Green Chemical Engineering xxx (xxxx) xxx

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Green Chemical Engineering

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Original Article

Renewable non-edible oils derived long chain (C24.1) bio-based

zwitterionic surfactant with ultralow interfacial tension between crude oil
and formation brine
Homely Isaya Mtui a, Fang-Hui Liu a, Wei Wang a, Jian-Qiao Lang a, Shi-Zhong Yang a, b, c,
Bo-Zhong Mu a, b, c, *
a
State Key Laboratory of Bioreactor Engineering and School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237,
China
b
Engineering Research Center of Microbial Enhanced Oil Recovery, Ministry of Education, East China University of Science and Technology, Shanghai, 200237, China
c
Shanghai Collaborative Innovation Center for Biomanufacturing Technology, Shanghai, 200237, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

NDAS surfactant could be prepared from

nervonic acid derived from non-edible
oils by a simple and effective method.

NDAS exhibited excellent interfacial ac-
tivity to an ultralow value (~104 mN/
m) at a very low dosage (0.05 g/L) for
EOR.

NDAS demonstrated high NaCl compat-
ibility up to 100 g/L, Ca2þ up to
200 mg/L, and temperature stability to
90  C.

A R T I C L E I N F O A B S T R A C T

Keywords: A new ultra-long chain monounsaturated 4-(N-nervonicamidopropyl-N,N-dimethylammonium) butane sulfonate

Bio-based surfactant (NDAS) zwitterionic surfactant with ultralow interfacial tensions was developed through the modification of
Interfacial tension nervonic acid derived from renewable non-edible seed oils by a simple and effective method. Its structure was
Salt tolerance
characterized by ESI-HRMS, 1H NMR, and 13C NMR. NDAS surfactant exhibited a strong interfacial activity
Enhanced oil recovery
Biodegradability
(~104 mN/m) between the crude oil and the formation brine at a very low surfactant dosage (0.05 g/L) and at
high salinity conditions, which is equivalent to 2% (w/w) of dosage of the most traditional surfactants used in the
enhanced oil recovery field. Meanwhile, at a very low concentration (0.05 g/L), NDAS demonstrated strong NaCl
compatibility up to 100 g/L, Ca2þ ions compatibility up to 200 mg/L, and temperature stability up to 90  C. The
surface tension, emulsification, and biodegradability parameters were also evaluated. This work consolidates our
hypothesis that increasing the hydrophobic chain length of a surfactant certainly contributes to the high inter-
facial activity and good compatibility of salts and temperatures. Hence, it will facilitate the design of a sustainable
alternative to petroleum-based chemicals to develop bio-based surfactants and extend the domain of bio-based
surfactants to new applications such as in enhanced oil recovery (EOR).

* Corresponding author. State Key Laboratory of Bioreactor Engineering and School of Chemistry and Molecular Engineering, East China University of Science and
Technology, Shanghai, 200237, China.
E-mail addresses: homelymtui@mail.ecust.edu.cn (H.I. Mtui), bzmu@ecust.edu.cn (B.-Z. Mu).

https://doi.org/10.1016/j.gce.2022.08.001
Received 17 April 2022; Received in revised form 12 July 2022; Accepted 2 August 2022
Available online xxxx
2666-9528/© 2022 Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communication Co. Ltd. This
is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article as: H.I. Mtui et al., Renewable non-edible oils derived long chain (C24.1) bio-based zwitterionic surfactant with ultralow
interfacial tension between crude oil and formation brine, Green Chemical Engineering, https://doi.org/10.1016/j.gce.2022.08.001
H.I. Mtui et al.
1. Introduction
Surfactants are surface-acting agents with a hydrophobic/lipophile
tail and a hydrophilic/hydrophile head in the same molecule [1]. Sur-
factants are not only widely used as detergents in daily household ap-
plications but are also used as patterns for constructing nanoparticles and
as carrier vehicles for drug delivery [2], catalysts in organic synthesis [3],
as well proved to be efficacious in the oil field industry, particularly in
chemically enhanced oil recovery [4]. According to records, surfactants
originating from fossil resource (usually crude oil-based) feedstocks,
notably petrochemical-based, are the most widely employed in enhanced
oil recovery (EOR) and other industrial domains [5]. On the other hand,
they cause the depletion of fossil resources and pollution to the envi-
ronment due to their low biodegradability and emission of greenhouse
gases during their production or uses, which pose a risk to microbial,
plant, and animal life [6]. To address these challenges, the production
and research on natural surfactants (bio-based surfactants) have drawn
attention in recent years [7,8]. Since the crude oil limits of the early
1970s and the beginning of the 1990s, the oil recovery field, surfactant
industry, and market have proved the renewable oleochemical feedstocks
to be a viable alternative to conventional crude oil-based systems. Palm
and coconut-derived oleochemicals have increased, with soybeans being
cited more recently [9]. However, oleo chemical-based feedstocks are
edible vegetable oils, which have created problems in recent years due to
fierce competition with food, biodiesel, and renewable surfactant pro-
duction requirements. And that causes a challenge in producing sufficient
renewable-based surfactants in the market, which drives surfactant
producers to find workable substitute feedstock sources that are also
renewable and less closely connected with petrol and oleo oil to support
the oil recovery field and the surfactant industry.
Central and Southern Europe, North America, the Balkans, South-
West Asia, and China are well-known for cultivating flowering plants.
They are mainly native to Malania oleifera and Lunaria species ‘honesty
plant’, which produce a massive amount of seeds from their fruits and are
considered environmental wastes [10]. Malania oleifera and Lunaria
seed oils (such as Lunaria biennis or Lunaria annua) are non-edible
vegetable oils and essential sources of nervonic acid (NA: C24.1).
Malania oleifera seed oil contains more than 55.7% of NA [11], while
Lunaria seed oils cover more than 20% of NA in triglyceride lipids [12]. It
is well noted that the ultra-long chain fatty acid level below 5% is only
acceptable for human health, and the standard level in an edible oil
should be less than 2%. Hence, the excess amount of nervonic acid be-
comes leftover, which can have great potential as an alternative to
traditional oleo- and petro-based chemicals as surfactant production
feedstock. It has also been well-identified that ultra-long chain fatty
acid-based surfactants have excellent properties on the aqueous solu-
tions, high surface activities, good rheological behaviors with high vis-
cosity, and are environmentally friendly [13,14]. Despite that, most
bio-based surfactants described and used in EOR are those invented
from typical/short vegetable fatty acids chained between carbon-8 and
carbon-18, owing to the ultra-long chain fatty acid-based surfactants'
inability to dissolve in water and restricted feedstocks. However, the type
of a hydrophilic group connected to its head part and the degree of
unsaturation on the hydrophobic tail part control their water solubility,
potentially lowering the Krafft temperature property of surfactants.
Generally, the solubility of ultra-long chain-based surfactants in pure
water can be improved by lengthening the hydrophilic part [15], the
usage of hydrotropes [16], or the addition of some amount of salts [17].
And compared to their saturated counterparts, the degree of unsaturation
of their hydrophobic component leads to an increase in the solubility rate
[18]. The surfactants yielded from the unsaturated hydrophobic chain
part are also readily decomposed at the unsaturated bond position at high
temperatures in the presence of air (oxygen), which primarily determines
the degradability, apart from increasing the polarity of surfactant in the
aqueous solution [19]. Currently, biomass-derived materials are
attracting a lot of interest [20]. However, the bio-based surfactant
2
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industry and the oil recovery field still face difficulty developing syn-
thetic approaches to ecologically benign products [21] and limited
biomaterial feedstocks.
In this study, we developed a new ultra-long chain bio-based zwit-
terionic surfactant 4-(N-nervonicamidopropyl-N,N-dimethylammonium)
butane sulfonate (NDAS) with ultralow interfacial tensions at a very low
dosage and high salinity by a simple and effective synthetic strategy
using a nervonic acid derived from bioresource non-edible Malania
oleifera and Lunaria seed oils as a feedstock. The intermediate product
and the final NDAS surfactant product structures were characterized
using electrospray ionization high-resolution mass spectrometry (ESI-
HRMS), proton nuclear magnetic resonance (1H NMR), and carbon nu-
clear magnetic resonance (13C NMR) techniques. The properties of NDAS
surfactant in aqueous solutions such as water solubility, surface tension
(SFT), interfacial tension (IFT), thermal stability, salt tolerance, emulsi-
fication, and biodegradability were evaluated. This study's innovation is
associated with introducing a new ultra-long-chain C24.1 bio-based
zwitterionic surfactant NDAS derived from the renewable feedstock, via
an inexpensive, simple, and effective synthetic pathway. NDAS surfactant
demonstrated an outstanding interfacial activity to ultralow at a very low
dosage, high salinities compatibility, and high temperatures stability,
which are significant results for EOR field applications, and is environ-
mentally friendly.
2. Experimental section
2.1. Materials and structural analyses
2.1.1. Materials
Commercial nervonic acid (> 90%, GC, Shaanxi Yikanglong
Biotechnology Co., Ltd.), N,N-dimethyl-1,3-propanediamine (99%, GC,
Shanghai Macklin Biochemical Co., Ltd.), 3,4,5-trifluorophenylboronic
acid (98.8%, GC, Leyan Mall-Chemical Reagent), 1,4-butanesultone (>
99.0%, GC, Tokyo Chemical Industry Co., Ltd.), ethyl acetate (99.7%, GC,
Collins Chemical Ltd.), methyl alcohol (99.9%, HPLC, TEDIA high purity
solvents), and phenyltrimethylammonium bromide (99%, DARUI Fine
Chemicals Co., Ltd.). All chemicals were analytical grade and didn't need
to be further purified or analyzed.
2.1.2. Structural analyses
1
H NMR and 13C NMR spectra were recorded on a Bruker Avance 300
spectrometer at 400 MHz for N-nervonicamidopropyl-N,N-dimethyl-
amine (NAPDMA) in CDCl3 and at 600 MHz for NDAS in deuterated
methanol (MeOD solvent) at room temperature. ESI HRMS spectra were
taken on a Bruker Daltonics Data Analysis 3.2 system. A high-
performance liquid chromatography-ultraviolet/visible spectrophotom-
eter (Vis: UV-2075 plus) was used to determine the percentage content of
the NDAS surfactant from the nervonic acid.
2.2. Water solubility tracing
Five different portions of the 1.0 g/L NDAS surfactant solution were
prepared in the presence of various phenyltrimethylammonium bromide
(PTMAB hydrotrope) concentrations (0, 0.05, 0.1, 0.25, and 0.5 mol/L,
respectively). And to investigate the solubilization efficiency in a specific
PTMAB concentration, different NDAS solutions were prepared at a
selected PTMAB concentration. Mind that all solutions were prepared from
pure water followed by agitation and boiled at 45–50  C for about 2 h to
facilitate the solubility. After that, solutions were allowed to cool to below
0  C. Finally, observations were made to see if there were any precipitates.
2.3. Surface and interfacial tension measurement
2.3.1. Surface tension measurement
Surface tension measurements of NDAS solutions (prepared with pure
water in 0.1 mol/L PTMAB) were performed using the plate method on a
H.I. Mtui et al.
Table 1
The properties of the simulated formation brine.
Inorganic salt Purity, % Amount/(mg/L)
Anhydrous sodium sulfate 99.0 18.1
Magnesium dichloride 98.0 91.6
Calcium chloride 96.0 113.2
Sodium carbonate 99.5 387.1
Sodium chloride 99.0 1601.5
Sodium bicarbonate 99.5 3182.1
DCAT 21 tensiometer machine (Dataphysics, Germany) at an equilibrium
stop of 0.01 mN/m at 25.0  0.1  C. The quartz plate was washed with
plenty of running pure water to achieve the equilibrium conditions. It
was dried by heating it above an alcohol burner until it was flaming red,
then allowed to cool to room temperature. Each concentration was
measured three times (Table S1), and an average value was calculated to
ensure the precision of the final results. The calibrated surface tension of
pure water at 25  C was 71.63 mN/m.
2.3.2. Interfacial tension determination
The spinning-drop method at 45  C and 4500 r/min using the TX-
500C interfacial tensiometer was used to measure dynamic interfacial
tension between Daqing crude oil and simulated formation brine vs. time
at various concentrations of NDAS surfactant (the composition of the
simulated formation brine found in Table 1, and fundamental properties
of the Daqing crude oil located in the Supporting Information). The
equilibrium precision was determined by taking successive readings from
the image of a spinning drop every 2 min for a maximum of 2 h. Other IFT
properties evaluated at an NDAS concentration of interest include ther-
mal stability by temperature fluctuations and salts tolerance by the
change in NaCl and Ca2þ concentrations. The calibrated interfacial ten-
sion between the oil drop of Daqing crude oil and the simulated forma-
tion brine was 12.55 mN/m at 45  C.
2.4. Salts tolerance measurement
The salts tolerance of the NDAS surfactant was determined using
standard salt tolerance test techniques [21,22]. 0.5 g/L NDAS surfactant
solutions with various NaCl and Ca2þ concentrations were prepared,
respectively. All of the produced solutions were centrifuged for 15 min at
2500 r/min before monitoring, observing, and recording the concentration
that precipitations occurred at 45  C for 24 h, and that concentration was
used to infer the NDAS surfactant's salts tolerance in aqueous solutions.
2.5. Emulsification test and biodegradation estimation
2.5.1. Emulsification test
Before the experiment, the Daqing crude oil and the 0.5 g/L NDAS
Scheme 1. The synthetic protocol of NDAS surfactant from nervonic acid extracted from non-edible oils.
3
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surfactant solution made in formation brine were separately preheated at
45  C for 1 h. The NDAS surfactant as an emulsifier was tested according
to the procedures mentioned in Zhang et al., 2015 [23], but the tem-
perature was constant at 45  C. The mixture made from 5 mL of 0.5 g/L
NDAS surfactant (in simulated formation brine) and 5 mL of crude oil was
prepared in a 10 mL graduated test tube and shaken vigorously for 1 min.
The time for separating 1 mL to the 5 mL volume of the aqueous phase
solution from the crude oil phase was recorded. The same procedures
were applied for measuring emulsification capacity and stability at
different NaCl and Ca2þ ions concentrations and temperatures variations.
Each test was repeated three times to ensure the result's precision
(Table S2).
2.5.2. Biodegradability estimation
The biodegradation estimation of NDAS was achieved on an EPI Suite
software on the BIOWIN-3 model. EPI Suite is frequently used to estimate
the biodegradation of organic chemicals in the environment. An ultimate
biodegradation prediction was computed from the BIOWIN-3 model of
biodegradation.
2.6. Synthesis
2.6.1. The yield of intermediate NAPDMA
The amidation reaction was tangled by the reaction between 20.13 g
(55 mmol) nervonic acid and 16.72 g (164 mmol) N,N-dimethylpropane-
1,3-diamine (DMPDA) in the presence of 3.85 g of 3,4,5-trifluorophenyl-
boronic acid (TFPB) as catalyst without a solvent, and the reaction
mixture was refluxed at 120  C for 8 h (Scheme 1). After the reaction time
was completed, the simple purification process was conducted so that the
byproduct H2O and remains of DMPDA were recovered by being evap-
orated under reduced pressure using a rotary evaporator in an oil bath.
Then, the flask of the product mixture of amide intermediate NAPDMA
and TFPB was cooled to room temperature before being dissolved in
ethyl acetate and followed by centrifugation to remove the TFPB catalyst.
Eventually, the purified intermediate product NAPDMA was obtained,
and its chemical structure was achieved as NAPDMA (C29H58N2OþESþ):
ESI HRMS-TOF MS ESþ: calculated; m/z ¼ 451.5 (Fig. S1). 1H NMR
(400 MHz, CDCl3) δ 7.05 (s, 1H), 5.35–5.27 (m, 2H), 3.32–3.26 (m, 2H),
2.37 (t, J ¼ 6.4 Hz, 2H), 2.23 (s, 6H), 2.14 (t, 2H), 2.00 (m, 4H),
1.71–1.54 (m, 4H), 1.26 (m, 32H), 0.88 (t, J ¼ 13.4 Hz, 3H) (Fig. S2).
2.6.2. The synthesis of NDAS
The quaternization reaction was performed based on the recognized
method [24]. 30.3 g (67 mmol) of the purified NAPDMA amidated
product was quaternized using 11.5 g (84 mmol) of 1,4-butanesultone,
which was dropped into the reactor in no more than 0.5 h, escorted by
strong mechanical magnetic stirrings and refluxed at 85  C for 3 h
(Scheme 1). After the reaction, the mixture was cooled to room
H.I. Mtui et al.
Fig. 1. The depiction of solubility of the NDAS surfactant in pure water before and after the addition of 0.1 mol/L PTMAB.
temperature and washed several times with ethyl acetate to remove
unreacted sultone and amide compounds. The washed cake was
concentrated by evaporation under reduced pressure and dried to remove
the remains of ethyl acetate before a single raw NDAS surfactant product
was obtained. Lastly, the final purified and dried NDAS surfactant
product was achieved at a yield of 87.7%. The percentage content
detected using HPLC/UV–Vis was higher than 85% (Scheme 1,
Figs. S3–S4) and was characterized as NDAS (C33H66N2O4SþESþ): ESI
HRMS-TOF MS ESþ: calculated; m/z ¼ 587.5 (Fig. S5). 1H NMR
(600 MHz, MeOD) δ 5.38 (m, 2H), 3.37–3.32 (m, 2H), 3.31–3.25 (m, 4H),
3.07 (s, 6H), 2.88 (t, J ¼ 7.1 Hz, 2H), 2.22–2.03 (m, 4H), 2.02 (m, 2H),
1.96 (t, J ¼ 4.8 Hz, 2H), 1.94–1.85 (m, 2H), 1.84 (m, 2H), 1.60 (m, 2H),
1.38–1.24 (m, 32H), 0.90 (t, J ¼ 7.0 Hz, 3H) (Fig. S6). 13C NMR
(151 MHz, MeOD) δ 175.32, 129.47, 129.45, 63.49, 63.46, 63.45, 61.86,
61.82, 61.79, 61.77, 61.09, 48.04, 47.89, 47.75, 47.47, 47.32, 47.18,
31.68, 29.45, 29.40, 29.38, 29.28, 29.22, 29.07, 29.03, 28.91, 26.71,
13.08 (Fig. S7).
3. Results and discussion
3.1. Structural characterizations
To minimize environmental pollution, the manufacturing of chemical
products by a green pathway with no waste or harmful byproducts is
vital. Through a simple and effective synthesis reaction scheme using a
renewable natural nervonic acid (derived from non-edible seed oils) as
the starting material, the NDAS surfactant product was achieved without
using any solvents and with no harmful byproducts. Preparing the amide
intermediate is a crucial first step in determining the final surfactant
product. Yet, the synthesis of amide intermediate without the con-
sumption of high temperature, longer reaction time, and waste genera-
tion is the main challenge [25]. Here, we used an effective TFPB as a
catalyst and succeeded in shortening the amidation reaction time to only
8 h at an average temperature of 120  C. No harmful byproduct was
yielded other than water and was readily isolated from the amide product
by reduced pressure evaporation. The synthetic scheme used in our work
was much easier and more robust to the high-yield of amide intermediate
compared to the past reports on ultra-long chain-based surfactants,
which took a tedious reaction time of 65 h [26] at high temperatures of
4
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155–160  C for 10 h and restricted to reaction conditions such as inert
atmospheric conditions [27]. In addition, a high yield of purified amide
intermediate was obtained without any need for solvent in the reactor,
which substantiates that the method used here was more economical and
sustainable compared with other reports that used large amounts of
organic solvent in the reactor, even to purify [26]. The intermediate was
then quaternized by 1,4-butanesultone to obtain the final product. Feng
et al. [17,26] used 1,3-propanesultone compound as a quaternization
reaction reagent, but this compound was found to be highly toxic, which
has proved to contribute a carcinogenic for mammals, and it has been
prohibited for industrial usage since then. Hence, herein we used 1,
4-butanesultone, which is less toxic than 1,3-propanesultone [24] and
is recommended to be used as a substitute compound in the industry.
Thus, this synthetic convention procedure was designed to meet the
current demand for sustainable chemistry and widen the industrial needs
for NDAS biobased surfactant.
3.2. Water solubility
The solubility of NDAS zwitterionic surfactant in pure water was ut-
terly invisible, even when its solution boiled at a temperature of 100  C,
which implies that the Krafft point (TK) of NDAS was higher than 100  C.
But, in the presence of 0.1 mol/L of PTMAB hydrotrope, it took about 2 h
to dissolve entirely into the pure water at 45–50  C, accompanied by
strong agitation. No any precipitates were formed after cooling even to
0  C (Fig. 1). NDAS surfactant solutions in PTMAB were stable and sol-
uble even when stored for months without forming any precipitates,
which proved that the TK was decreased to below 0  C and water solu-
bility was significantly improved (as shown in Figs. S8–S9). So, the water
solubility challenge of this ultralong chain-based surfactant was resolved.
The wide applications of ionic surfactants are manifested by their ability
to be soluble in aqueous solutions [28].
Fundamentally, the solubility point of the surfactants in aqueous so-
lutions is commonly determined at the temperature acknowledged as the
TK, the point at which the ionic surfactant's solubility is usually equal to
its critical micelle concentration (cmc). The solubility of ultra-long chain
surfactants is very challenging because of the longer hydrophobic tail
chain, which increases TK value and impedes their practical applications.
Hence, studying their water solubility parameters in pure water is vital.
H.I. Mtui et al.
Fig. 2. Surface tension (SFT) plotted as a function of NDAS surfactant concen-
tration in 0.1 mol/L PTMAB hydrotrope at 25  C.
The TK value of the surfactant increases with the broadening of its hy-
drophobic tail chain and point of saturation, decreases with the intro-
duction of an unsaturated bond onto the tail and depends on the type of
the hydrophilic group attached to the surfactant's head part [17,29]. The
saturated fatty acid-based surfactants with non-polar components more
extended than 18 carbon atoms in the chain typically have poor water
solubility even in boiling pure water compared to unsaturated ones [18].
It was also reported that the long-chain bearing (C18–C22) sulfobetaine
surfactants were utterly insoluble in the pure water since they had a TK
value higher than 73  C but decreased sharply only after the addition of
NaCl [17]. However, the demand for NaCl salt as a food ingredient, a
laboratory chemical, or a medical component continues to be high.
Unlike in pure water, the NDAS surfactant's solubility in the simulated
formation brine was completely visible with clear solutions due to the
inorganic salt compositions in brine which could dissociate into ions and
increase the solution conductivity and polarity. This phenomenon could
displace the zwitterionic nature in the head part more readily and tends
to disassemble the packing surfactant tail, resulting in increased surfac-
tant solubility to the aqueous solution.
In our work, the solubility challenge of NDAS zwitterionic surfactant
in pure water was successfully resolved by the presence of a mono-
unsaturated double bond in the hydrophobic tail, the introduction of an
amido-based group on its head part, and the addition of 0.1 mol/L
PTMAB hydrotrope. Also, cationic nitrogen and an anionic sulfonate
form a zwitterionic nature on its head part (Fig. 1), which contribute ions
to the aqueous solution and increase the polarity of the NDAS. As a result,
the solubility was improved, making the NDAS bio-based zwitterionic
surfactant certainly applications extensive. And, unless there is a special
note, all of the samples examined under pure water in this work contain
0.1 mol/L PTMAB to ensure good NDAS solubility.
Table 2
NDAS bio-based zwitterionic surfactant surface tension results compared with other zwitterionic surfactants.
Surfactant Hydrophobic length cmc/(106 mol/L) γcmc/(mN/m)
NDAS C24 3.58 36.81
EHSB C22 5.64 31.41
EDAB C22 5.98 35.09
SPODP C18 þ Phenyl 71 32.5
C18DmB C18 140 – 9.27
C16DmB C16 150 – 5.49
5
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3.3. Surface activity evaluation
By extrapolation of two-linear parts of the surface tension plot, the
cmc of NDAS (made in pure water) in 0.1 mol/L PTMAB hydrotrope at a
surface tension of 36.81 mN/m was 3.58  106 mol/L (Fig. 2, Table 2).
Because of the longer hydrophobic chain tail, the NDAS surfactant had a
lower cmc and a better tendency to accumulate at the air/water interface
than surfactants bearing short hydrophobic tail counterparts.
The decrease of the surface tension of pure water indicates an
inversely proportional function of the increase in the concentration of
surfactant, with the repercussions of decreasing the surface tension until
it reaches a constant point known as cmc. The Gibbs adsorption isotherm
Eq. (1) is commonly used to compute the maximum surface excess con-
centration at cmc (Γ cmc ) at constant temperature and pressure conditions
[21,30,31]:
1 ∂γ
Γ cmc ¼  ð Þ (1)
2:303nRT ∂logC
Where R is the value of a molar gas constant, T is the constant temper-
∂γ
ature (K), C is the concentration of surfactant (mol/L), and ð∂logC Þ stands
for the slope below the cmc in the surface tension vs. NDAS concentration
plot. The value of n is denoted as the constant number of NDAS zwit-
terionic surfactant species at the interface, which was presumed to be 1.
Also, the occupied area per the NDAS surfactant molecule adsorbed at the
air/aqueous solution interface (Acmc) was calculated using an equation
reported in the past reports (Eq. (2)) [17,21,31]:
1
Аcmc ¼  1016 (2)
LΓ cmc
L stands for Avogadro’s constant.
As the hydrophobic tail chain part of the surfactant is extended, it will
influence high surface activity by the surfactant's greater tendency to
adsorb at the air/water interface and form a strong monolayer at the
interface [32]. In the comparison to the previously reported short-chain
surfactants (Table 2), the occupied area of the NDAS zwitterionic sur-
factant at the air/water interface (Acmc) was much better as it could reach
as low as 0.23 nm2/molecule with the maximum value of adsorption at
the interface, which mainly attributed by its longer hydrophobic tail
chain. However, the value of surface tension at cmc of NDAS (γcmc) was
slightly higher because an ultra-long hydrophobic tail chain causes a
steric effect, as well as the result of hydrophobic–lipophilic interaction
within the molecule. This phenomenon makes the surfactant prone to
form pre-micelle aggregates (or submicelle aggregates) in the solution,
which is inverse to the surfactants with hydrophobic tail chains shorter
than C24 fatty acid. As shown in Table 2, compared to NDAS surfactant,
which has the most extended hydrophobic chai tail, the largest Acmc
demonstrated by erucyl dimethyl amidopropyl hydroxy sulfobetaine
(EHSB) is mainly associated with the establishment of hydrogen bonds
between hydroxyl groups in its head and H2O molecules.
The fascinating thing is that the SFT results obtained in this study are
closely related to other reports relating to ultra-long chain surfactants
such as erucyl dimethyl amidopropyl carboxybetaine (EDAB) and EHSB.
Since all of them showed a cmc value in the magnitude of 106 mol/L,
which is relatively lower than that of surfactants from short-chain
Γ cmc/(103 mmol/m2) Acmc/(nm2/molecule) Ref.
7.43 0.23 This work
2.98 0.56 [17]
3.94 0.42 [17]
5.23 0.31 [22]
1.8 [21]
3.0 [21]
H.I. Mtui et al.
Fig. 3. (a) The plot of IFT vs. NDAS surfactant concentration at 45  C. (b) The
dynamic IFT between Daqing crude oil and NDAS surfactant concentration vs.
time at 45  C. (c) Consequence of temperature variations to the IFT vs. time at
0.05 g/L NDAS concentration.
counterparts such as N,N-dimethyl-N-[2-hydroxy-3-sulfo-propyl]-N0 -
phenyloctadecanoyl-1,3-diaminopropane (SPODP), N-hexadecyl-N,N-
dimethyl-2-ammonio-1-ethanecarbonate (C16DmB), and N-octadecyl-
6
Green Chemical Engineering xxx (xxxx) xxx
N,N-dimethyl-2-ammonio-1-ethanecarbonate (C18DmB). The lower cmc
with maximum surface excess adsorption and small value of Acmc results
prove that NDAS surfactant has higher performance at a low dosage. In
this way, it helps to address the environmental challenges associated
with using short hydrophobic-chain surfactants, because they are used in
large quantities with low performances, resulting in severe environ-
mental pollution [33]. And the results prove that NDAS bio-based sur-
factant has potential in the EOR industrial field and can be applied in
many daily household applications such as detergent, fabric softener,
shampoo, etc.
3.4. Interfacial activity evaluation
As shown in Fig. 3a and 3b, 0.05 g/L of NDAS surfactant could reduce
the interfacial tension between the Daqing crude oil and simulated for-
mation brine to 4.7  10-4 mN/m at 45  C. Also, there was no significant
difference in the decrease of the Daqing crude oil-water interface at
NDAS concentrations higher or equal to 0.05 g/L, since all those con-
centration ranges were able to reach the ultralow values in the magnitude
of 10-4 mN/m (Table 3). As illustrated in Fig. 3c, at 0.05 g/L NDAS, the
dynamic interfacial tension between crude oil and simulated formation
brine with time at different temperatures was studied to pattern the
thermal stability of NDAS chemical structure. The minimum and equi-
librium interfacial tensions could reach ultralow levels (~10-3 mN/m) at
45  C to 90  C (Table 3). As exemplified in Fig. 4a and Fig. 4b, the var-
iations of interfacial tension with time between Daqing crude oil and
0.05 g/L NDAS concentration at 45  C were also studied by adding extra
NaCl and Ca2þ ions, respectively. IFTs between Daqing crude oil and
formation brine of 0.05 g/L NDAS could reach an ultra-low level of
~103 mN/m at NaCl concentrations less than 150 g/L (Fig. 4a, Table 3).
When the Ca2þ ions' concentrations in 0.05 g/L NDAS were less than or
equal to 200 mg/L, the interfacial tensions could still reach ultra-low
levels (the magnitude of 103 mN/m) (Fig. 4b, Table 3). Interestingly,
the NDAS's ultra-long hydrophobic chain part guaranteed exceptional
activity at the crude oil-water interface to an ultralow value of 104 mN/
m at a dosage of 0.05 g/L. This NDAS dosage is very low, equivalent to
lower than 2% (w/w) of the highest reference concentration (3 g/L)
commonly used in the EOR field. This achieved result could be the
newest and likely result ever discovered in the ultra-long chain bio-based
surfactant field.
In the EOR industrial field, 0.5 g/L (lowest concentration) and 3 g/L
(highest concentration) are used as reference surfactant concentrations
for treatment in the oil reservoir flooding systems [23,34,35]. A fasci-
nating result was obtained in this work, as only 0.05 g/L NDAS con-
centration (equivalent to 10% (w/w) dosage from the common 0.5 g/L)
was required to reduce the Daqing crude oil-simulated formation brine
interface to an ultralow value equal to 4.7  104 mN/m. And it still
could reach the magnitude of 103 mN/m for a 0.03 g/L NDAS con-
centration, corresponding to 1% (w/w) dosage relationship from the
standard 3 g/L EOR surfactant dosage. It should be noted that all of the
experiments and measurements were conducted in an alkali-free envi-
ronment. The readily IFT reduction mechanism was associated with the
Daqing crude oil, which covers more than 65% as hydrocarbons with
primary alkanes ranging from C13 to C31, and resins compositions are
more than 24%, making it have high compatibilities with the NDAS
surfactant's long alkyl chain tail composed of C24 by non-polar covalent
interaction and part polar covalent bond interactions, respectively. Also,
the dipole-dipole interactions between the surfactant polar head and
brine sub-phase resulted in the decrease of the IFTs to ultra-low levels
relating to the increased tertiary oil recovery.
Alkali additives have traditionally been employed to boost the
effectiveness of petrochemical-based surfactants or plant-derived sur-
factants in lowering crude oil-water interfacial tensions to ultra-low
levels [35–37]. On the other hand, alkali addition poses a severe issue
regarding well bore scaling, stratum degradation, and surfactant
permeability fading [38]. The result of ultralow interfacial tension
H.I. Mtui et al. Green Chemical Engineering xxx (xxxx) xxx

Fig. 4. Dynamic IFT between Daqing crude oil and simulated formation brine of 0.05 g/L NDAS surfactant vs. time at 45  C: (a) at different NaCl contents and (b) with
the variation of Ca2þ ions' concentrations.

(~103 mN/m) of surfactants in formation of brine is a critical compo-
nent for tertiary oil recovery technologies [39]. Independent of alkali
addition, NDAS surfactant showed an ability to decrease the crude
oil-water interface to an ultralow value. Mechanistically, at the start,
with the increase in concentrations of NDAS, the crude oil-water inter-
face could be reduced to a very low level, which was attributed to the
surfactant molecules' mainly accumulating at the oil-water interface. As
the NDAS surfactant molecules continued to diffuse onto the oil phase
before saturation point, the interfacial tension slowly reached equilib-
rium, and eventually the interfacial tension value was also steady
(Fig. 3a). Furthermore, as the temperature was raised, the duration of the
dynamic interfacial tension reaching the ultra-low level was decreased,
possibly due to an increase in the surfactant's solubility [22,40], which
also demonstrates the thermal stability of NDAS and its ability to work in
surfactant flooding systems with higher temperature degrees at a very
low concentration (Fig. 3c).
Apart from that, the addition of salt ions into the aqueous solutions
was noted to sink the performance of NDAS surfactant since the extreme
amount of Ca2þ or Naþ ions acted as counter ions that diminished the
hydration of the surfactant head. They caused the surfactant to move
from the oil-water interface to the oil phase, impacting the gradually
increased interfacial tension. With reference to many oil fields in China,
the salt concentrations of many oil wells are commonly less than or equal
to 16 g/L for NaCl concentrations and not higher than 0.3 g/L for con-
centrations of Ca2þ ions [23,41]. As shown in Fig. 4, with the addition of
a small amount of Naþ/Ca2þ ions, the IFT decreased slightly because the
Naþ/Ca2þ ions acted as counter ions, which waned the interaction of
þ
SO2
3 . And as the concentration of Na /Ca
2þ
in the NDAS solution
increased, the excessive Naþ/Ca2þ ions hampered surfactant hydration,
causing the surfactant to transfer from the water-oil interface to the
non-polar oil phase and increase the IFT.
In addition, the NDAS’s zwitterionic nature of the head part governs
the performance over a wide range of pH in the oil reservoir. Hence,
according to the results we obtained here and those facts, the ultra-long
hydrophobic chain part of the NDAS zwitterionic surfactant proves
excellent performance in reducing the oil-water interface without adding
any chemicals like alkalis. It still had outstanding interfacial activity at
low dosage in high salinity conditions, and its impressive result ever

Table 3
The summary of the effect of NDAS surfactant on IFT between Daqing crude oil and simulated brine at different parameters.
Concentrations/(g/L) At 0.05 g/L NDAS concentration

0.05–3 0.03  0.01 Temperature/ C NaCl/(g/L) Ca2þ/(mg/L)

45–75 90 105–120 0–25 50–100  150 0–40 100–200  400

104 mN/m ✓ ⨯ ⨯ ✓ ⨯ ⨯ ✓ ⨯ ⨯ ✓ ⨯ ⨯
103 mN/m ✓ ✓ ⨯ ✓ ✓ ⨯ ✓ ✓ ⨯ ✓ ✓ ⨯
 102 mN/m ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓ ✓

Fig. 5. Photographs of the salt tolerability test results of 0.5 g/L NDAS surfactant solutions made from the simulated formation brine: (a) at different NaCl con-
centrations and (b) with the variation of Ca2þ ions' concentrations.

7
H.I. Mtui et al. Green Chemical Engineering xxx (xxxx) xxx

Table 4 Testing the salts tolerance of the surfactants is crucial and has been
The comparison of salt tolerances of various surfactants at 45  C. well presented in previous research works relating to EOR [21]. But
Surfactant NaCl/(g/ Ca2þ/(mg/ Ref. remarkably, the salts tolerance results of ultra-long fatty acid chain-based
L) L) surfactants are first exposed in this work. When the salts tolerance result
Petroleum sulphonates 14 18 [42] of NDAS surfactant was compared to that of other previously reported
Linear alkylbenzene sulfonates 22 133 [22] short-chain surfactants, it was discovered that NDAS is noticeably more
Nonylphenol alkyl sulphonate 42 216 [43] robust than those of petroleum sulphonates [42], linear alkylbenzene
surfactants sulfonates (LAS) [22], and nonylphenol alkyl sulphonate surfactants
NDAS  200  250 This
work
(C12-NPAS) [43] (Table 4). And with reference, this result proves that
the NDAS zwitterionic surfactant can be more prominent in EOR,
particularly in harsh reservoir conditions, as it has strong compatibility in
revealed in the ultra-long chain bio-based surfactant industry. The result such high salinity conditions.
guaranteed the great potential of NDAS with widely applied functions,
especially in EOR.
3.6. Emulsification analysis

3.5. Salts tolerance evaluation
As shown from the photographs in Fig. 5a, no precipitation occurred
after adding any concentration of NaCl higher up to 200 g/L in 0.5 g/L
NDAS surfactant solution (0.5 g/L ¼ EOR field reference concentration)
made in simulated formation brine. Also, no precipitation was observed
when adding Ca2þ concentration to 250 mg/L at 45  C for 24 h (Fig. 5b).
During the experiment, before the solutions were allowed to settle for
more than 24 h for observations and inferences, the centrifugation of all
of the prepared solutions was performed to confirm whether the solu-
bilization of the NDAS surfactant and extra salt molecules was completed
with a homogenous solution in the formation brine.
As shown in Fig. 6, the time for the separation rate of 20%, 40%, 60%,
80%, and 100% of aqueous solutions from the emulsion (a fused mixture
of crude oil and 0.5 g/L NDAS surfactant) at 45  C were 2, 3, 5, 20, and
301 min, respectively (the time average was calculated after three times
experiments as shown in Table S2). Meanwhile, the separation rate at
different NaCl and Ca2þ concentrations was achieved in the maximum
duration of 30 min, as shown in Tables S3–S4. The increase in temper-
ature could manifest the emulsion stability longer to the maximum of
519 min (Table S5). The results indicate that the NDAS surfactant could
ensure the emulsion capacity and stability roughly to 5 h, and more than
8 h when the temperature was raised to 65  C.
Mechanistically, it substantiates that the hydrophobic chain part of

Fig. 6. Photographs of the separation rate of aqueous phase from the crude oil phase in the presence of 0.5 g/L NDAS surfactant at different times measured at 45  C.

Fig. 7. Illustration of biodegradation estimation obtained by EPI SUITE-BIOWIN-3 model software.

8
H.I. Mtui et al.
NDAS surfactant had a lot of contact with the crude oil molecules due to
the covalent electronic interaction by van der Waal force which exists
between carbon atoms in crude oil and alkyl chain tail in surfactant. In
contrast, because of the ionic nature of amido and sulfonate, the polar
part had a lot of connections with water molecules via dipole or ion-
dipole interactions. And this result demonstrates that NDAS is a strong
emulsifier because it took longer to stabilize than the branched short-
chain surfactants like N-phenyl fatty amidopropyl-N,N-dimethylcarbox-
ylbetaine [23]. It also notable results in the ultra-long chain surfactants
field relating to the emulsification parameter.
3.7. Biodegradability estimation
Fig. 7 shows NDAS surfactant's biodegradability estimation ratings.
An ultimate biodegradability estimation time for NDAS surfactant after
being released to the environment was in months since it had a BIOWIN-3
model scored at 2.34, which was expected that the NDAS surfactant could
have longer or no biodegradability time, but it was vice versa here as
NDAS showed a good biodegradability (high score) just in the order of
months. This is due to the presence of a monounsaturated double bond in
its tail, which is easily degradable in the presence of oxygen, and also the
presence of an amido functional group in its head (Fig. S10). In addition,
NDAS because of sulfonate hydrophilic head group which significantly
undergoes hydrolysis under the high acidity condition and when there is
high temperature. Also oxidation of the long alkyl chain is anticipated to
occur if there is a presence of a high abundance of oxidants.
Environmental protection and sustainability concerns are quite pre-
vailing nowadays, and the development of environmentally friendly
surfactants and other highly degradable compounds has a lot of promise.
As a result of this finding, it was confirmed that NDAS is safer in the
environment because it appears to be biodegradable in a short period,
just months. Song et al. [44] (2014) elucidated that the more significant
score obtained in the ultimate biodegradation estimation model indicates
the probability of total degradation speed is faster. Scores above 2.8 are
in the biodegradable order of weeks, while scores between 2.0 and 2.8
are in the months’ category [23]. Our developed NDAS bio-based zwit-
terionic surfactant's biodegradation score was in the order of months,
which is ideal for EOR, where the surfactant's environmental stability is
recommended to be around a month. Because of this intriguing degrad-
ability speed result, it also helps to conserve the environment and ensure
the sustainability concern while it is in use.
4. Conclusions
In summary, we developed a new ultra-long chain bio-based zwit-
terionic surfactant NDAS from nervonic acid extracted from non-edible
malania oleifera and Lunaria seed oils as the main starting material
through a simple and effective method. The NDAS surfactant demon-
strated outstanding performance on the aqueous solutions, such as the
reduction of interfacial tensions to an ultra-low value (4.7  104 mN/m)
at a very low dosage (0.05 g/L), in high salinities and high temperatures.
The result confirms that the ultra-long hydrophobic chain part of the
surfactant plays a significant role in the interfacial activity. The ultralow
interfacial tension value, high salts compatibility, low cmc at SFT
(~106 mol/L), renewable feedstock, and good biodegradability are the
main factors that make NDAS surfactant to be a promising conventional
bio-based surfactant alternative to petrochemical and oleo chemical-
based surfactants in applications, markets, and industries, particularly
in the EOR field. We further urge more research on the wettability,
foamability, and flooding mechanisms of the NDAS bio-based surfactant
for EOR. Also, given the negative impacts of malania oleifera and Lunaria
seeds on the environment as wastes, they could be significantly reduced
by producing an abundant NDAS surfactant's primary starting material
(nervonic acid) from their squeezed seed oils, thus creating more value
for such seeds, and ultimately conserving the environment. And with the
recent concern about environmental protection with green chemistry, the
9
Green Chemical Engineering xxx (xxxx) xxx
synthesis procedure used in this work is advised to be used in bio-based
surfactants on an industrial scale to scale up the production of NDAS
surfactants.
CRediT authorship contribution statement
All authors contributed to the writing of the manuscript. Homely
Isaya Mtui: conceptualization, methodology, synthesis, detection, anal-
ysis, first draft writing, final draft reviewing, and editing. Fang-Hui Liu's
responsibilities include investigation and guidance. Wei Wang was in
charge of conducting thermal stability experiments. Jian-Qiao Lang:
moderation and guidance. Shi-Zhong Yang: methodology, analysis, and
supervision. Bo-Zhong Mu was in charge of conceptualization, supervi-
sion, fundraising, project management, review, and editing. All authors
have approved the final version of the manuscript.
Declaration of competing interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research was financially supported by the National Key Research
and Development Program of China (No. 2017YFB0308900), the Na-
tional Natural Science Foundation of China (No. 51574125), and the
Fundamental Research Funds for the Central Universities of China (No.
50321101917017). Additional support was provided by Research Pro-
gram of State Key Laboratory of Bioreactor Engineering. The authors are
grateful for the financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.gce.2022.08.001.
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