Cite this article Research Article

Wang W, Liang MY, Lang JQ et al. Paper 2200070

A new thermal-tolerant bio-based zwitterionic surfactant for enhanced oil recovery. Received 08/08/2022; Accepted 16/01/2023
Green Materials,
https://doi.org/10.1680/jgrma.22.00070 Published with permission by the ICE under the
CC-BY 4.0 license.
(http://creativecommons.org/licenses/by/4.0/)

Green Materials

A new thermal-tolerant bio-based

zwitterionic surfactant for enhanced oil
recovery
Wei Wang
State Key Laboratory of Bioreactor Engineering and School of Chemistry
and Molecular Engineering, East China University of Science and
Technology, Shanghai, People’s Republic of China
Ming-Yue Liang
State Key Laboratory of Bioreactor Engineering and School of Chemistry
and Molecular Engineering, East China University of Science and
Technology, Shanghai, People’s Republic of China
Shi-Zhong Yang
State Key Laboratory of Bioreactor Engineering and School of Chemistry
and Molecular Engineering, East China University of Science and
Technology, Shanghai, People’s Republic of China; Engineering Research
Center of MEOR, East China University of Science and Technology,
Shanghai, People’s Republic of China; Department of Platform Operation,
Shanghai Collaborative Innovation Center for Biomanufacturing
Technology, Shanghai, People’s Republic of China

Jian-Qiao Lang Bo-Zhong Mu

State Key Laboratory of Bioreactor Engineering and School of Chemistry
and Molecular Engineering, East China University of Science and
Technology, Shanghai, People’s Republic of China
Homely Isaya Mtui
State Key Laboratory of Bioreactor Engineering and School of Chemistry
and Molecular Engineering, East China University of Science and
Technology, Shanghai, People’s Republic of China
State Key Laboratory of Bioreactor Engineering and School of Chemistry
and Molecular Engineering, East China University of Science and
Technology, Shanghai, People’s Republic of China; Engineering Research
Center of MEOR, East China University of Science and Technology,
Shanghai, People’s Republic of China; Shanghai Collaborative Innovation
Center for Biomanufacturing Technology, Shanghai, People’s Republic of
China (corresponding author: bzmu@ecust.edu.cn)

Bio-based surfactants are increasingly important as an alternative to traditional petro-based surfactants owing to
their renewable feedstocks and various applications in many industrial fields such as enhanced oil recovery (EOR). In
this study, a new bio-based zwitterionic surfactant with a strong interfacial activity at high temperatures of up to
120°C was developed through the modification of methyl oleate derived from renewable non-edible oils. The
synthetic route was optimized to promote the conversion rate of quaternization by precisely controlling and timely
monitoring the residues of intermediates, and the interfacial activity of the final product was greatly improved after
the optimization. This work consolidated the authors’ hypothesis that the removal of the residual intermediates of
amidation and promotion of the conversion rate of quaternization certainly contribute to enhancing the interfacial
activity of the final product, and it will facilitate the design of a sustainable alternative to petro-based chemicals
used in EOR.

Keywords: biochemical/bio-based zwitterionic surfactant/biomass conversion/enhanced oil recovery/renewable resources

Notation widely used in the ternary alkali–surfactant–polymer (ASP)

ACMC occupied area per molecule at the critical micelle flooding system to reduce the oil–brine interfacial tension (IFT) to
concentration an ultralow level (~10−3 mN/m) for EOR in recent decades.7–9
C concentration of the surfactant However, it was found that the alkali in ASP systems resulted in
IFTequ equilibrium interfacial tension both serious damage to reservoir permeability, due to the
NA Avogadro’s constant dispersion and migration of clay, and alkaline scaling in
R molar gas constant formations.10–12 Many studies from both the laboratory and
r minor axis radius industrial fields have proved that in the absence of alkali, a kind
SFTCMC surface tension at the critical micelle concentration of additive for co-reducing IFTs with surfactants, most of the
T temperature traditional surfactants in flooding systems failed to meet the
GCMC surface adsorption amount at the critical micelle required ultralow IFT and consequently failed in EOR.13–15 As a
concentration comparison, bio-based surfactants are highly competitive in alkali-
Dr density difference between crude oil and water free flooding systems in oil recovery, particularly in oil reservoirs
w rotating rate with harsh conditions such as high temperature and salinity.16,17

1. Introduction Bio-based zwitterionic surfactants derived from non-edible plant

Bio-based surfactants are increasingly important as an alternative
to traditional surfactants due to their renewable feedstocks,
environmental friendliness and wide range of applications in
many industrial fields such as enhanced oil recovery (EOR).1–6
Traditional surfactants, known as petro-based surfactants, were
oils as feedstocks are a group of bio-based surfactants owing to
their excellent interfacial activity. Various renewable materials,
including lignin, sugar and different non-edible plant oils, have
been used as feedstocks to produce bio-based surfactants with
different properties.18–20 Lignin was used to produce lignin

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 Green Materials
sulfonate (an anionic surfactant) as a dispersing agent in cement
admixtures and dye solutions.21 It was also used to synthesize
lignin polyoxyethylene ether (a non-ionic surfactant) as a stabilizer
for emulsion polymerization,22 carboxymethylated lignin (an
anionic surfactant) as a dispersant in the mining industry (ore
suspensions)23 and lignin polyether sulfonate (an anionic surfactant)
with a good interfacial activity for EOR.24,25 Meanwhile, sugar was
used to produce bio-based surfactants, such as sugar ester (a non-
ionic surfactant) and alkyl polyglycoside (a non-ionic surfactant),
and widely applied in medicine, food, cosmetics and agriculture
owing to its good surface activity and emulsifying capacity.26–31
However, non-edible plant oils, including a vast amount of waste
cooking oil,32 accounted for a large majority of renewable
feedstocks in producing bio-based surfactants, because of their
extensive renewable sources, environmentally friendly and cost-
effective performance and flexible structural modifiability in
production. Castor oil as a kind of non-edible plant oil was used to
produce polyoxyethylated castor oil as an emulsifier,33 ethoxylated
castor oil acid methyl ester (a non-ionic surfactant) with good
detergency and biodegradability as a detergent constituent34 and
ricinoleic acid methyl ester sulfonate (an anionic surfactant) with a
good interfacial activity for EOR.35 More importantly, fatty acids
and esters derived from waste cooking oil were successfully used
for producing anionic surfactants (e.g. fatty acid methyl ester
sulfonate) with excellent detergency and stable foamability as a
phosphide-free detergent constituent36,37 and zwitterionic
surfactants (e.g. phenyl fatty amide carboxyl and sulfo quaternary
ammonium) with good ability to reduce substantially oil–water
IFTs,17,38 which are therefore very promising for EOR in the oil
industry.
The interfacial activity of bio-based zwitterionic surfactants
derived from non-edible plant oils strongly depends on reaction
routes adopted in the synthesis strategy in production, and the
synthesis strategy, including reaction conditions, control of
intermediate residues and the conversion rates of each step and
the final step, is accordingly constrained by the cost and
environmental factors in production and feasibility in applications.
In general, the synthesis of bio-based zwitterionic surfactants
using non-edible oils as their feedstocks took three steps of
alkylation using aluminum trichloride as the catalyst, amidation
using 3,4,5-trifluorophenylboronic acid as the catalyst and
quaternization using sodium carbonate as the catalyst.17 For this
synthetic route, many studies proved that under laboratory
conditions, a catalyst such as aluminum trichloride showed a
relatively high catalytic efficiency,17,38–40 but it was difficult to
recover and reuse such a kind of catalyst, which naturally resulted
in a large amount of secondary waste and would be limited in
practical industrial production. In addition, the excessive residues
and low conversion rates of intermediates in these steps may have
a negative impact on the final product of bio-based zwitterionic
surfactants. Yet the mechanism by which intermediate residues
and conversion rates affect the performance of the final product
remained unclear, and the knowledge about its role in cost-
2
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A new thermal-tolerant bio-based
zwitterionic surfactant for enhanced oil
recovery
Wang, Liang, Lang et al.
effectively produced bio-based zwitterionic surfactants using non-
edible oils as their feedstocks is still limited.
In this study, methyl oleate was used as the starting material to
develop a new bio-based zwitterionic surfactant (tolyloleamide
ethyl hydroxysulfonyl quaternary ammonium salt (TEHSQA)) with
ultralow IFTs between crude oil and formation brine at high
temperature using an effective strategy realized by increasing the
conversion rate of quaternization and controlling the residues of
intermediates. The reason why methyl oleate was used as the
starting material is that compared with nervonic acid, which is
scarce and expensive, methyl oleate has more potential for
production with a lower cost. Furthermore, the removal of the
catalyst of alkylation requires washing with water, while using oleic
acid with higher hydrophilicity as the starting material will lead to
emulsification during this procedure, which makes it difficult to
separate the alkylated product. The conversion rate of each step
was monitored by gas chromatography (GC)–mass spectrometry
(MS) and high-performance liquid chromatography (HPLC)–MS to
optimize reaction conditions in a timely manner, and the structure
of the final product obtained after the optimization of reaction
conditions was characterized by hydrogen-1 (1H) nuclear magnetic
resonance spectroscopy (NMR). The thermal stability, surface
properties and IFTs of TEHSQA were evaluated, and its potential
application in EOR in reservoirs with harsh conditions such as high
temperature and salinity is discussed in this paper.
2. Experimental section
2.1 Materials
The raw material and reagents used in this study included methyl
oleate (Aladdin, 99%), toluene (SCR, 99.5%), methanesulfonic acid
(Meryer, 99%), N,N-dimethyl ethylenediamine (Aladdin, 98%),
sodium hydroxide (Hushi, 99.7%), 3-chloro-2-hydroxypropane
sulfonate (Meryer, 95%), sodium carbonate (Aladdin, 99.7%),
ethanol (Aladdin, 99.5%), methanol (Maclin, 99.5%) and sodium
chloride (Aladdin, 99.5%).
The crude oil was from the Daqing oil field, and the composition
of the simulated formation brine is summarized in Table S1 in the
online supplementary material.
2.2 Synthesis method
The target surfactant was synthesized from methyl oleate after
alkylation, amidation and quaternization. In alkylation,
methanesulfonic acid was used as the catalyst to replace
aluminum chloride, avoiding the production of wastewater
containing aluminum. Methyl oleate, toluene and methanesulfonic
acid were reacted at a molar ratio of 1:5:6 at 65°C for 6 h. After
alkylation, methanesulfonic acid was removed by water washing,
and excess toluene was recycled by atmospheric distillation. In
amidation, the one-step method (direct amidation) was used to
replace the two-step method (first acyl chlorination and then
amidation), the alkylated product reacted with five times the
 Green Materials
molar amount of N,N-dimethyl ethylenediamine at 155°C for 6 h
and 1 wt% sodium hydroxide was added as the catalyst. For half
of the amidated product, excess N,N-dimethyl ethylenediamine
was removed by atmospheric distillation, while for the other half
of the amidated product, vacuum distillation was used. In
quaternization, the amidated product reacted with an equal molar
amount of sodium 3-chloro-2-hydroxypropane sulfonate at 95°C
for 6 h, and the same molar amount of sodium carbonate acted as
the catalyst while a mixture of ethanol/water (volume ratio 2:1)
was used as the solvent. All the reactions were conducted in a 5 l
reactor that can be operated at high temperature and pressure.
After quaternization, the solvent was removed from the final
product by atmospheric distillation and collected for subsequent
use. The dried product was then dissolved in methanol to remove
sodium carbonate and the by-product sodium chloride since they
do not dissolve in methanol. Finally, methanol was recycled from
the final product by atmospheric distillation, and the purified final
product TEHSQA was obtained. The whole route of synthesis is
shown in Scheme 1.
2.3 Identification of the products and calculation
method of the conversion rate
The alkylated and amidated products were detected by GC–MS
(Shimadzu TQ-8040), and the conversion rates of the two reactions
were determined by using the peak area of the raw material and
product while the causes of peaks of the raw material and products of
alkylation and amidation were confirmed by MS. The quaternized
product was detected by HPLC–MS (Shimadzu LCMS-8045) with
the mobile phase of methanol (0.1% formic acid). The conversion rate
of quaternization was determined by using the peak area of the
residual amidated product and quaternized product, and the causes of
peaks of the residual amidated product and quaternized product were
confirmed by MS as well. The detailed calculation method of the
conversion rate is summarized in the online supplementary material.
The high-purity quaternized product was further identified by
hydrogen-1 NMR (Bruker Avance III, 400 MHz).
2.4 Determination of surface tensions
The surface tension of the TEHSQA solution was measured by
using a surface tension meter (Data Physics DACT-21) using the
plate method. TEHSQA solutions with different concentrations
were prepared using deionized water, and then the surface
tensions were measured at 25.0 ± 0.1°C.
O Three steps O and interfacial performance was determined by using a mixture of
+
C OCH3 C N N SO3−
H OH
TEHSQA
Alkylation Quaternization
O Amidation O
C OCH3 C N N of TEHSQA was determined by testing the dynamic IFT between
H
Scheme 1. Synthetic route of TEHSQA
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A new thermal-tolerant bio-based
zwitterionic surfactant for enhanced oil
recovery
Wang, Liang, Lang et al.
The adsorption amount GCMC and occupied area per molecule
ACMC of TEHSQA were calculated by using the Gibbs adsorption
isotherm equation, where h is 1 for zwitterionic surfactants, R is
the molar gas constant (8.314 J/(mol K)), SFT is surface tension
and NA is Avogadro’s constant (6.02 × 1023 mol−1).41,42
 
1 ∂ SFT
GCMC ¼−
1. 2:303hRT ∂ lg C T
2. ACMC ¼ NA G−1
CMC
2.5 Contact angle measurement
The contact angles of formation brine with and without TEHSQA on
a simulated rock surface were measured at 25°C with a contact angle
measuring instrument (Krüss DSA-25S). The rock surface was
simulated by using a quartz sheet infiltrated with Daqing crude oil.
2.6 Determination of the decomposition temperature
The decomposition temperature of TEHSQA was determined by
using a thermogravimetric analyzer (Shimadzu TGA-50). A
sample of TEHSQA was heated from 30 to 800°C at a heating
rate of 20°C/min with nitrogen purging (20 ml/min).
2.7 Determination of IFT
The IFT between Daqing crude oil and formation brine was
measured by using a spinning drop IFT meter (Krüss SDT) with a
rotating rate of 4500 revolutions per min (rpm). The instrument
can calculate the IFT automatically by using Equation 3, where
Dr, w and r are the density difference between crude oil and
water, the rotating rate and the minor axis radius, respectively.43
The dynamic IFTs between Daqing crude oil and formation brine
with different concentrations of the surfactant were measured at
45°C (reservoir temperature of the Daqing oil field) to confirm the
relationship between IFT and the concentration of the surfactant.17
Drw 2 r3
IFT ¼
3. 4
The effect of the quaternization conversion rate was confirmed by
preparing the surfactant solution using quaternized products when
adopting atmospheric distillation and vacuum distillation. The
detailed relationship between the quaternization conversion rate
the amidated product and quaternized product. The temperature
resistance of TEHSQA was determined by measuring the dynamic
IFT between Daqing crude oil and the surfactant solution, and the
test temperature changed from 45 to 120°C. The salinity tolerance
Daqing crude oil and the surfactant solution, and extra sodium
chloride and calcium chloride were added until the IFT could not
be kept at an ultralow level.
3
 Green Materials A new thermal-tolerant bio-based
zwitterionic surfactant for enhanced oil
recovery
Wang, Liang, Lang et al.

The effect of adsorption on the rock surface was determined. The
detailed experiment was as follows: first, 5.0 g of quartz sand was
mixed with 45 ml of 3.0 g/l TEHSQA solution, which was prepared
using formation brine in a 250 ml conical flask with a plug, and
then the mixture was oscillated at 45°C for 24 h in a thermostatic
water bath.17 After the aforementioned procedures, the mixture was
centrifuged at 8000 rpm to obtain the supernatant. The dynamic IFT
between Daqing crude oil and the supernatant was measured at
4500 rpm at 45°C. After that, the supernatant was mixed with one-
ninth weight of quartz sand to be oscillated again. The
aforementioned procedures were repeated until the equilibrium IFT
(IFTequ) could not be kept at an ultralow level.
Obviously, the conversion rate of the quaternization was very low and
this low rate certainly had a very negative impact on the expected
interfacial activity of the surfactant. To solve this issue, an insight into
the reactants and reaction pathways in the synthesis process was
made, and it was found that the excess residue of N,N-dimethyl
ethylenediamine in the reaction system was a key factor that inhibited
the conversion rate of quaternization, since 1 mol of the residue of N,
N-dimethyl ethylenediamine consumed up to four times the
quaternization reagent (sodium 3-chloro-2-hydroxypropane sulfonate)
in the reaction system (Scheme 2) and consequently resulted in a low
conversion rate of quaternization.

3. Results and discussion

NaO3S
3.1 Identification of intermediates and optimization of Cl SO3Na HO
the synthetic route OH
H2N
The GC–MS and HPLC–MS showed that the conversion rates of the N NaO3S N+
N+ SO3Na
OH
alkylation, amidation and quaternization products when adopting Mass ratio = 1:4 OH OH
atmospheric distillation in the synthesis process were 92.9, 97.5 and
SO3Na
61.1%, respectively, according to the corresponding peak areas of the
alkylated product (Figures S1–S3 in the online supplementary Scheme 2. Reaction mechanism of N,N-dimethyl ethylenediamine
material), amidated product (Figures S4–S6 in the online and sodium 3-chloro-2-hydroxypropane sulfonate
supplementary material) and quaternized product (Figure 1).

500
Intensity: milli-absorbance units

After atmospheric distillation

O
399 +
C N
H N SO3 −
After vacuum distillation
OH
298

O
197
C N
H N
96

−5
0 2 4 6 8 10 12 14 16 18 20
Time: min
(a)
100 605.3965 100 445.4157

O O
+ +
% C N
H
N SO3Na % C N N H
OH H

606.3992 446.4189

445.4161 467.3983 627.3780

482.3773 447.4216
396.3252
0 0
100 150 200 250 300 350 400 450 500 550 600 650 700 100 140 180 220 260 300 340 380 420 460 500
m/z m/z
(b) (c)

Figure 1. (a) HPLC of the residual amidated product and quaternized product obtained when adopting atmospheric distillation and
vacuum distillation; mass spectra of the (b) quaternized product and (c) residual amidated product

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 Green Materials
To improve further the conversion rate of quaternization, instead
of atmospheric distillation, vacuum distillation was adopted to
remove efficiently the residue N,N-dimethyl ethylenediamine in
the reaction system, and it greatly promoted the conversion rate of
quaternization. The HPLC-MS results showed that the conversion
rate of quaternization in the synthesis process when adopting
vacuum distillation increased to 92.1% (Figure 1(a), dashed line)
from a rate of 61.1% when adopting atmospheric distillation
(Figure 1(a), solid line).
Figure 2 shows the dynamic IFTs between Daqing crude oil and
formation brine with different concentrations of the quaternized
products when adopting atmospheric distillation (Figure 2(a)) and
vacuum distillation (Figure 2(b)). For the quaternized product when
adopting vacuum distillation, the IFTs between Daqing crude oil and
formation brine can be reduced to an ultralow level (~10−3 mN/m) at
a minimum concentration of 0.3 g/l, corresponding to only one-tenth
of the dosage of conventional surfactants used in oil recovery, and to
an ultralow level on the order of ~10−4 mN/m at a minimum
concentration of 0.5 g/l (Figure 2(b)), which consolidated the authors’
hypothesis that the promotion of the conversion rate of quaternization
certainly contributed to enhancing the interfacial activity of such bio-
based zwitterionic surfactants.
Figure 3 shows the dynamic IFTs between Daqing crude oil
and formation brine with a 1.0 g/l mixture of the amidated
product and quaternized product at different mass ratios.
Unsurprisingly, the amidated product showed very poor interfacial
activity, and increasing the mass fraction of the amidated product
in the mixture would further damage the interfacial activity
(Figure 3(a)). In contrast, with the increase in the mass fraction of
the quaternized product in the mixture, the IFTs between Daqing
crude oil and formation brine were accordingly reduced to an
ultralow level (~10−3 mN/m) at and above a mass fraction of
1 1
0.3 g/l
0.5 g/l
0.1 1 g/l
3 g/l
IFT: mN/m
IFT: mN/m
0.01
0.001
0.0001
0 2000 4000 6000 8000
t: s
(a)
Figure 2. Dynamic IFTs between Daqing crude oil and formation brine with different concentrations of quaternized product when
adopting (a) atmospheric distillation (purity: 61.1%) and (b) vacuum distillation (purity: 92.1%)
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A new thermal-tolerant bio-based
zwitterionic surfactant for enhanced oil
recovery
Wang, Liang, Lang et al.
36.8% of the quaternized product in the mixture and reduced to
an ultralow level on the order of ~10−4 mN/m at 92.1%
quaternized product (Figure 3(b)).
The poor interfacial performance of the amidated product can be
attributed to its poor hydrophilicity, which makes it stay in the oil
phase rather than at the oil–water interface. The low interfacial
amount makes it unable to reduce the IFT effectively. Therefore, a
high quaternization conversion rate is essential to having a good
interfacial performance. As the ultralow IFT is an important
measuring index, the purity of the final product should be higher than
36.8% to ensure that a good effect in oil flooding can be obtained.
In addition, the confirmed structure of the quaternized product when
adopting vacuum distillation (TEHSQA) using hydrogen-1 NMR
analysis showed the following results (Figure S11 in the online
supplementary material): (400 MHz, deuterated methanol (CD3OD)):
d 8.57 (–CO–NH–), 7.15–7.00 (–C6H4–), 4.62 (–CH2–CH(OH)–),
4.15–4.11 (–CH2–CH(OH)–), 3.84–3.56 (–NH–CH2–; –CH2–SO3−),
3.37–3.26 (–CH2–N(CH3)2–), 3.09–2.89 (–N(CH3)2–), 2.72
(–CH–C6H4–), 2.33–2.20 (–CH2–CO–; –C6H4–CH3), 1.61–1.55
(–CH2–CH(C6H4–CH3)–; –CH2–CH2–CO–),1.31–1.23(–(CH2)n−3
–CH2–CH2–CO–; –(CH2)m−1–CH3), 0.92–0.85 (–CH2–CH3).
3.2 Surface activity
The surface tensions of TEHSQA in solution decreased with the
increase in surfactant concentration (Figure S12(a) in the online
supplementary material). The critical micelle concentration
(CMC) and the surface tension at CMC (SFTCMC) obtained at the
inflection point of the broken line were 1.20 × 10−5 mol/l and
32.10 mN/m, respectively. The contact angle of the formation
brine without TEHSQA on the simulated rock surface was 62.3°
(Figure S12(b) in the online supplementary material), and the
contact angle of the formation brine with 1.0 g/l TEHSQA
0.3 g/l
0.5 g/l
0.1 1 g/l
3 g/l
0.01
0.001
0.0001
0 2000 4000 6000 8000
t: s
(b)
5
 Green Materials A new thermal-tolerant bio-based
zwitterionic surfactant for enhanced oil
recovery
Wang, Liang, Lang et al.

Mass ratio of quaternized product in amidated product: %

1 1
0% 36.8% 73.7%
18.4% 55.3% 92.1%

0.1 0.1

IFT: mN/m
IFT: mN/m

0.01 0.01

0.001 0.001

0.0001 0.0001
0 2000 4000 6000 8000 0 20 40 60 80 100
t: s Mass ratio of quaternized product in amidated product: %
(a) (b)

Figure 3. Dynamic (a) IFT and (b) IFTequ between Daqing crude oil and formation brine with a 1.0 g/l mixture of the amidated product and
quaternized product at different mass ratios

decreased from 62.3 to 42.5° (Figure S12(c) in the online
supplementary material).
The surface properties of TEHSQA are compared with that of a
zwitterionic surfactant N, N-Dimethyl-N-[2-hydroxy-3-sulfo-
propyl]-N¢-phenyloctadecanoyl-1, 3-diaminopropane (SPODP)
and an anionic surfactant 4-(1-heptadecyl) benzene sodium
sulfonate (9FC17S) in Table 1.17,44 TEHSQA showed a lower
CMC and a lower SFTCMC than those of SPODP and 9FC17S,
which implied that TEHSQA possessed higher efficiency in
reducing surface tension. The decrease in contact angle suggested
that TEHSQA inherited a good ability to alter the wettability of
the simulated rock surface, and the alteration in wettability toward
hydrophilic in oil reservoirs consequently contributed to EOR in
the oil production process.45,46
3.3 Thermal resistance
To evaluate the thermal stability of TEHSQA, both the
decomposition temperature and IFTs between crude oil and
the formation brine at different temperatures were determined. The
thermogravimetric analysis (TGA) thermogram of the TEHSQA
sample (Figure 4(a)) showed that the sample had a little weight loss
(5%) when heated from 30 to 270°C and a large weight loss (65%)
when heated from 270 to 490°C, and afterward, the weight loss
showed little change up to a temperature of 800°C. As shown in
Figure 4(a), for the TEHSQA sample, the very little weight loss
(5%) with heating from 30 to 270°C corresponded to bound water
Table 1. Surface properties of TEHSQA, SPODP and 9FC17S in
water at 25°C
CMC: SFTCMC: GCMC:
Surfactant
mmol/l mN/m mmol/m2
TEHSQA 0.012 32.10 7.87
SPODP 0.071 32.50 5.23
9FC17S 0.807 32.54 4.27
and a small amount of light volatiles released from the TEHSQA
sample.47 Its decomposition temperature stood at 270°C, which
promised good compatibility in a wide range of oil reservoir
temperatures.48–50 The 45% weight loss from 270 to 412°C could
be attributed to the fracture of the quaternary ammonium bond,
while the 20% weight loss from 412 to 490°C could be due to the
breaking of the amide bond. Finally, the hydrophobic carbon chain
broke gradually from 490 to 800°C.
The change in dynamic IFTs between Daqing crude oil and the
formation brine with a TEHSQA concentration of 1.0 g/l against
temperature showed that the equilibrium IFTs (IFTequ) remained at
ultralow levels on the order of ~10−3 mN/m at temperatures up to
120°C and on the order of ~10−4 mN/m at temperatures up to 90°C
(Figures 4(b) and 4(c)), which suggests good stability of the
interfacial performance of TEHSQA as a bio-based surfactant at high
temperatures. As shown in Figure 4(c), IFTequ can remain at an
ultralow level (~10−3 mN/m) up to 120°C, which is higher than that
of most reported bio-based surfactants.16,17,24–38 When the
temperature rose from 45 to 60°C, the ionization degree of the
hydrophilic head was improved; thus, the hydrophilicity of surfactant
molecules increased. As a rule, the benzene ring and the long carbon
chain would certainly offer considerable hydrophobicity, and an
increase in hydrophilicity would be beneficial to the balanced
arrangement of surfactant molecules at the interface and consequently
result in reducing the IFTs. However, when the temperature further
rose, the hydrophilicity of surfactant molecules tended to decline
owing to the breakage of hydrogen bonds between surfactant
molecules and water molecules.51 The decline of the hydrophilicity
induced the surfactant molecules to leave the oil–water interface and
finally altered the IFTs.
ACMC:
nm2/molecule 3.4 Salinity tolerance
0.21 The dynamic IFTs between Daqing crude oil and the formation
0.31 brine with 1.0 g/l TEHSQA against concentrations of sodium
0.39
chloride (NaCl) and calcium (Ca2+) ions are shown in Figure 5.

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 Green Materials A new thermal-tolerant bio-based
zwitterionic surfactant for enhanced oil
recovery
Wang, Liang, Lang et al.

0.1 0.1
100 45ºC 90ºC
5%
60ºC 105ºC
75ºC 120ºC
80
Weight: %

45% 0.01 0.01

IIFT: mN/m

IFT: mN/m
60

40 20% 0.001 0.001

20
270 412 490
0.0001 0.0001
200 400 600 800 0 2000 4000 6000 8000 45 60 75 90 105 120
Temperature: °C t: s Temperature: °C
(a) (b) (c)

Figure 4. (a) TGA curve of TEHSQA; (b) dynamic IFT and (c) IFTequ between Daqing crude oil and formation brine with 1.0 g/l TEHSQA at
different temperatures

1 0 g/l 1
0 mg/l
5 g/l
1000 mg/l
10 g/l
2000 mg/l
0.1 15 g/l 0.1
2500 mg/l
20 g/l
3000 mg/l
IFT: mN/m

IFT: mN/m

0.01 0.01

0.001 0.001

0.0001 0.0001
0 2000 4000 6000 8000 0 2000 4000 6000 8000
t: s t: s
(a) (b)

Figure 5. Dynamic IFTs between Daqing crude oil and formation brine with 1.0 g/l TEHSQA and different concentrations of (a) sodium
chloride and (b) calcium ions

As shown in Figure 5(a), IFTequ increased with increasing
concentrations of sodium chloride, and IFTequ could remain at an
ultralow level until the concentration of sodium chloride reached
15 g/l. When the concentration of sodium chloride increased,
sodium (Na+) ions complexed with the sulfonyl group and
chloride (Cl−) ions complexed with the quaternary ammonium
groups owing to their charges, which affected the reduction of the
self-interaction of surfactant molecules. As a result, the
arrangement of surfactant molecules at the oil–water interface
became loose and further resulted in the increase in IFTequ.52
The equilibrium IFTs (IFTequ) remained at an ultralow level on
the order of ~10−3 mN/m at concentrations of calcium ions of up
to 2500 mg/l (Figure 5(b)). Compared with sodium chloride,
calcium ions had a more notable effect on the interfacial
performance of the surfactants owing to their greater positive
charge.53 IFTequ showed a little decrease first at a concentration of
calcium ions of up to 1000 mg/l, which suggested that at a low
concentration, calcium ions may undergo complexation with
multiple surfactant molecules and consequently contribute to the
tight arrangement of surfactant molecules at the oil–water
interface. However, the IFTs increased with a further increase in
the concentration of calcium ions up to 2500 mg/l, which implied
that at high concentrations of calcium ions, the electrostatic
attraction between the anionic groups of surfactant molecules and
calcium ions with a strong binding capacity destroyed the self-
electrostatic attraction between surfactant molecules. Meanwhile,
the electrostatic repulsion between the cationic groups of
surfactant molecules remarkably reduced their interfacial
concentration and increased the equilibrium IFT.53
3.5 Adsorption on quartz sands from formation brine
The dynamic IFTs between Daqing crude oil and formation brine
with 3.0 g/l TEHSQA against adsorption times are shown in
Figure 6. It shows that IFTequ could remain at an ultralow level
on the order of ~10−3 mN/m after four iterations of adsorption on

7
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 Green Materials
0.1
1 time 2 times 4 times
3 times 5 times
0.01
IIFT: mN/m
0.001
0.0001
0 2000 4000 6000
t: s
(a)
Figure 6. Dynamic (a) IFT and (b) IFTequ between Daqing crude oil and formation brine with 3.0 g/l TEHSQA after different iterations of
adsorption
the quartz sands from formation brine. As shown in Figure 6(b),
IFTequ increased with the increase in adsorption iterations and
could remain at an ultralow level at up to four iterations of
adsorption, which suggests that TEHSQA possesses an acceptable
anti-adsorption stability. As the adsorption of surfactant molecules
is an exothermic process, the adsorption of zwitterionic
surfactants on the sandstone rock surface will decrease at high
temperatures, which is unacceptable for anionic and non-ionic
surfactants.54,55 As a result, the anti-adsorption stability of
TEHSQA can be better at high temperature.
4. Conclusions
In summary, the conversion rate of quaternization had a great effect
on the interfacial activity of the final product and it played a key
role among the three steps in the synthetic process of a bio-based
zwitterionic surfactant from waste oil as feedstock. By using the
strategy of vacuum distillation to remove the residual intermediates
of amidation and to promote the conversion rate of quaternization,
the authors developed a new thermally stable bio-based zwitterionic
surfactant, TEHSQA, from methyl oleate derived from waste oil
that possessed a good interfacial activity at temperatures of up to
120°C. This is strong evidence to support the hypothesis that the
removal of the residual intermediates of amidation and promotion
of the conversion rate of quaternization in the synthesis of the bio-
based zwitterionic surfactant contribute to the interfacial activity of
the final quaternized surfactant. The IFT between Daqing crude oil
and formation brine can be reduced to an ultralow level on the
order of 10−4 mN/m at a very low dosage of 1.0 wt% of the
surfactant TEHSQA in the formation brine under alkali-free
conditions, which makes it highly competitive against most of the
reported zwitterionic surfactants. Moreover, the bio-based
zwitterionic surfactant TEHSQA demonstrated good thermal
stability, strong salt tolerance, high wetting ability and acceptable
adsorption behaviors. At a very low dosage of 1.0 wt% of the
surfactant TEHSQA in the formation brine, the IFTs can be reduced
8
Downloaded by [] on [18/03/23]. Published with permission by the ICE under the CC-BY license
A new thermal-tolerant bio-based
zwitterionic surfactant for enhanced oil
recovery
Wang, Liang, Lang et al.
0.1
0.01
IFT: mN/m
0.001
0.0001
8000 1 2 3 4 5
Adsorption iterations
(b)
to an ultralow level (~10−3 mN/m) at a temperature up to 120°C. In
addition, the IFTs remain at an ultralow level at calcium ion
concentrations of up to 2500 mg/l and sodium chloride
concentrations of up to 15 000 mg/l in the formation brine, which is
promising for meeting the urgent needs of highly efficient
surfactants for EOR in oil reservoirs under harsh conditions such as
high temperature and salinity.
Acknowledgements
This research was supported by the National Key Research and
Development Program of China (number 2017YFB0308900), the
National Natural Science Foundation of China (number 51574125)
and the Fundamental Research Funds for the Central Universities of
China (number 222201817017).
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