IFT between Xinjiang crude oil and the brine solutions of the LSBA-3 (0.4 wt%) ence of Na2CO3. Especially, the IFT between LSBA-3 and Xinjiang crude
or the mixed LSBA-3 (0.4 wt%)/HPAM (0.1 wt%) at 28.7 °C. oil could reach ultra-low values with the range of Na2CO3 concentration
 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82
from 0 to 0.8 wt%. The more effective surfactant molecules were
adsorbed on the oil/water interface, a lower interfacial tension was
achieved according to the Gibbs adsorption theory. The results indicated
that the LSBA surfactants exhibited stable and better interfacial behavior
on Xinjiang crude oil compared to that of Huabei crude oil.
In the practical application of surfactant flooding in EOR, polymers
were usually introduced into the surfactant solution to increase the vis-
cosity of displacement formula, thereby increasing the swept volume of
flooding solution and improving the oil displacement efficiency [47,48].
The effect of additional HPAM (0.1 wt%) on the IFT between Xinjiang
crude oil and brine containing 0.4 wt% LSBA-3 was investigated. As
shown in Fig. 9, there was a slight increase in the IFT of surfactant/poly-
mer system compared to that of individual surfactant system. The poly-
mer molecules with weak interfacial activity in solution could be
adsorbed on the oil/water interface and affected the adsorption density
of surfactant molecules on the interface, resulting in a slight increase of
IFT. Furthermore, the surfactant/polymer system with high viscosity
slowed the adsorption rate of surfactant molecules on the interface,
leading to a longer time to reach stable IFT. However, the values of equi-
librium IFT for both systems were in the same order of magnitude even
if the additional polymer affected the ordered arrangement of surfactant
molecules on the oil/water interface.
4. Conclusions
In this work, a series of lignin sulphobetaine zwitterionic surfactants
were synthesized through sulfonation, quaternization and alkylation re-
action with low-cost and renewable alkali lignin as raw materials. FT-IR
spectrum, UV spectrum and 1H NMR spectrum were employed to con-
firm the structure of lignin sulphobetaine surfactants. The HLB values
of LSBA-1, LSBA-2 and LSBA-3 were 14, 11 and 10, which indicated
that the synthesized lignin sulphobetaine surfactants were relatively
hydrophilic if the carbon chain length of incoming tertiary amine was
relatively short. The lignin sulphobetaine surfactants showed high sur-
face activity with low surface tension and the cmc of LSBA-1, LSBA-2
and LSBA-3 were 4.36 × 10− 4 mg/L, 4.45 × 10−4 mg/L and 1.04
× 10−3 mg/L, respectively.
For Huabei crude oil, the lowest IFT could be achieved at the appro-
priate surfactant concentration (0.4 wt%). LSBA-1 could effectively de-
crease the IFT between Huabei crude oil and brine down to 10−3 mN/
m with 0.4 wt% Na2CO3. Similar interfacial activities were found with
LSBA-1 and LSBA-2 for Xinjiang crude oil. Especially, LSBA-3 could re-
duce the IFT between Xinjiang crude oil and brine to ultra-low level in
the absence of alkali, exhibiting satisfactory interfacial activity on
Xinjiang crude oil. In addition, the additional polymer had little impact
on the reducing ability of IFT between Xinjiang crude oil and brine
with LSBA-3. The present study demonstrated that the synthesized sur-
factant LSBA could be used as a prominent candidate for the practical
application of surfactant flooding in EOR.
Acknowledgements
This work was supported by the National Key Technology Support
Program (grant numbers 2014BAD02B03); the National Key R&D Pro-
gram of China (grant numbers 2016YFE0131300).
References
[1] A.A. Adasani, B. Bai, Analysis of EOR projects and updated screening criteria, J. Pet.
Sci. Eng. 79 (2011) 10–24.
[2] B. KošiKová, M. Ďuriš, V. Demianová, Conversion of lignin biopolymer into surface-
active derivatives, Eur. Polym. J. 36 (2000) 1209–1212.
[3] T. Austad, S. Ekrann, I. Fjelde, K. Taugbøl, Chemical flooding of oil reservoirs Part 9.
Dynamic adsorption of surfactant onto sandstone cores from injection water with
and without polymer present, Colloids Surf. A Physicochem. Eng. Asp. 127 (1997)
69–82.
81
[4] P. Jiang, N. Li, J.J. Ge, G.C. Zhang, Y. Wang, L.F. Chen, L. Zhang, Efficiency of a
sulfobetaine-type surfactant on lowering IFT at crude oil–formation water interface,
Colloids Surf. A Physicochem. Eng. Asp. 443 (2014) 141–148.
[5] N. Li, G. Zhang, J. Ge, L. Zhang, X. Liu, J. Wang, Ultra-low interfacial tension between
heavy oil and betaine-type amphoteric surfactants, J. Dispers. Sci. Technol. 33
(2012) 258–264.
[6] S.Y. Chen, Q.F. Hou, G.Q. Jian, Y.Y. Zhu, Y.S. Luo, Z. Wang, W.J. Li, Synthesis and per-
formance evaluation of novel alcohol ether carboxylate surfactants for alkali-
surfactant-polymer flooding, Int. J. Oil Gas Coal T. 7 (2014) 52–67.
[7] Z.H. Wang, T.Y. Yu, X.Y. Lin, X.W. Wang, L.S. Su, Chemicals loss and the effect on for-
mation damage in reservoirs with ASP flooding enhanced oil recovery, J. Nat. Gas.
Sci. Eng. 33 (2016) 1381–1389.
[8] S.M. Lee, J.Y. Lee, H.P. Yu, J.C. Lim, Synthesis of environment friendly nonionic surfac-
tants from sugar base and characterization of interfacial properties for detergent ap-
plication, J. Ind. Eng. Chem. 38 (2016) 157–166.
[9] B.L. Song, X. Hu, X.Q. Shui, Z.G. Cui, Z.J. Wang, A new type of renewable surfactants
for enhanced oil recovery: dialkylpolyoxyethylene ether methyl carboxyl betaines,
Colloids Surf. A Physicochem. Eng. Asp. 489 (2016) 433–440.
[10] P. Alvira, E. Tomás-Pejó, M. Ballesteros, M.J. Negro, Pretreatment technologies for an
efficient bioethanol production process based on enzymatic hydrolysis: a review,
Bioresour. Technol. 101 (2010) 4851–4861.
[11] S.M. Roopan, An overview of natural renewable bio-polymer lignin towards nano
and biotechnological applications, Int. J. Biol. Macromol. 103 (2017) 508–514.
[12] J.H. Lora, W.G. Glasser, Recent industrial applications of lignin: a sustainable alterna-
tive to nonrenewable materials, J. Polym. Environ. 10 (2002) 39–48.
[13] A. Vishtal, A. Kraslawski, Challenges in industrial applications of technical lignins,
Bioresources 6 (2011) 3547–3568.
[14] H. Hatakeyama, T. Hatakeyama, Lignin structure, properties, and applications, Adv.
Polym. Sci. 232 (2010) 1–63.
[15] M.A. Lara, A.J. RodriGuez-Malaver, O.J. Rojas, O. Holmquist, A.M. González, J. Bullón,
N. Peñaloza, E. Araujo, Blackliquor lignin biodegradation by Trametes elegans, Int.
Biodeterior. Biodegrad. 52 (2003) 167–173.
[16] M.V. Alonso, M. Oliet, J.M. Perez, F. Rodriguez, J. Echeverria, Determination of curing
kinetic parameters of lignin-phenol-formaldehyde resole resins by several dynamic
differential scanning calorimetry methods, Thermochim. Acta 419 (2004) 161–167.
[17] N. Cachet, S. Camy, B. Benjelloun-Mlayah, J.S. Condoret, M. Delmas, Esterification of
organosolv lignin under supercritical conditions, Ind. Crop. Prod. 58 (2014)
287–297.
[18] P. Cinelli, I. Anguillesi, A. Lazzeri, Green synthesis of flexible polyurethane foams
from liquefied lignin, Eur. Polym. J. 49 (2013) 1174–1184.
[19] S.Y. Chen, S.C. Shen, X. Yan, J. Mi, G.H. Wang, J.A. Zhang, Y.J. Zhou, Synthesis of sur-
factants from alkali lignin for enhanced oil recovery, J. Dispers. Sci. Technol. 37
(2016) 1574–1580.
[20] H. Sun, Q. Liu, S.Y. Chen, X. Yan, L.M. Dai, Y.J. Zhou, J.A. Zhang, Study on synthesis and
performance of lignin polyether sulfonate surfactants for enhanced oil recovery, J.
Dispers. Sci. Technol. 38 (2017) 1124–1128.
[21] Y.H. Jiao, Z.G. Xu, W.H. Qiao, Z.S. Li, L.B. Cheng, Research on synthesis and perfor-
mance of novel modified lignosulfonate surfactants, J. Dalian Univ. Technol. 44
(2004) 44–47.
[22] V. Hornof, G. Neale, P. Bourgeois, Synergistic surfactant mixtures containing ligno-
sulfonates, Can. J. Chem. Eng. 59 (1981) 554–556.
[23] V. Hornof, G. Neale, F. Jacovella, Enhancement of interfacial activity of petroleum
sulfonates by addition of sulphite, Can. J. Chem. Eng. 60 (1982) 33–332.
[24] X.P. Ouyang, Z.X. Lin, Y.H. Deng, Oxidation degradation of soda lignin assisted by mi-
crowave irradiation, Chin. J. Chem. Eng. 18 (2010) 695–702.
[25] A. Mancera, V. Fierro, A. Pizzi, Physicochemical characterization of sugar cane ba-
gasse lignin oxidized by hydrogen peroxide, Polym. Degrad. Stab. 95 (2010)
470–476.
[26] S.A. Gundersen, M.H. Ese, J. Sjoblom, Langmuir surface and interface films of ligno-
sulfonates and Kraft lignins in the presence of electrolyte and asphaltenes: correla-
tion to emulsion stability, Colloids Surf. A Physicochem. Eng. Asp. 182 (2001)
199–218.
[27] C. Asada, S. Basnet, M. Otsuka, C. Sasaki, Y. Nakamura, Epoxy resin synthesis using
low molecular weight lignin separated from various lignocellulosic materials, Int.
J. Biol. Macromol. 74 (2015) 413–419.
[28] G. Sivasankarapillai, A.G. McDonald, Synthesis and properties of lignin-highly branched
poly (ester-amine) polymeric systems, Biomass Bioenergy 35 (2011) 919–931.
[29] L.Y. Qi, Y. Fang, Z.Y. Wang, N. Ma, L.Y. Jiang, Y.Y. Wang, Synthesis and physicochem-
ical investigation of long alkylchain betaine zwitterionic surfactant, J. Surfactant
Deterg. 11 (2008) 55–59.
[30] Q.Q. Zhang, B.X. Caia, W.J. Xua, H.Z. Gang, J.F. Liu, S.Z. Yang, B.Z. Mu, Novel zwitter-
ionic surfactant derived from castor oil and its performance evaluation for oil recov-
ery, Colloids Surf. A Physicochem. Eng. Asp. 483 (2015) 87–95.
[31] T. Yoshimura, T. Ichinokawa, M. Kaji, K. Esumi, Synthesis and surface-active proper-
ties of sulfobetaine-type zwitterionic gemini surfactants, Colloids Surf. A
Physicochem. Eng. Asp. 273 (2006) 208–212.
[32] A. Kumar, A. Mandal, Synthesis and physiochemical characterization of zwitterionic
surfactant for application in enhanced oil recovery, J. Mol. Liq. 243 (2017) 61–71.
[33] A. Mafi, D. Hu, K.C. Chou, Interactions of sulfobetaine zwitterionic surfactants with
water on water surface, Langmuir 32 (2016) 10905–10911.
[34] F. Li, G.Z. Li, J.B. Chen, Synergism in mixed zwitterionic-anionic surfactant solutions
and the aggregation numbers of the mixed micelles, Colloids Surf. A Physicochem.
Eng. Asp. 145 (1998) 167–174.
[35] H. Pobiner, Improved inflection points in the non-aqueous potentiometric titration
of acid functionalities in lignin chemicals by using internal standardization and
ion exchange, Anal. Chim. Acta 155 (1983) 57–65.
82 S. Chen et al. / Journal of Molecular Liquids 249 (2018) 73–82
[36] R.C. Sun, Q. Lu, X.F. Sun, Physico-chemical and thermal characterization of lignins
from Caligonum monogoliacum and Tamarix spp, Polym. Degrad. Stab. 72 (2001)
229–238.
[37] S. Paria, K.C. Khilar, A review on the experimental studies of surfactant adsorption at
the hydrophilic-solid interface, Adv. Colloid Interf. 110 (2004) 75–95.
[38] E. Carrero, N.V. Queipo, S. Pintos, L.E. Zerpa, Global sensitivity analysis of alkali-
surfactant-polymer enhanced oil recovery process, J. Pet. Sci. Eng. 58 (2007) 30–42.
[39] Y.Y. Zhu, P.P. Shen, Synthesis, Properties and Application of Chemical Combination
Flooding Surfactants, first ed. Petroleum Industry Press, Beijing, 2002.
[40] H. Schott, J. Pharm, Solubility parameter and hydrophilic-lipophilic balance of non-
ionic surfactants, J. Pharm. Sci. 73 (1984) 790–792.
[41] S. Kumar, A. Mandal, Studies on interfacial behavior and wettability change phe-
nomena by ionic and nonionic surfactants in presence of alkalis and salt for en-
hanced oil recovery, Appl. Surf. Sci. 372 (2016) 42–51.
[42] K. Wang, H.Q. Yin, W. Sha, J.B. Huang, H.L. Fu, Temperature-sensitive aqueous sur-
factant two-phase system formation in cationic-anionic surfactant systems, J. Phys.
Chem. B 111 (2007) 12997–13005.
[43] J. Rudin, D.T. Wasan, Mechanisms for lowering of interfacial tension in alkali/acidic
oil systems 2. Theoretical studies, Colloids Surf. A Physicochem. Eng. Asp. 68 (1992)
81–94.
[44] A. Samanta, K. Ojha, A. Mandal, Interactions between acidic crude oil and alkali and
their effects on enhanced oil recovery, Energy Fuel 24 (2011) 1642–1649.
[45] Y. Touhami, D. Rana, V. Hornof, G.H. Neale, Effects of added aurfactant on the dy-
namic interfacial tension behavior of acidic oil/alkaline systems, J. Colloid Interface
Sci. 239 (2001) 226–229.
[46] M. Nedjhioui, N. Moulai-Mostefa, A. Morsli, A. Bensmaili, Combined effects of poly-
mer/surfactant/oil/alkali on physical chemical properties, Desalination 185 (2005)
543–550.
[47] X.H. Cui, L. Zhang, L. Luo, L. Zhang, S. Zhao, J.Y. Yu, Interfacial dilational properties of
model oil and chemical flooding systems by relaxation measurements, Colloids Surf.
A Physicochem. Eng. Asp. 369 (2010) 106–112.
[48] A.A. Olajire, Review of ASP EOR (alkaline surfactant polymer enhanced oil recovery)
technology in the petroleum industry: prospects and challenges, Energy 77 (2014)
963–982.