Colloids and Surfaces A: Physicochem. Eng.

Aspects 483 (2015) 8795

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Novel zwitterionic surfactant derived from castor oil and its

performance evaluation for oil recovery
Qi-Qi Zhang a , Bang-Xin Cai a , Wen-Jie Xu a , Hong-Ze Gang a , Jin-Feng Liu a ,
Shi-Zhong Yang a , Bo-Zhong Mu a,b,
a
State Key Laboratory of Bioreactor Engineering and Institute of Applied Chemistry, East China University of Science and Technology, Shanghai 200237,
PR China
b
Shanghai Collaborative Innovation Center for Biomanufacturing Technology, Shanghai 200237, PR 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

CPDB could be prepared from castor

oil using a facile and high-yield route.
exhibited excellent surface/interfacial, wetting and foaming
performance.
CPDB is greatly potential application
in enhanced oil recovery.

CPDB

a r t i c l e

i n f o

Article history:
Received 30 March 2015
Received in revised form 13 May 2015
Accepted 19 May 2015
Available online 26 July 2015
Keywords:
Non-edible oil
Bio-based surfactant
Zwitterionic surfactant
Enhanced oil recovery
Oil spill disposal processing

a b s t r a c t
Bio-based surfactants have attracted increasing attention due to their renewable resources and excellent
surface properties. Novel zwitterionic surfactant derived from castor oil was prepared using a facile
and high-yield route and its performance for oil recovery was also evaluated. The surface tension of the
surfactant solution reached 30.7 mN/m at its critical micelle concentration value of 7.08 106 mol/L. The
interfacial tension between crude oil and water could be reduced to ultra-low value as 5.4 103 mN/m
at a low dosage of 0.010 g/L in aqueous solution with the absence of any extra alkali. When used as
dispersant, the dispersion effectiveness of crude oil was 64.69%. Meanwhile, the bio-based surfactant
demonstrated strong electrolyte tolerance, temperature resistance and thermostability, better wetting
and foaming performance, which implied bio-based surfactants had great potential to replace traditional
petroleum-based surfactants in petroleum industries, in particular, in enhanced oil recovery and oil spill
disposal processing.
2015 Elsevier B.V. All rights reserved.

1. Introduction

Corresponding author.
E-mail address: bzmu@ecust.edu.cn (B.-Z. Mu).
http://dx.doi.org/10.1016/j.colsurfa.2015.05.060
0927-7757/ 2015 Elsevier B.V. All rights reserved.

Traditional surfactants are generally petroleum-based and have

been widely used not only as detergents in daily life but also in
industrial elds such as in enhanced oil recovery (EOR) and oil
spill disposal processing (OSDP). However, bio-based surfactants

88

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795

have received increasing attention from industrial and scientic

elds, due to their renewable resource, outstanding physicochemical property, efcient production and low costs [1]. Compared with
petroleum-based surfactants, bio-based surfactants are mainly
using biomass as their raw materials, such as proteins [2], carbohydrates [3] and vegetable oils, which inherit environmental
compatibility, harvestable sustainability and high output capability. Biomass is seen as the most potent substitute to petroleum
chemicals to be used as alternative resource of surfactants [48].
Non-edible vegetable oil, which is one of the most common
kinds in biomass, has become an area of great interests as platform chemicals for surfactants, biodiesel, biopolymers etc., due to
their universal availability, inherent biodegradability and low costs
[912]. Castor oil is a kind of non-edible oil with high production,
and the global castor seed production is estimated over one million tons per year. Castor oil has been applied to produce anion
surfactants, sodium N-acyl isoleucines, which show better surface
properties than that of commercial surfactants [2]. The outstanding performance of bio-based zwitterionic surfactants from fatty
acids has attracted peoples eyes [1315]. However, the knowledge
about castor oil-based zwitterionic surfactants and their applications is still limited. Here we report a novel zwitterionic surfactant
derived from castor oil and its interfacial performance evaluation
in enhanced oil recovery and oil spill disposal processing.
2. Materials and methods
2.1. Materials
AlCl3 (99%, Aladdin, Shanghai, China), benzene (AR, Shanghai
Lingfeng Chemical Reagent Co., Ltd, Shanghai, China), hydrochloric
acid (AR, Shanghai Lingfeng Chemical Reagent Co., Ltd, Shanghai,
China), thionyl chloride (AR, Shanghai Lingfeng Chemical Reagent
Co., Ltd, Shanghai, China), trichloromethane (AR, Shanghai Chemical Reagent Co., Ltd, Shanghai, China), acetone (AR, Shanghai
Lingfeng Chemical Reagent Co., Ltd, Shanghai, China), N,Ndimethyl-1,3-propanediamine (99%, GC, Sigma, Shanghai, China),
methanol (AR, Sinopharm Chemical Reagent Co., Ltd, Shanghai,
China), sodium chloroacetate (99%, Aladdin, Shanghai, China),
ethanol (AR, Sinopharm Chemical Reagent Co., Ltd, Shanghai,
China), ethyl acetate (AR, Shanghai Lingfeng Chemical Reagent Co.,
Ltd, Shanghai, China) were used without further purication. Castor
oil was purchased from supermarkets, and its saponication value
was determined as 185.27 mg KOH/g.
The acid value, density and viscosity of dehydrated and degassed
Daqing crude oil are 0.062 mg KOH/g, 0.84 g/cm3 , and 19.2 mPa s at
50 C, respectively. The main compositions of Daqing crude oil are
hydrocarbon (65.88 wt%), resins (24.12 wt%), asphaltene (8.12 wt%)
and organic acids (0.13 wt%). Hydrocarbons are mainly alkanes with
chain ranging from C13 to C31, among which tricosane (C23) is the
most abundant.
2.2. Characterization
Gas chromatography mass spectrometry (GCMS) was recorded
on Agilent 6890N Network GC system and 5975 inert Mass Selective
Detector. Electrospray ionization high resolution mass spectrometry (ESI HRMS) was recorded on the Waters LCT Premier XE Mass
Spectrometers. 1 H nuclear magnetic resonance (1 H NMR) spectra of CPDB were recorded on a Bruker Avance 400 spectrometer
(400 MHz) in CDCl3 at room temperature. Tetramethylsilane (TMS)
was used as reference.
2.3. Synthesis method of zwitterionic surfactants from castor oil
20.00 g castor oil and 30 mL NaOH methanol/water solution
(3 M, vmethanol /vwater = 2:1) were added into a round bottom ask

and reuxed at 70 C for 6 h of alkali hydrolysis. After hydrolysis, the

mixture was neutralized and further acidied using hydrochloric
acid (6 M), until the pH value of the solution was about 2. Fatty acids
and glycerol were separated by hot water. The oil phase was washed
using hot water till the pH value of the aqueous phase was about 6.
The aqueous phase was collected to recycle glycerol. Then the fatty
acids mixture, 1, was dried by azeotropic distillation of water using
cyclohexane as water-carrying agent. 5.00 g (17 mmol) 1, 2.27 g
(17 mmol) AlCl3 and 25 mL benzene were added to a dried roundbottom ask and reuxed at 65 C, and anhydrous CaCl2 was placed
in a dried tube above the reactor. After 6 h of alkylation reaction,
the product was washed by 15 mL hydrochloric acids (1.0 M) for 3
times, then residue benzene was recycled on a rotary evaporator
giving 5.80 g 2. A solution of 2 (5.80 g, 17 mmol) in trichloromethane
(25 mL) was added dropwise to a dried ask with 1.45 mL SOCl2
(20 mmol) in it, and the mixture was stirred at 40 C for 2 h. Then the
mixture was distilled to remove the solvent and residue SOCl2 . The
product was dissolved in 10 mL acetone, and 2.30 mL N,N-dimethyl1, 3-propanediamine (20 mmol) was slowly added in it at 0 C. The
reaction mixture was then warmed to 40 C and stirred for 2 h. The
residue diamine and solvent were removed on a rotary evaporator giving 6.72 g 3. 3 were quaternized using sodium chloroacetate
with a molar ratio of 1:1.25 in a solvent mixture of methanol and
water (vmethanol /vwater = 1:1). The nal products were reuxed at
75 C for 12 h; the mixture was vaporized off under reduced pressure, then dissolved in ethanol and ltered. The ltrate was distilled
to remove ethanol and puried by recrystallization in ethyl acetate.
6.61 g precipitate 4, castor-based N-phenylfattyamidopropyl-N,Ndimethylcarboxyl betaine (CPDB), was received and characterized
with ESI-HRMS and 1 H NMR.
2.4. Measurement of surface tension
Aqueous solutions of CPDB were prepared at different concentration from 1.6 107 mol/L to 2 104 mol/L by double distilled
water. The surface tensions (SFT) of these solutions were performed
with the plate method using a DCAT 21 tensiometer (Dataphysics,
Germany) and the temperature was controlled at 25.0 0.1 C [16].
The measurement was repeated three times and an average value
was obtained. The surface tension between air and double distilled
water was 71.8 mN/m at 25 C.
Surface excess at CMC ( CMC ) is derived from the Gibbs adsorption isotherm equation [17].
CMC =

1
2.303RT

SFT
lgC

(1)
T

where C is the concentration of the surfactant aqueous solution,

R = 8.314 J/mol/K, T = 298.15 K, SFT is expressed in mN/m,  was set
to 1 for zwitterionic surfactants, since no counterion adsorption is
expected if the cationic and anionic portions of the molecule are
genuinely internally associated [18]. The occupied per surfactant
molecule (ACMC ) at CMC on air/water interface is related to the
surface excess  CMC as follows [17].
ACMC = (NA CMC )

1016

(2)

where NA is the Avogadro constant.

2.5. Measurement of interfacial tension
Solutions of CPDB were prepared at different concentration
from 0.010 g/L to 0.500 g/L with Daqing oil eld simulated formation water. Interfacial tensions (IFT) between Daqing crude oil and
these solutions were measured by the spinning-drop method at
50 0.1 C (the average stratum temperature of Daqing oileld,
China) using a SVT 20 tensiometer (Dataphysics, Germany) [15].

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795

The interfacial tension between Daqing crude oil and simulated

formation water was 9.70 mN/m at 50 C.
2.6. Measurement of contact angle
The contact angles of 0.500 g/L CPDB solution were measured
by sessile drop technique at 25 C [19]. The measurements were
repeated 5 times for every sample and the average value was gured out. Double distilled water showed an average contact angle
as 92.04 on the hydrophobic acrylic substrate at 25 C.
2.7. Measurement of foaming property
The foaming property of 0.500 g/L CPDB solution was obtained
according to RossMiles test at 40 C [2]. The foam heights at 0 and
10 min were recorded (h/mm). The experiments were repeated for
3 times.

89

2.10. Toxicity prediction

Toxicity properties of the target compounds were predicted
using admetSAR web-based application [20]. Simplied molecular input line entry specication (SMILES) of the target molecules
was obtained through drawing the chemical structure of bio-based
surfactants. The toxicity properties could be calculated through the
web data system.
2.11. Biodegradation prediction
Ultimate biodegradation of the bio-based zwitterionic surfactants was determined by EPI Suite, BIOWIN3 biodegradation model
[21], which is frequently used to estimate the degradation of
organic chemicals. Ultimate biodegradation could be calculated by
inputting the SMILES of the molecule.
3. Results and discussion

2.8. Measurement of adsorption on quartz sand

3.1. The yield and structural characterization

Surfactant adsorption is commonly measured through static or

dynamic (core ooding) experiments. In this paper, the former was
selected. The procedure was as follows: rst, the quartz sand was
cleaned with acid. Then, 5.000 g quartz sand and 45 mL surfactant
solution were added to a 250 mL conical ask, which was oscillated
for 24 h at 50 C in a thermostatic water bath. After that, the clear
liquid was separated quickly from the mixtures, and the concentration of the surfactant was measured by two-phase extraction
method (See Supplementary Materials). Static adsorption was calculated according to Eq. (3).

The castor oil was hydrolyzed and its acid values before and
after the hydrolysis process were 1.39 mg KOH/g and 183.32 mg
KOH/g, respectively, which yielded a hydrolysis efciency of
98.4%. Consequently, ve major constitutes of fatty acids including
palmitic acid, stearic acid, oleic acid, linoleic acid and ricinoleic
acid from castor oil were determined using GCMS chromatography as listed in Table 1. The fatty acids were used as starting
materials to produce the castor-based N-phenylfattyamidopropylN,N-dimethylcarboxyl betaine (CPDB), as shown in Fig. 1, and a
yield of 78.5% was obtained. The synthesis method was modied
from our previous reported method [15], avoiding the traditional
harsh condition as high temperature or high pressure [22,23].
The chromatograms of ESI HRMS and 1 H NMR were shown in
Supplementary Materials. The molecular weight of the CPDB was
determined by ESI-MS and the ionization way of ESI-MS was positive ion mode with Na+ . The mass-to-charge ratios (m/z) of main
peaks were 421.3421, 449.3716, 523.3867 and 525.4054, respectively, which indicated the surfactants derived from palmitic acid,
stearic acid, linoleic/ricinoleic acid and oleic acid. The molecular
weight of CPDB was 497.01 g/mol. The exact mass of them with Na+
were calculated as 421.3406, 449.3719, 523.3875 and 525.4134,
respectively. From the results of ESI-MS, the ultimate product of
ricinoleic acid predominated in the nal mixture (as shown in
Fig. 1). Ricinoleic acid ((9Z,12R)-12-hydroxy-9-octadecenoic acid)
contains a double bond and a hydroxyl group. In the alkylation
reaction, the hydroxyl group reacted with AlCl3 prior to the double
bond, generating a structure with a double bond and a phenyl. Due
to the nearness of double bond and phenyl, the steric hindrance
of the phenyl prevented the addition reaction of the double bond.
The product of ricinoleic acid had a long carbon chain with a
double bond and a phenyl (see Supplementary Materials). The
product of linoleic acid had similar structure as that of ricinoleic
acid. In the alkylation reaction, one double bond reacted with
AlCl3 , generating an active carbenium ion, then the carbenium ion
reacted with benzene. The activity of carbenium ion would cause
the rearrangement of carbon chain, a conjugated structure of the
other double bond and the phenyl have got according to several
repeated experiment results (see Supplementary Materials).
Due to the activity and instability of hydroxyl group and double
bond in fatty acids, adding or substituting a phenyl group could
increase the stability of the nal surfactants in high temperature
environment, like oil reservoir. On the other hand, the interaction
of surfactants with a phenyl group could be enhanced and the
arrangement of surfactants could be more compact, due to the
stacking interaction between phenyl groups [24,25].

 =

(C0 C)V
m

(3)

where  is the adsorption of the surfactant per gram of quartz sand

(mg/g), C0 and C are the concentrations of the surfactant before
and after the adsorption, respectively (mg/g), V is the volume of
the surfactant solution added to the conical ask (mL), and m is the
mass of quartz sand (g).
2.9. Measurement of dispersion effectiveness
The dispersion effectiveness (DE) was evaluated according to
the state standard GB 18181-2000 and bafed ask test (BFT). A
volume of 50 mL simulated seawater (the salinity is 33,000 mg/L)
was added to a conical ask with stopper. 0.050 g Daqing crude oil
was carefully dispensed directly onto the surface of the simulated
seawater. The dispersant was prepared according to the conventional type in the state standard GB 18181-2000, in which 30% of
the component is surfactant, 70% is solvent. In this work, deionized
water was chosen to be the solvent. The dispersant was then dispensed onto the center of the oil slick by using a pipettor, giving a
volumetric ratio of oil-to-dispersant of 30:1, 20:1, 10:1. The ask
was then placed on a vortex shaker and mixed for 10 min at a rotation speed of 200 rpm. At the end of the mixing period, the ask
was removed from the shaker and allowed to remain stationary for
30 s or 10 min. After the quiescent period, the rst 2 mL of sample
was discarded, then 10 mL sample was collected. The sample was
transferred to a 125 mL separatory funnel and extracted with 5 mL
fresh dichloromethane twice. The extract was adjusted to a nal
volume of 10 mL. Then the absorbance value of the extract was
determined under 650 nm using fresh dichloromethane as reference. The concentration of oil dispersed to water was calculated
using the absorbance values and the standard curves of Daqing
crude oil. Then DE was obtained. The standard curves of Daqing
crude oil was shown in Supplementary Materials.

90

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795

Table 1
The main fatty acid compositions (wt%) of castor oil.
Plant oil

Palmitic acid
C16:0

Stearic acid
C18:0

Oleic acid
C18:1

Linoleic acid
C18:2

Ricinoleic acid
C18:1( OH)

Castor Oil

1.50

1.71

4.81

5.81

86.08

The hydrogen atoms in CPDB were identied according

to their chemical environment using 1 H NMR. The signals
in the range of 0.8561.238 ppm were attributed to the
hydrogen atoms on the long carbon chains. Peaks in the
range of 1.5781.563 ppm indicated the hydrogen atoms in
CH2 CH C6 H5 and CH2 CH2 CO . The resonances of the
hydrogen atoms neighboring the carbonyl and benzene rings were
in the range of 2.142 and 2.4472.428 ppm, respectively. The
prominent signal at 3.221 ppm was assigned to the resonances of H
in N(CH3 )2 . The peaks in 3.6723.645 ppm were assigned to the
resonances of H of CH2 between N(CH3 )2 and COO . The resonances at 3.8523.847, 1.9681.959, and 3.483 ppm were assigned
to the H of CH2 in NH CH2 CH2 CH2 N(CH3 )2 , respectively.
The signals in the range of 4.1444.090 ppm were ascribed to the
hydrogen atoms in double bonds. The chemical shift of the hydrogen atom in CO NH was shown as a broad peak at 6.921 ppm.

The resonances of the hydrogen atoms in the benzene ring were in

the range of 7.1597.116 ppm.
3.2. Surface properties
Equilibrium surface tension as a function of CPDB concentrations at 25.0 C was illustrated in Fig. 2. Surface excess ( CMC )
and the area occupied per surfactant molecule (ACMC ) at CMC on
air/water interface were calculated by Eqs. (1) and (2), respectively, and listed in Table 2. As shown in Fig. 2, the critical micelle
concentration (CMC) and surface tension at CMC (SFTCMC ) were
estimated from the breakpoints of these plots. The CMC of CPDB
was as low as 7.08 106 mol/L with a SFTCMC of 30.7 mN/m. The
CMC value was at least two orders of magnitude lower than that
of surfactants with shorter hydrophobic chains and different zwitterionic hydrophilic groups [2629], and was slightly higher than

Fig. 1. The synthetic route of novel zwitterionic surfactants derived from castor oil.

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795

91

Table 2
Surface properties, contact angle and foaming property of CPDB.
Oil resource

CMC (mol/L)

SFTCMC (mN/m)

SFTmin (mN/m)

 CMC (mol/m2 )

ACMC (nm2 /molecule)

 average

Foam height (mm)

Initial

After 10 min

Castor oil

7.08 106

30.7

27.6

3.80

0.44

38.79

62

58

that of the ones with longer hydrophobic chains [13,14].  CMC of

CPDB was slightly higher than that of the one with same zwitterionic hydrophilic groups and unsaturated C18 hydrophobic chain
[14], and was obviously higher than that of the ones with shorter
hydrophobic chains [2629].
There was a special phenomenon that the surface tension kept
decreasing with CPDB concentration above the CMC point. This
might be due to the double bond in the major comment of CPDB (as
shown in Fig. 1). Double bonds are mostly cis-formed, hydrophobic chain with a double bond has lager space volume, and the
arrangement of surfactants molecules is incompact. When reaching the CMC of CPDB, the arrangement of the surfactant molecules
on the surface is relatively loose. When increasing the surfactant
concentration, the airwater surface could accommodate more surfactant molecules. Hydrophobic chains with double bonds could
be compressed to decrease space volume. Surfactant molecule
arrangement was more compact and the surface tension of the solution was lower. Similar phenomenon of anionic surfactants with
double bond hydrophobic chain had been reported [30].
3.3. Interfacial properties
Dynamic interfacial tensions (DIFT) between Daqing crude oil
and simulated formation water at the different concentrations of
CPDB in solutions at 50.0 C were shown in Fig. 3(a). As Fig. 3(a)
showed, the DIFT rst gradually decreased to the minimum value,
followed by a slow increase to a nal equilibrium. That is because
of the dynamic equilibrium between adsorption and desorption of
surfactant molecules. When the aqueous phase and the oil phase
contact, surfactant molecules will begin to diffuse from the bulk to
the interface and adsorb onto the interface. At rst, adsorption rate
of molecules onto the interface is higher than desorption rate of
molecules from the interface, so DIFT decreases. With time passes,
adsorption rate is lower than desorption rate, and DIFT increases.
Finally when adsorption and desorption reach a balance, the DIFT
reaches a steady value [26].
All the minimums of DIFT were in 103 mN/m order of magnitude. The IFT in 103 mN/m order of magnitude was critically
required for effectively displacement of residual crude oil from
the pores and capillaries of petroleum reservoirs [31]. Traditional petroleum-based surfactants, such as petroleum sulfonates
[32] and alkyl benzene sulfonates [33,34] are widely used in oil

Fig. 2. The surface tensions vs. the concentration of CPDB at 25.0 C. The error bars
represent standard deviations of the mean for triplicate measurements.

recovery accompanying with strong alkali (NaOH or Na2 CO3 ). The

system of 0.8 g/L alkyl benzene sulfonates and 0.2 M Na2 CO3 could
reach a stable ultra-low IFT between crude oil and water. The
acidic component (petroleum acid) in crude oil can react with alkaline solution to produce in situ surfactant, which can interact with
petroleum-based surfactants and reduce the IFT between crude oil
and water remarkably [3438]. However, the addition of strong
alkali has resulted in well bore scaling, stratum damage and permeability decline at the same time [39,40]. Therefore, ultra-low IFT
between crude oil and water is necessary for EOR in oilelds with
the absence of any extra alkali. Recently, many researches have
indicated that zwitterionic surfactants can be used in enhanced
oil recovery, due to their remarkable surface/interfacial properties,
insensitivity to temperature and electrolyte [26,29,41,42]. CPDB
could reduce crude oil/water IFT to ultra-low values at low concentrations without the aid of extra alkali, and it well matched the
screening criteria of surfactants used in EOR. It was also found that
the time interval for DIFT to reach the minimum value decreased
with increasing CPDB concentrations, which was possibly due to
the accelerated diffusion of surfactant molecules caused by the
larger surfactant concentration gradient between the bulk solution
and the oilwater interface. On the other hand, the equilibrium
values of DIFTs increased with increasing CPDB concentrations.
High surfactant concentration might enhance the solubilization
or distribution of surfactant molecules in the oil phase, resulting in a decreased amount of single surfactant molecule on the
interface, leading to increased equilibrium values of DIFTs. In the
practical application, in addition to achieving ultra-low interfacial tension, lower usage of the surfactants is also preferred. As
a result, the subsequent experiment selected the concentration
of 0.010 g/L as the research basis, at which concentration the
minimum value of DIFT was 0.0053 mN/m. This concentration
of CPDB solution was much lower than that of single surfactant
in our precious work and exhibited better interfacial properties
[15], which was due to the synergism among different structural
surfactants.
The comparison of IFTs between crude oil and four simulated
formation water and sea water (salinity: 33,000 mg/L) was shown
in Fig. 3(b). The salinity of Daqing, Shengli, Xinjiang and Huabei
oil eld were 5318 mg/L, 10,039 mg/L, 12,223 mg/L and 3663 mg/L,
respectively. The concentrations of main ions in the four formation
water were shown in Table 3. As presented in Fig. 3(b), CPDB could
reduced the IFT between crude oil and water to ultra-low values
in the four formation water and sea water, which was a support to
CPDB application in diverse salinity.
The effect of Ca2+ on dynamic interfacial tensions between
Daqing crude oil and 0.010 g/L CPDB solutions at 50.0 C was evaluated and the results were shown in Fig. 3(c). As Fig. 3(c) showed,
CPDB showed a strong calcium tolerance. When the concentration
of Ca2+ was below 200 mg/L, the IFTmin between Daqing crude oil
and 0.010 g/L CPDB solutions could reach ultra-low range.
Fig. 3(d) showed the effect of sodium chloride (NaCl) on the DIFT
between 0.010 g/L CPDB solution and Daqing crude oil. As seen in
Fig. 3(d), with increasing sodium chloride concentration, the equilibrium values of DIFT (DIFTequ ) decreased rst, and reached the
lowest DIFTequ at NaCl concentration of 10.00 g/L, then increased,
which could be explained that NaCl was benecial to promote surfactant molecules to transfer from the bulk solution to oilwater
interface, compress the electrical double layer and form compact

92

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795

Fig. 3. The interfacial properties of CPDB. (a) Dynamic interfacial tensions between Daqing crude oil and different concentrations CPDB solutions in simulated formation
water at 50.0 C. (b) Dynamic interfacial tensions between Daqing crude oil and 0.010 g/L CPDB solutions in four simulated formation water and sea water at 50.0 C. (c)
Dynamic interfacial tensions between Daqing crude oil and 0.010 g/L CPDB solutions with adding different concentration of extra Ca2+ at 50.0 C. (d) Dynamic interfacial
tensions between Daqing crude oil and 0.010 g/L CPDB solutions with adding different concentration of extra NaCl at 50.0 C. (e) The effect of pH on dynamic interfacial
tensions between Daqing crude oil and 0.010 g/L CPDB solutions at 50.0 C.

Table 3
The concentrations of main ions in formation water of different oil elds.
Oil eld

Shengli
Xinjiang
Huabei
Daqing

pH

7.78
8.13
8.20
8.29

The concentration of ions (mg/L)

Salinity

Cl

SO4 2

HCO3

CH3 COO

Na+

K+

Ca2+

Mg2+

10,039
12,223
3663
5318

3850
5336
819
1068

2244
125
32
12

264
2039
1597
2307

32
344
58
216

3313
4196
1064
1665

94
35
22
0

196
103
53
41

46
45
18
0.45

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795

93

Table 4
The interfacial stability of CPDB at different temperatures.
Temperature
50 C
50 C
50 C
50 C
50 C
50 C
20 C
20 C
20 C
20 C
4 C
4 C
4 C
4 C

Storage days

IFTmin (mN/m)

0 day
20 days
40 days
60 days
80 days
100 days
0 day
1 days
7 days
14 days
0 day
1 days
7 days
14 days

0.0023
0.0024
0.0028
0.0028
0.0029
0.0031
0.0023
0.0025
0.0024
0.0026
0.0023
0.0024
0.0024
0.0025

surfactant molecule arrangement on the interfacial layer. However,

the high concentration of NaCl would shield charges of ionic surfactants, destroy hydrated construction around ions, and enhance the
hydrophobicity of the surfactant, which would lead more surfactant
molecules to transfer into oil phase and reduce the amount of surfactant molecules on oilwater interface, and then the equilibrium
value of IFT increased [31].
The salinities of most oil elds in China, are commonly below
16,000 mg/L and the concentrations of Ca2+ are below 300 mg/L
[43]. The present results suggested that CPDB could remain acceptable interfacial properties in a wide range of salinity, which implied
that it should be practical in application in most oil elds.
CPDB is a carboxyl betaine kind zwitterionic surfactant, the isoelectric point of which is about 8.2 [44]. The pH of the water has
a signicant impact on its ionization and surface and interfacial
performance in aqueous solutions. When the pH of the water was
below the isoelectric point of CPDB, H+ could combine with CPDB,
generating corresponding cationic surfactant. However, when the
pH of the water was above the isoelectric point of CPDB, CPDB
remained as zwitterionic surfactant. The effect of pH on dynamic
interfacial tensions between Daqing crude oil and 0.010 g/L CPDB
solutions at 50.0 C was evaluated and the dynamic interfacial tensions were shown in Fig. 3(e). When pH was 3, the corresponding
cationic surfactant of CPDB could not reduce the IFT between crude
oil and water to ultra-low values. When pH was 712, the interfacial properties of CPDB were not affected too much by the pH
of water. Most of the oil eld formation water samples were neutral or weak alkaline, therefore, CPDB could be used in neutral and
alkaline formation water.
In the surfactant ooding, the entire displacement process took
roughly 90 days. This case required that the interfacial properties
of the surfactant needed remain active in the 90 days at reservoir
temperature. We chose Daqing oil eld average reservoir temperature, 50 C, as a high temperature condition for preservation. The
IFTmin were measured every 20 days and were given in Table 4. As
shown in Table 4, CPDB still maintained a strong interfacial activity
after 100 days preservation at 50 C. In the practical application of
surfactant, surfactant solution is usually stored outdoors. In northern China, especially in winter, the night temperature is extremely
low, freezing phenomenon of surfactant solution appears in the
outdoor storage process. Some of surfactant solution will appear
stratication phenomenon in the process of freezing and thawing, resulting in the decrease of interfacial properties. Therefore,
the study of the stability of surfactant solution in low temperature preservation was of great help for its practical application. We
chose 20 C and 4 C, as low temperature condition for preservation. The IFTmin were measured in 14 days and were listed in Table 4.
As shown in Table 4, the interfacial properties of CPDB were nearly
the same, CPDB still maintained a strong interfacial activity. The

Fig. 4. Static adsorption of low concentrations CPDB solutions on quartz sand at

50 C.

stability of interfacial properties results demonstrated that CPDB

could maintain a strong interfacial activity at different temperature preservation, which provided a foundation data for its future
application in EOR.
3.4. Wetting and foaming properties
The contact angle  average of air/water/solid was obviously
reduced from 92.04 to 38.79 , when the concentration of CPDB
was 0.500 g/L. The results of RossMiles test showed that the initial foam height of 0.500 g/L CPDB solution was 62 mm, and after
5 min and 10 min the foam height were 61 mm and 58 mm, respectively. The foaming performance of CPDB was stronger than that of
anionic surfactants derived from vegetable oils [2,11] and similar as
other zwitterionic surfactants with long hydrophobic chains [28].
3.5. Adsorption on quartz sand
The effect of CPDB concentration on the static adsorption behavior on quartz sand surface was evaluated at 50 C, wherein the
solid-to-liquid weight ratio was 1:9. The results are shown in Fig. 4.
An increase in the CPDB concentration led to an increase in the
adsorption capacity on sand surfaces. The adsorption amount of
CPDB on quartz sand was as low as 0.342 mg/g at the initial concentration of 0.20 g/L, which is much lower than amine oxide with
shorter carbon chain [29] and in the same order of magnitude as
betaine type zwitterionic surfactants with different hydrophobic
chains [45]. Low adsorption of surfactants could relieve the reduction of effective concentration caused by surfactant adsorption
on a reservoir rock surface. Therefore, these results further indicated that CPDB possessed excellent interfacial performance and
low adsorption amount on quartz sand at low concentration, and
made itself a promising alternative to petroleum-based surfactants
in enhanced oil recovery.
3.6. Dispersion effectiveness
The dispersion effectiveness (DE) of Daqing crude oil with CPDB
used as dispersant at different oil-to-dispersant ratio at room temperature was showed in Fig. 5. When oil-to-dispersant ratio was
10:1, the DE of instant emulsifying power (standing for 30 s) and
emulsion stability (standing for 10 min) were 64.69% and 47.85%,
respectively. Results showed that the DE of CPDB was well matched
the criterion of the state standard GB 18181-2000 and National
Contingency Plan of the United States [46]. When oil-to-dispersant
ratio was 30:1, the DE declined obviously. However, the DE was
still higher than that of the criterion of National Contingency Plan
of the United States, dispersants listed on which the DE needed at
least 45%. These results indicate that CPDB has the potential to be
used in OSDP.

94

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795

4. Conclusion

Fig. 5. Dispersion effectiveness of Daqing crude oil with different oil-to-dispersant

ratio at room temperature.

Large amount oil had been released into the sea in oil spills in
reported accidents, which occurred frequently in the process of
petroleum exploitation, transportation and consumption around
the world, and leaded to devastating damage to the marine environment. Using chemical dispersants is an efcient mean to reduce
the adverse environmental impact of spilled oil. Dispersants are
added to reduce the interfacial tension between oil and water and
cause the oil slick to form small size water-soluble micelles, which
can be rapidly diluted and spread in a large volume of water [47,48].
Dispersants could accelerate the degradation of the spilled oil by
natural processes and eliminate or signicantly reduce the impact
on sensitive shorelines and habitats [49].

3.7. Toxicity prediction

The predicted toxicity properties, LC50 for fathead minnow
were ranged from 3.335.24 mol/L. If the LC50 value of a compound was more than 0.5 mmol/L, it was assigned as high acute
fathead minnow toxicity compound, otherwise it was assigned as
low acute fathead minnow toxicity compounds [50]. In addition
to the dispersion effectiveness, toxicity is another important index
for evaluating a dispersant. As a kind of chemical, if a dispersant
has acute toxicity to marine aquatic organisms, using it can cause
secondary pollution [51]. Based on the predicted values, all the
compounds may not show either acute toxicity according to the
calculated LC50 values nor carcinogenicity. On the other hand, the
toxicity of alkyl benzene sulfonate (ABS) and alkyl naphthalene
sulfonate (ANS), which were commonly used in EOR, were also predicted. LC50 for fathead minnow of ABS and ANS were 3.08 mol/L
and 2.43 mol/L, respectively. These results demonstrated that the
toxicity of CPDB was lower than ABS and ANS.

3.8. Biodegradability prediction

Ultimate biodegradation scores for the surfactants derived from
palmitic acid, stearic acid, linoleic/ricinoleic acid and oleic acid in
CPDB were ranged from 2.64 to 2.92. Scores above 2.8 were in the
order of weeks, and scores between 2.0 and 2.8 were in order
of months. These results suggested that bio-based zwitterionic
surfactants are biodegradable. And the degradation time of surfactants is appropriate for EOR and OSDP. Meanwhile, the ultimate
biodegradation scores of ABS and ANS were also predicted using
EPI Suite. The predicted result of CPDB was similar to that of ABS
(2.592.84) and was slightly higher than that of ANS (2.482.73).
These results indicated that the degradation period of CPDB and
ABS was shorter than that of ANS.

Bio-based zwitterionic surfactant derived from non-edible

vegetable oil was successfully synthesized via a facile and highyield chemical modication. The CMC of CPDB was as low as
7.08 106 mol/L with a SFTCMC of 30.7 mN/m. The DIFTmin of
crude oil and 0.010 g/L CPDB concentration was 0.0053 mN/m
without extra alkali, CPDB showed strong electrolyte tolerance
and resistance of temperature and pH. Meanwhile, CPDB exhibited good wetting, foaming properties and appropriate dispersion
effectiveness of crude oil. Moreover, different from feedstock of
petroleum-based surfactants, waste cooking oil and various nonedible vegetable oils are a kind of renewable resources with
huge production and environmentally friendly performance. The
bio-based surfactant would consequently made itself a promising alternative to petroleum-based surfactants, and implied great
potential applications in many industrial elds, in particular, in
enhanced oil recovery and oil spill disposal processing.
Acknowledgments
This research was supported by National Science Foundation
of China (Grant No. 21203063), the 863 Program (Grant No.
2013AA064403) and the Fundamental Research Funds for the Central Universities of China (Nos. WK1213003, WJ1214066).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.colsurfa.2015.05.
060
References
[1] P. Foley, A. Kermanshahi pour, E.S. Beach, J.B. Zimmerman, Derivation and
synthesis of renewable surfactants, Chem. Soc. Rev. 41 (2012) 14991518.
[2] M. Sreenu, B.V.S.K. Rao, R.B.N. Prasad, P. Sujitha, G.K. Chityala, Synthesis, surface
and biological properties of sodium N-acyl isoleucines, Eur. J. Lipid Sci. Technol.
116 (2014) 193206.
[3] F. Rajabi, R. Luque, An efcient renewable-derived surfactant for aqueous esterication reactions, RSC Adv. 4 (2014) 51525155.
[4] A. Corma, S. Iborra, A. Velty, Chemical routes for the transformation of biomass
into chemicals, Chem. Rev. 107 (2007) 24112502.
[5] I. Johansson, M. Svensson, Surfactants based on fatty acids and other natural
hydrophobes, Curr. Opin. Colloid Interface Sci. 6 (2001) 178188.
[6] C.S.K. Lin, L.A. Pfaltzgraff, L. Herrero-Davila, E.B. Mubofu, S. Abderrahim, J.H.
Clark, A.A. Koutinas, N. Kopsahelis, K. Stamatelatou, F. Dickson, S. Thankappan,
Z. Mohamed, R. Brocklesby, R. Luque, Food waste as a valuable resource for
the production of chemicals, materials and fuels. Current situation and global
perspective, Energy Environ. Sci. 6 (2013) 426464.
[7] J.A. Melero, J. Iglesias, A. Garcia, Biomass as renewable feedstock in standard
renery units. Feasibility, opportunities and challenges, Energy Environ. Sci. 5
(2012) 73937420.
[8] M.J. Climent, A. Corma, S. Iborra, Conversion of biomass platform molecules into
fuel additives and liquid hydrocarbon fuels, Green Chem. 16 (2014) 516547.
[9] S.D. Miao, P. Wang, Z.G. Su, S.P. Zhang, Vegetable-oil-based polymers as future
polymeric biomaterials, Acta Biomater. 10 (2014) 16921704.
[10] U. Biermann, U. Bornscheuer, M.A.R. Meier, J.O. Metzger, H.J. Schfer, Oils and
fats as renewable raw materials in chemistry, Angew. Chem. Int. Ed. 50 (2011)
38543871.
[11] M.H. Wu, L.Z. Wan, Y.Q. Zhang, A novel sodium N-fatty acyl amino acid surfactant using silkworm pupae as stock material, Sci. Rep. 4 (2014) 4428.
[12] Q.Q. Zhang, B.X. Cai, W.J. Xu, H.Z. Gang, J.F. Liu, S.Z. Yang, B.Z. Mu, The rebirth
of waste cooking oil to novel bio-based surfactants, Sci. Rep. 5 (2015) 9971.
[13] Z.L. Chu, Y.J. Feng, Vegetable-derived long-chain surfactants synthesized via a
green route, ACS Sustain. Chem. Eng. 1 (2013) 7579.
[14] D. Feng, Y.M. Zhang, Q.S. Chen, J.Y. Wang, B. Li, Y.J. Feng, Synthesis and surface
activities of amidobetaine surfactants with ultra-long unsaturated hydrophobic chains, J. Surfactants Deterg. 15 (2012) 657661.
[15] Q.Q. Zhang, B.X. Cai, H.Z. Gang, S.Z. Yang, B.Z. Mu, A family of novel biobased zwitterionic surfactants derived from oleic acid, RSC Adv. 4 (2014)
3839338396.
[16] H. Wang, H.Z. Gang, R.Q. Ye, B.Z. Mu, Interaction between biosurfactant surfactin and cationic surfactant cetyl trimethyl ammonium bromide in mixed
micelle, Colloid Polym. Sci. 292 (2014) 31693176.

Q.-Q. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 8795
[17] T. Lu, Y.R. Lan, C.J. Liu, J.B. Huang, Y.L. Wang, Surface properties, aggregation
behavior and micellization thermodynamics of a class of gemini surfactants
with ethyl ammonium headgroups, J. Colloid Interface Sci. 377 (2012) 222230.
[18] J. Eastoe, S. Nave, A. Downer, A. Paul, A. Rankin, K. Tribe, J. Penfold, Adsorption of
ionic surfactants at the airsolution interface, Langmuir 16 (2000) 45114518.
[19] M. Nedyalkov, L. Alexandrova, D. Platikanov, B. Levecke, T. Tadros, Wetting
properties of aqueous solutions of hydrophobically modied inulin polymeric
surfactant, Colloid Polym. Sci. 286 (2008) 713719.
[20] F.X. Cheng, W.H. Li, Y.D. Zhou, J. Shen, Z.R. Wu, G.X. Liu, P.W. Lee, Y. Tang,
AdmetSAR: a comprehensive source and free tool for assessment of chemical
ADMET properties, J. Chem. Inf. Model. 52 (2012) 30993105.
[21] S.J. Song, M.Y. Song, L.Z. Zeng, T. Wang, R.Z. Liu, T. Ruan, G.B. Jiang, Occurrence and proles of bisphenol analogues in municipal sewage sludge in China,
Environ. Pollut. 186 (2014) 1419.
[22] A. Behr, M. Fiene, C. Bu, P. Eilbracht, Hydroaminomethylation of fatty acids
with primary and secondary amines a new route to interesting surfactant
substrates, Eur. J. Lipid Sci. Technol. 102 (2000) 467471.
[23] Z.L. Chu, Y.J. Feng, A facile route towards the preparation of ultra-long-chain
amidosulfobetaine surfactants, Synlett (2009) 26552658.
[24] Y. Li, J. Reeve, Y. Wang, R.K. Thomas, J. Wang, H. Yan, Microcalorimetric study
on micellization of nonionic surfactants with a benzene ring or adamantane in
their hydrophobic chains, J. Phys. Chem. B 109 (2005) 1607016074.
[25] K. Kano, H. Minamizono, T. Kitae, S. Negi, Self-aggregation of cationic porphyrins in water. Can stacking interaction overcome electrostatic
repulsive force? J. Phys. Chem. A 101 (1997) 61186124.
[26] J.H. Zhao, C.L. Dai, Q.F. Ding, M.Y. Du, H.S. Feng, Z.Y. Wei, A. Chen, M.W. Zhao, The
structure effect on the surface and interfacial properties of zwitterionic sulfobetaine surfactants for enhanced oil recovery, RSC Adv. 5 (2015) 1399314001.
[27] L.Y. Qi, Y. Fang, Z.Y. Wang, N. Ma, L.Y. Jiang, Y.Y. Wang, Synthesis and physicochemical investigation of long alkylchain betaine zwitterionic surfactant, J.
Surfactants Deterg. 11 (2008) 5559.
[28] L.P. Nong, C.L. Xiao, Z.S. Zhong, Physicochemical properties of novel phosphobetaine zwitterionic surfactants and mixed systems with an anionic surfactant,
J. Surfactants Deterg. 14 (2011) 433438.
[29] J. Zhao, C. Dai, J. Fang, X. Feng, L. Yan, M. Zhao, Surface properties and adsorption
behavior of cocamidopropyl dimethyl amine oxide under high temperature and
high salinity conditions, Colloids Surf. A 450 (2014) 9398.
[30] M. Sreenu, R.R. Nayak, R.B.N. Prasad, B. Sreedhar, Synthesis, surface and micellar
properties of sodium N-oleoyl amino acids, Colloids Surf. A 449 (2014) 7481.
[31] W.H. Qiao, J. Li, Y.Y. Zhu, H.Y. Cai, Interfacial tension behavior of double
long-chain 1,3,5-triazine surfactants for enhanced oil recovery, Fuel 96 (2012)
220225.
[32] W.L. Ng, D. Rana, G.H. Neale, V. Hornof, Physicochemical behavior of mixed
surfactant systems: petroleum sulfonate and lignosulfonate, J. Appl. Polym. Sci.
88 (2003) 860865.
[33] X.H. Dai, J.S. Suo, X. Duan, Z.W. Bai, L. Zhang, A study of the technical route of the
synthesis of alkylbenzenes for use as an oil displacement agent, J Surfactants
Deterg. 11 (2008) 111115.
[34] H. Wang, H.Z. Gang, S.Z. Yang, R.Q. Ye, B.Z. Mu, Interfacial behaviors of a mixture
of microbial lipopeptide and heavy alkylbenzene sulfonate in aqueous solution,
Int. J. Pet. Sci. Technol. 8 (2014) 7986.

95

[35] L.F. Chen, G.C. Zhang, J.J. Ge, P. Jiang, J.Y. Tang, Y.L. Liu, Research of the heavy
oil displacement mechanism by using alkaline/surfactant ooding system, Colloids Surf. A 434 (2013) 6371.
[36] M.G. Tang, G.C. Zhang, J.J. Ge, P. Jiang, Q.H. Liu, H.H. Pei, L.F. Chen, Investigation
into the mechanisms of heavy oil recovery by novel alkaline ooding, Colloids
Surf. A 421 (2013) 91100.
[37] X.T. Zhao, Y.R. Bai, Z.B. Wang, X.S. Shang, G.M. Qiu, L.F. Chen, Low interfacial
tension behavior between organic alkali/surfactant/polymer system and crude
oil, J. Dispers. Sci. Technol. 34 (2013) 756763.
[38] Q. Liu, M.Z. Dong, X.A. Yue, J.R. Hou, Synergy of alkali and surfactant in emulsication of heavy oil in brine, Colloids Surf. A 273 (2006) 219228.
[39] F.Z. Chen, H.Q. Jiang, X.H. Bai, W. Zheng, Evaluation the performance of sodium
metaborate as a novel alkali in alkali/surfactant/polymer ooding, J. Ind. Eng.
Chem. 19 (2013) 450457.
[40] J.R. Hou, Z.C. Liu, S.F. Zhang, X.A. Yue, J.Z. Yang, The role of viscoelasticity of
alkali/surfactant/polymer solutions in enhanced oil recovery, J. Pet. Sci. Eng. 47
(2005) 219235.
[41] X. Song, L. Dong, X. Cao, Z. Xu, C. Wang, L. Zhang, L. Zhang, S. Zhao, Dynamic
interfacial tensions of p-(n-lauryl)-benzyl polyoxyethylene ether carboxybetaine solutions, J. Pet. Sci. Eng. 124 (2014) 2734.
[42] P. Jiang, N. Li, J.J. Ge, G.C. Zhang, Y. Wang, L.F. Chen, L. Zhang, Efciency of
a sulfobetaine-type surfactant on lowering IFT at crude oilformation water
interface, Colloids Surf. A 443 (2014) 141148.
[43] L.Y. Wang, R.Y. Duan, J.F. Liu, S.Z. Yang, J.D. Gu, B.Z. Mu, Molecular analysis of the
microbial community structures in water-ooding petroleum reservoirs with
different temperatures, Biogeosciences 9 (2012) 46454659.
[44] S.J. Dong, Y.L. Li, Y.B. Song, L.F. Zhi, Synthesis, characterization and performance of unsaturated long-chain carboxybetaine and hydroxy sulfobetaine,
J. Surfactants Deterg. 16 (2013) 523529.
[45] N. Li, G.C. Zhang, J.J. Ge, L.C. Jin, J.Q. Zhang, B.D. Ding, H.H. Pei, Adsorption
behavior of betaine-type surfactant on quartz sand, Energy Fuels 25 (2011)
44304437.
[46] G. Sorial, A. Venosa, K. Koran, E. Holder, D. King, Oil spill sispersant effectiveness protocol. II. Performance of revised protocol, J. Environ. Eng. 130 (2004)
10851093.
[47] Z.K. Li, K. Lee, T. King, M.C. Boufadel, A.D. Venosa, Evaluating crude oil chemical
dispersion efcacy in a ow-through wave tank under regular non-breaking
wave and breaking wave conditions, Mar. Pollut. Bull. 58 (2009) 735744.
[48] R.R. Lessard, G. DeMarco, The signicance of oil spill dispersants, Spill Sci.
Technol. Bull. 6 (2000) 5968.
[49] Q.G. Chen, M.T. Bao, X.N. Fan, S.K. Liang, P.Y. Sun, Rhamnolipids enhance
marine oil spill bioremediation in laboratory system, Mar. Pollut. Bull. 71 (2013)
269275.
[50] C.L. Russom, S.P. Bradbury, S.J. Broderius, D.E. Hammermeister, R.A. Drummond,
Predicting modes of toxic action from chemical structure: acute toxicity in
the fathead minnow (Pimephales promelas), Environ. Toxicol. Chem. 16 (1997)
948967.
[51] R.S. Judson, M.T. Martin, D.M. Reif, K.A. Houck, T.B. Knudsen, D.M. Rotroff, M.H.
Xia, S. Sakamuru, R.L. Huang, P. Shinn, C.P. Austin, R.J. Kavlock, D.J. Dix, Analysis
of eight oil spill dispersants using rapid, in vitro tests for endocrine and other
biological activity, Environ. Sci. Technol. 44 (2010) 59795985.