J Surfact Deterg
DOI 10.1007/s11743-016-1813-z
ORIGINAL ARTICLE
Synthesis, Characterization and Exploratory Application
of Anionic Surfactant Fatty Acid Methyl Ester Sulfonate
from Waste Cooking Oil
Yueming Jin1 • Senlin Tian1 • Jiali Guo1 • Xiao Ren1 • Xinyan Li1
Shumei Gao1
Received: 15 November 2015 / Accepted: 14 March 2016
Ó AOCS 2016
Abstract The environmentally friendly anionic surfac-
tant fatty acid methyl ester sulfonate (MES) was prepared
by esterification of waste cooking oil (WCO), a low-cost
raw material, followed by sulfonation with chlorosulfonic
acid. MES production from WCO (W-MES) gave yields up
to 78 %. Such a value is only slightly lower than the one
obtained from soybean oil (S-MES), 82 %, and almost the
same as that from reused cooking oil (R-MES), 76 %.
According to the two-phase titration results, the content of
the active component, a-MES, in S-MES, R-MES and
W-MES was equal to 76.82, 69.19 and 66.60 %, respec-
tively. The disalt, RCH(CO2Na)SO3Na, contents were
instead 3.2, 3.8 and 4.7 %, respectively. As proved by the
results of the FTIR and NMR characterizations, the
chemical structure of W-MES is almost the same as that of
S-MES and R-MES. The critical micelle concentration of
W-MES is 5.38 mmol/L and the corresponding surface
tension is 32.3 mN/m. The hydrophile-lipophile balance
value of W-MES is 12.33, which indicates that it can form
oil/water emulsions. The three MES demonstrated the same
adsorption efficiency, yielding a pC20 value of 3.22, and
similar foam stability. Their detergency can be up to 75 %
at a concentration of 400 mg/kg and the tolerance to Ca2?
is higher than the one exhibited by linear alkylbenzene
sulphonic acid and alpha olefin sulfonate. Additionally,
W-MES shows a considerable solubilization capacity
towards polycyclic aromatic hydrocarbon as the molar
solubilization ratios to pyrene, phenanthrene and
& Senlin Tian
tiansenlin@outlook.com
1 research and industrial application. The industrial prepa-
Faculty of Environmental Science and Engineering,
Kunming University of Science and Technology,
Kunming 650500, Yunnan, China
•
acenaphthene in a 30 mmol/L solution are 1.22 9 10-3,
2.67 9 10-3 and 3.81 9 10-3, respectively.
Keywords Waste cooking oil  Fatty acid methyl ester
sulfonate  Anionic surfactant  Chlorosulfonic acid 
Esterification  Sulfonation
Introduction
The anionic surfactant fatty acid methyl ester sulfonate
(MES), which can be easily synthesized by using biological
oil as the raw material, is widely used in the chemical
industry because of its excellent surface-activity and self-
assembly behavior. In comparison to common commercial
surfactants, such as linear alkyl benzene sulfonate (LAS),
alpha olefin sulfonate (AOS) and alcohol ethoxy sulfate
(AES), MES finds wider application as a phosphide-free
detergent because of its low oil/water interfacial tension and
eco-friendliness [1, 2]. In particular, the advantages of MES
are (1) excellent water solubility and water hardness sta-
bility, (2) low viscosity and good wetting power, (3) non-
toxicity, as it is only slightly irritant to humans and presents
good biodegradability [3, 4]. MES consists of carbon chains
and a sulfonic group, which represent the hydrophobic and
hydrophilic groups of the molecule, respectively. A good
amphipathic property makes MES a good candidate in
surfactant-enhanced remediation (SER), especially in
organic-contaminated soils [5, 6]. Furthermore, as a
degradable surfactant, MES has the advantage over other
surfactants of having a lower impact on the environment.
MES has attracted great attention in both scientific
ration of MES is commonly based on the two technical
routes. The first route generally uses fatty acids as raw
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materials, which are processed through esterification, sul-
fonation, re-esterification, bleaching, and neutralization
[7]. MES prepared on the basis of this method can be
obtained through a re-esterification process because of its
low disodium salt content. Another possible route consists
in the sulfonation of fatty acids with either SO3 or
chlorosulfonic acid and subsequent esterification, bleach-
ing, and neutralization to integrate the MES product [8–
10]. Regardless of the production procedure adopted,
vegetable oil is the most commonly used starting material
in MES production and about 80 % of the total production
cost of methyl ester, the intermediate product of MES, is
linked to the oil source [11]. Though the synthesis proce-
dure of MES is simple, the shortage and relatively high
cost of raw materials is becoming the major economic
constraint in its production and commercialization. Several
studies have been carried out with the aim of reducing
MES production costs, but the majority of these works are
focused on the improvement of the synthesis method and
an increase in yield [8, 10, 11]. On the other hand, the idea
of developing a new, low-cost, oil source to replace veg-
etable oil should become the primary consideration in the
MES production industry.
Synthesis of MES from waste cooking oil (WCO) can
lower the production cost of MES and represent an efficient
use of biomass. Indeed the global production of WCO can
be up to 29 million tonnes per year [12]. WCO is a
domestic waste, generated as the result of cooking food
with edible oil. These oils are not re-useable for human
consumption, due to presence of toxic components [13].
Rancid oil can damage the cytochrome enzymes and other
enzyme systems of the human organism, and different
forms of cancer can be caused by the aflatoxin, which is
produced through high oxidation of oil. Furthermore, the
lack of standardized collection systems implies that, in the
long run, the disposal of WCO will represent a serious
environmental and economic issue [13]. WCO shares the
common components of unsaturated fatty acids as well as
numerous organics, impurities and water. Uncontrolled
emissions will lead to pollution of land resources and water
as well as representing a waste of biomass [14–16]. All
these considerations make the disposal of WCO a major
task, worthy of being tackled.
Although vegetable oils, such as soybean and palm oils,
are still widely used to synthesize MES industrially, its
production from WCO has the additional advantage of
producing methyl esters as an intermediate. This has
increased interest towards the use of WCO since methyl
ester, also known as biodiesel, can be a good alternative to
petroleum-based diesel [16–18]. Production of MES from
WCO therefore has obvious advantages associated with
reduced production costs and recycling of waste oil to give
high added value products [13, 19, 20].
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J Surfact Deterg
The purpose of this study was to confirm the feasibility
of preparing MES from WCO without changing the reac-
tion conditions adopted when using different raw materials,
aiding in the commercialization of W-MES. The quality of
W-MES was evaluated by comparing its properties to those
of MES obtained from soybean and reused cooking oils as
starting materials. The products of the three different
synthesis oil materials have been characterized by FTIR
spectra, 13C-NMR and 1H-NMR. Surface chemical prop-
erties, tolerance to calcium ion, and detergency, foaming,
and solubilization ability have also been fully studied.
Experimental Section
Materials
WCO with an iodine value of 129 g I2/100 g and an acid
value of 0.83 mg KOH/g was obtained from Dingsheng
Biological Energy Co. Ltd. (Yunnan, China); chlorosul-
fonic acid (AR-grade, 99 %) was obtained from Xiya
Reagent Research Center, (Shandong, China); dehydrated
methanol (AR-grade) and trichloromethane (AR-grade)
were supplied by Fuchen Chemical Reagent Co. Ltd.
(Tianjin, China); n-hexane (AR-grade) and potassium
hydroxide were supplied by Kelong Chemical Reagent Co.
Ltd. (Chengdu, China); hydrogen peroxide (30 wt%) was
supplied by Yanglin (Shandian industrial district, Yunnan,
China); Double-distilled water further deionized using
Milli Q (Millipore Corp., USA) was used for all
experiments.
Preparation of MES
MES was synthesized through a simple five-step reaction
process, followed by esterification of WCO with metha-
nol, sulfonation of methyl esters with chlorosulfonic acid,
aging of sulfonation product, bleaching of the aged pro-
duct with H2O2 and neutralization of the bleached product
with NaOH. The procedure was slightly modified from
the reported methods [8, 9, 21]. Firstly, WCO and
dehydrated methanol were stirred moderately in a three-
necked flask at 60 °C for 1 h in the presence of 1 wt%
KOH catalyst. The reaction mixture was then transferred
into a separating funnel and cooled to room temperature.
The lower layer of the separated mixture was composed
of unreacted methyl esters and glycerol. Methyl esters in
the upper stratum were separated and washed with warm
water; n-hexane washed with saturated NaCl was then
added to get the canary oily liquid [22, 23]. In the second
step, oily methyl esters and chloroform were stirred in a
three-necked flask for half an hour, after which chloro-
sulfonic acid was added drop-wise in the solution. Once
J Surfact Deterg
Scheme1 Synthetic procedure
of MES
the addition was completed, the reaction mixture was
stirred for another 1.5 h at 60 °C under a N2 atmosphere
(1 atm) [24]. Subsequently, the reacted mixture was left
in a flask at 80 °C for 2 h, this aging process was nec-
essary to complete the reaction and improve the conver-
sion rate [4]. After the aging stage, the obtained MES was
intensely colored owing to the high reaction temperature
and chlorosulfonic acid molar ratio. A bleaching process
was therefore needed. 30 % hydrogen peroxide (with
10 mL methanol) was added to the aged product and
stirred in a flat flask for 1 h at 60 °C to neutralize the
reaction mixture [25]. Finally, 30 and 5 wt% NaOH
solutions were added drop-wise while stirring to increase
the pH of the bleached product up to 6–7 [26]. A pale,
yellow, sticky liquid MES product was obtained by
keeping the mixture neutralized and dehydrated. The
reaction mechanism is shown in Scheme 1.
Analysis and Characterization
The methyl ester content was analyzed by a gas chro-
matography-mass spectrometer (GC–MS, Trace1300-ISQ,
Thermofisher. USA) equipped with a flame ionization
detector (FID) and capillary chromatographic column
(Elite-5MS, 30 m 9 250 lm). An aliquots (150 lL) of the
sample were dissolved in 1.5 mL of n-hexane and about
1 lL of the solution was injected in the column. The auto
injection temperature was 250 °C. Helium was used as
carrier gas. The oven was started at a temperature of 80 °C,
which was increased to 200 °C at a rate of 7 °C/min. The
temperature was held at this value for 5 min, further
increased to 280 °C, at a rate of 10 °C/min, and held for
3 min. The FID temperature was set at 380 °C [8, 27, 28].
The chemical structure of MES was characterized
through FTIR and NMR analyses. The FTIR analysis was
performed in the range 4000–400 cm-1 at 25 °C using
TENSOR27 spectrometer (Bruker Germany). 1H-NMR and
13
C-NMR were recorded using the Bruker DRX500 spec-
trometer with CDCl3 as the solvent.
Surface Tension Measurements
MES aqueous solutions ranging from 0.001 to 0.1 mol/L
were prepared with ultrapure water. Surface tension mea-
surements of solutions having different concentrations
were carried out by a method of Wilhelmy plate using the
BZY-101 Automatic surface tensiometer (Fangrui Co. Ltd.,
Shanghai, China). The measurements were detected three
times until the surface tension remained constant [29, 30].
Salt Tolerance and Detergency Experiment
To determine the tolerance of MES to calcium ions, CaCl2
aqueous solutions of different concentrations were added
into the MES solution at 60 °C, which was then cooled to
25 °C. The highest concentration of CaCl2 solution that can
be added before the MES aqueous solution becomes turbid
defines the maximum tolerance of the surfactant to calcium
ions [31, 32]. The detergency of three MES solutions was
tested by using an agitation/mixing appliance, this test was
carried out under the conditions of a temperature of 25 °C,
pH of 7.8, a rotation speed of 120 rpm. 5 g of MES was
added in 1 L of water, washing for 15 min and two rinsing
cycles, each being 5 min long. The soiled cotton dyeing
with starch and caramel pigment was cut into a size of
5 cm 9 5 cm and three sheets of cotton were used for each
test [33].
Foaming and Foam Stability
Foam stability was tested by preparing 50 mL of MES
aqueous solutions at 25 °C having micelle concentrations
corresponding to 0.5 times, one time, and two times the
CMC, respectively. Different quality foams were generated
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Fig. 1 Composition of three
MES intermediates from
different oil materials
by high-speed (3000 rpm) stirring of the solutions for
5 min [32].
Solubilization of Polycyclic Aromatic Hydrocarbon
(PAH)
Solubilization of PAH in MES solutions was carried out in
40 mL glass tubes with Teflon-lined screw caps at 25 °C.
10 mL of MES surfactant solutions with concentrations
ranging from 0.003 to 0.03 mol/L were added into the
tubes, PAH were then added into each tube in amounts
greater than those required to saturate the solutions. The
samples were subsequently vibrated on a thermostatic
oscillator for 36 h at 25 °C to achieve equilibrium solubi-
lization. 1 mL of MES aqueous solution was removed and
mixed with 10 mL of n-hexane, to be analyzed by ultra-
violet–visible spectrophotometry (Shimadzu UV-2600) at
maximum absorption wavelength. The maximum absorp-
tion wavelengths of pyrene, phenanthrene, and acenaph-
thene are 333, 250, and 227 nm, respectively [29].
Results and Discussion
Composition of Methyl Ester Intermediate Derived
from Various Oil Materials
Methyl esters are the crucial intermediate in MES
preparation. In this work, methyl esters were prepared by
esterification of oils with methanol. Soybean and reused
cooking oils were used as reference materials and com-
pared with WCO. No significant difference was observed
in the methyl ester yield obtained from the three oils
tested. After 60 min of reaction, the methyl ester yields
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J Surfact Deterg
were equal to 82, 78, and 76 % for soybean, WCO, and
reused cooking oil, respectively. The lower yield obtained
from WCO compared to soybean oil may be attributed to
the higher fat content present in the former oil, which
cannot be esterified by a base catalyst; furthermore, the
presence of impurities increases the percentage of unre-
acted oil, reducing the overall yield. Despite these
drawbacks, the use of a conventional KOH catalyst, a
simple experimental procedure, and mild reaction condi-
tions, allowed the achievement of a methyl ester yield
that is only marginally lower for WCO compared to
soybean oil; furthermore, these yields are very close to
the reference values for vegetable and waste oils treated
with a new catalytic system and improved synthetic
methods [8, 11, 12].
The methyl esters obtained from the three different oil
materials were analyzed by GC–MS, the compositions of
the three samples are reported in Fig. 1. The results show
that the predominant components of methyl esters derived
from soybean oil are octadecadienoic acid methyl ester,
octadecenoic acid methyl ester, and c-linolenic acid methyl
ester. The component present in the highest percentage is
octadecadienoic acid methyl ester, which accounts for
32.8 % of the entire intermediated. Methyl esters derived
from reused cooking oil and WCO mainly consist of
octadecenoic acid methyl ester, octadecadienoic acid
methyl ester, and hexadecanoic acid methyl ester. The
main component is octadecenoic acid methyl ester, which
is present with a percentage of 31 %. The percentage of
unsaturated acid methyl esters in the methyl esters derived
from soybean oil is 79.78 %, higher than the ones obtained
from reused cooking oil (64.71 %) and WCO (56.1 %).
The predominant component of the three methyl esters is
similar, especially when comparing reused cooking oil and
J Surfact Deterg

WCO which have similar starting compositions. Actually
reused cooking oil is the greatest constituent of WCO. Both
yield and composition of methyl esters derived from WCO
are in line with the methyl esters derived from soybean oil,
indicating that the production of methyl esters from WCO
is feasible without the need of modifying the reaction
conditions (e.g. temperature, ratio of reactants) of the
current commercial method.
Characterizations of MES
As the FTIR data for MES prepared from three oil mate-
rials shows in Table 1, the results are very close to the
theoretical values, indicating that the product properties are
in line with those of MES derived from vegetable oil [34].
The FTIR spectra are compatible with the proposed
structures shows in Table 1.
The typical characteristic peaks of C-H vibration (at
2927 cm-1), C=O bond (at 1737 cm-1) and S=O bond (at
1169 cm-1) are observed in the FTIR results for the three
final compounds. The peak observed at 1638 cm-1 can be
ascribed to H2O, whose presence is caused by an incom-
plete de-hydration. The characteristic bands of the three
final products are approximately the same and the FTIR
spectra data agrees with the structure of pure MES. The
compositions of the three synthesized products were con-
firmed by 1H-NMR and 13C-NMR and the results are
shown in Tables 2 and 3.
According to the 1H-NMR data, the signal relative to a
proton attaching to the carbon atom bearing the sulfonate
group (–SO3) appears at d = 3.66. Signals for protons in
the hydrocarbon chain are observed between d = 0.87 and
2.29, and the signal for the proton attaching to the carbon
atom bearing an ester group (–COO) appears at d = 3.42.
The 13C-NMR spectra indicate that the carbon for the
terminal methyl appears at d = 14.42. The carbon directly
attached to the sulfonate group (–SO3Na–CH–) is observed
at d = 77.21. The signal for carbon directly attached to the
ester group (–OCH3–) is observed at d = 50.66 and the
carbon in the ester group appears at d = 173.27.
For the three final products, the signal responses corre-
sponding to the terminal CH3–, –OCH3, –CO– and CH2–
are observed. The responses obtained are very similar to
each other, especially between R-MES and W-MES, this
result is in accordance with the one obtained for methyl
esters, indicating that the properties of WCO are close to
those of the reused cooking oil. Both FTIR and NMR
results are in good agreement with the results obtained
from the literature and prove that synthetic products are the
target MES product [34, 35].
Contents of Active Ingredients in Final MES
Products
MES contains two kinds of active matters: RCH(CO2-
Me)SO3Na, which will be referred to as a-MES, and

Table 1 FTIR spectra data of

Wavenumber (cm-1) Assignments
MES prepared from the three oil
materials Soybean oil Reused oil WCO

2927 2927 2927 CH2– asymmetric stretching vibration

2855 2855 2854 CH2– symmetrical stretching vibration
1737 1720 1737 C=O vibration reduction
1638 1637 1636 H2O
1169 1169 1169 S=O vibration reduction
1353 1353 1353 S=O vibration reduction
1042 1043 1041 S=O vibration reduction

Table 2 1H-NMR spectra data

Stock of MES Terminal CH3– –(CH2)n– CH2– linked with –CH– –OCH3 –CH–
of MES prepared from the three
oil materials Soybean oil 0.78 1.15–1.18 2.18–2.19 3.31 3.56
Reused oil 0.88 1.25 2.30 3.43 3.66–3.68
WCO 0.87 1.24 2.29 3.42 3.66

Table 3 13C-NMR spectra data

Stock of MES Terminal CH3– Adjacent CH2– (CH2)n– –OCH3 –CH– –CO–
of MES prepared from the three
oil materials Soybean oil 14.40 22.94 25.22–34.38 50.34 77.38 174.68
Reused oil 14.44 23.00 25.29–39.93 50.63 77.28 173.69
WCO 14.42 23.03 25.31–34.50 50.66 77.21 173.27

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 J Surfact Deterg

RCH(CO2Na)SO3Na, referred to as disalt. A higher disalt

content leads to a lower surface activity of MES and lower
hardness, as its Krafft point is higher than that of a-MES
[35]. Since an excess of disalt content in MES will have
negative impacts on its application, its concentration must
be lower than 5 % [8]. The a-MES and disalt concentra-
tions in MES have been determined through the two-phase
titration method [36]. It was found that the contents of a-
MES in the final products synthesized from soybean oil,
reused cooking oil and WCO is 76.82, 69.19, and 66.60 %,
respectively; while the of disalt content is 3.2, 3.8, and
4.7 %, respectively. These results are consistent with
results reported by Xie, Asselah, and Jiang [8, 37, 38]. It
should be noted that the WCO used in the present experi-
ment has been simply processed by dehydration, decol-
oration and deodorization. This means that the properties of
WCO could be improved through an industrial pretreat-
ment process to optimize the yield of MES, making it a
potential substitute of vegetable oil in commercial pro-
duction after pretreatment.

Surface Tension of MES

The surface tensions of the three MES were determined

through the Wilhelmy plate method. The relationship
between the concentration of MES in aqueous solution and
surface tension at 25 °C is shown in Fig. 2. The surface
tension initially decreases continuously with increasing
MES concentration until its values stabilize as the solution/
air interface becomes saturated with surfactant molecules.
The break point in the plot of surface tension versus sur-
factant concentration is taken as the critical micelle con-
centration (CMC) value. Based on these results, the CMC
value of W-MES is 5.38 mmol/L and the corresponding Fig. 2 Surface tension curves of MES from: a soybean oil b reused
surface tension (cCMC) is 32.3 mN/m. Compared with MES oil c waste cooking oil
synthesized from the other two oils, the surface tension of
W-MES at CMC is slightly higher than S-MES surfactant is adsorbed at the air–water interface and the
(cCMC = 31.5 mN/m) and almost same with R-MES more efficiently the surface tension is reduced [39]. The
((cCMC = 32.6 mN/m), the CMC value are also approxi- pC20 values of W-MES, S-MES and R-MES are all equal
mate as CMC of S-MES and R-MES are 5.49 and to 3.22.
4.96 mmol/L. This result may due to the fact that WCO
contains more impurities than soybean oil; surfactant Salt Tolerance and Detergency
molecules could arrange more closely to the surface, rais-
ing the hydrophilic ability and reducing surface tension. MES consists of alkyl, ester and sodium sulfonate groups.
The adsorption efficiency (pC20) is defined as the The base group constants are 0.475 (single carbon atom),
adsorption ability of the surfactant in correspondence of the 2.4 and 11.0, respectively. According to the Davies
air–water interface and can be determined through the method, the hydrophilic lipophilic balance (HLB) value of
following equation: W-MES is 12.33 (HLB = 7 ? 2.4 ? 11 - 17 9 0.475),
indicating that MES possesses good solubility in aqueous
pC20 ¼  logðC20Þ ð1Þ
solutions. The surface properties of the surfactant can be
where C20 is the surfactant concentration for which the interfered with by the action of salt ions present in aqueous
surface tension of the pure solvent is reduced by 20 mN/m. solutions. Compared with other commercial surfactants,
The larger the value of pC20, the more efficiently the such as LAS and AOS, W-MES shows stronger tolerance

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Fig. 3 Influence of surfactant concentration on the detergency of

MES from the three oils

ability towards salt ions as the concentration of Ca2?

necessary for the solution to become turbid is higher in
MES (1150 mg/L) than in LAS (240 mg/L) and AOS
(800 mg/L).
As shown in Fig. 3, the detergency of the three MES can
all be up to 75 % at a Ca2? concentration of 400 mg/kg.
Good detergency of MES should be caused by due to the
presence of a carbomethoxy group near the sulfonate group
in the MES molecule, which can forma a metastable mi-
celle, avoid the action of calcium and magnesium ions.

Foaming Properties

The foam stability of MES was evaluated based on the

half-life, corresponding to the time necessary for the foam
volume to decay to half of its initial values [38]. Based on
the measurements made, the foamability and foam stability
of three the MES in ultrapure water are very poor at the
concentrations of half the CMC. The initial foam volumes
of the three MES are lower than 2 mL and their half-life is
in the order of a few seconds. The foamability of the three
MES increases with increasing concentration, until a
maximum value is reached, beyond which concentration no
longer has an effect. This concentration is always higher
than the CMC value. Such a result is due to the fact that
foam stability can be affected by the properties of the
liquid. The micelles in the liquid will change its structure
and lead to change of foam stability. Surfactant molecules
also help in maintaining the foam structure. The results
obtained indicate that S-MES has best foamability dis-
playing a stable foam volume of 12 mL, followed by
R-MES and W-MES, whose stable foam volumes are 10.3
and 9.8 mL, respectively. It can be seen that the foama-
bility of MES is related to surfactant concentration rather
than the starting oil material.
Fig. 4 Solubilization of PAH by MES solution
Solubilization of PAH
Taking pyrene, phenanthrene and acenaphthene as typical
target contaminants, the water solubility of PAH in dif-
ferent concentrations of W-MES aqueous solution was
studied. As is clear from Fig. 4, the apparent solubilities of
pyrene, phenanthrene and acenaphthene in water are sig-
nificantly enhanced by an increase in surfactant concen-
tration. The values of the apparent solute solubility at a
surfactant concentration, S*w, determined for pyrene,
phenanthrene and acenaphthene in 30 mmol/L W-MES
solution are 3.65 9 10-5, 8.147 9 10-5 and 1.18 9 10-4
mol/L, respectively. While solubilities in water are
6.4 9 10-7, 6.6 9 10-6 and 2.6 9 10-5 mol/L, respec-
tively [40], W-MES shows significant solubilization

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capacities toward PAH especially when the concentration
is higher than the CMC.
The effectiveness of W-MES in solubilizing PAH can be
evaluated by the molar solubilization ratio (MSR), which
may be determined according to the following Eq. (2):
S  SCMC
MSR ¼ ð2Þ
CS  CMC
In Eq. (2), S is apparent solubility of a PAH at a par-
ticular surfactant concentration, CS is the corresponding
surfactant concentration and SCMC is the solubility when
the solute concentration is at CMC. According to the
Eq. (2), the MSR of W-MES to pyrene, phenanthrene and
acenaphthene are 1.22 9 10-3, 2.67 9 10-3 and
3.81 9 10-3, respectively.
Another parameter to describe the solubilization of
surfactants is the solute partition coefficient, Kmc
Kmc ¼ Xm=Xa ð3Þ
where Xm is the mole fraction of the solute in the micellar
phase and Xa is the mole fraction of the solute in the
aqueous phase. In dilute solutions, Xa & SCMC˙ Vw and Vw is
1.8 9 10-2 L/mol. Since Xms = (S-SCMC)/(CS-CCMC ? S-
SCMC) = MSR (1 ? MSR), The Kmc value can be calcu-
lated using the following formula:
55:4 MSR
Kmc ¼ ð4Þ
SCMC ð1 þ MSRÞ
According to the MSR and log (Kmc) values, W-MES
shows good solubilization capacities toward PAH, which
confirms that it could meet the requirements of the SER
process. The log (Kmc) of PAH follows the order
pyrene [ phenanthrene [ acenaphthene, with values of
3.93, 3.90 and 3.87, respectively, which are well in line
with the octanol/water distribution coefficients, log (Kow).
The values of log (Kow) of pyrene, phenanthrene and ace-
naphthene are 4.48, 4.46 and 3.92, respectively.
Conclusions
Fatty acid methyl ester sulfonate (RCHSO3NaCOOCH3)
was easily synthesized from WCO through an esterifica-
tion-sulfonation process. Without changing the molar ratios
and reaction conditions used when working with different
raw materials, a final product with an a-MES concentration
of 66.60 % and a disalt concentration of 4.7 % was pre-
pared successfully. The FTIR and NMR results indicated
that the chemical structure of W-MES is very similar to
that of S-MES. In addition, the physico-chemical proper-
ties were investigated and surface tension measurements
showed that MES exhibits low CMC and cCMC values.
Compared with other anionic surfactants, W-MES also
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shows stronger tolerance to calcium ions. Excellent deter-
gency and stable foamability also make MES a potential
detergent material. Meanwhile, as a green surfactant MES
shows preferable solubilization capacity toward
hydrophobic pollutants. All these results indicate that
synthesizing MES with WCO is an economic and feasible
method. It can not only reduce the production cost, but also
provide a new method for waste oil disposal.
Acknowledgments This study was supported by National Natural
Science Foundation of China (Nos. 21077048 and 20607008),
National Training Program of Innovation and Entrepreneurship for
Undergraduates (No. 201210674018) and State Scholarship Fund
under Grant 201208535049 from China Scholarship Council.
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Yueming Jin is a graduate student working under the supervision of
Dr. Senlin Tian at the Faculty of Environmental Science and
Engineering, Kunming University of Science and Technology, and
she received her B.Sc. in 2013 from Nanchang University. She is
engaged in research on surfactants, colloid science and environmental
chemistry.
Senlin Tian is a professor at the Faculty of Environmental Science
and Engineering, Kunming University of Science and Technology,
Kunming, Yunnan, China. He obtained his Ph.D. in environmental
chemistry at Zhejiang University, China. Dr. Tian’s research focuses
on interface chemistry and its environmental applications.
Jiali Guo is an undergraduate student in the B.Sc. program at the
Faculty of Environmental Science and Engineering, Kunming
University of Science and Technology. She studied integrated
utilization of waste cooking oil under the supervision of Dr. Tian
with the support of the National Training Program of Innovation and
Entrepreneurship for Undergraduates.
Xiao Ren is an undergraduate student in the B.Sc. program at the
Faculty of Environmental Science and Engineering, Kunming
University of Science and Technology. She studied integrated
utilization of waste cooking oil under the supervision of Dr. Tian
with the support of the National Training Program of Innovation and
Entrepreneurship for Undergraduates.
Xinyan Li is an undergraduate student in the B.Sc. program at the
Faculty of Environmental Science and Engineering, Kunming
University of Science and Technology. He studied integrated
utilization of waste cooking oil under the supervision of Dr. Tian
with the support of the National Training Program of Innovation and
Entrepreneurship for Undergraduates.
Shumei Gao is an undergraduate student in the B.Sc. program at the
Faculty of Environmental Science and Engineering, Kunming
University of Science and Technology. She studied integrated
utilization of waste cooking oil under the supervision of Dr. Tian
with the support of the National Training Program of Innovation and
Entrepreneurship for Undergraduates.
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