Petroleum Science and Technology

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The Composition and Interfacial Activity of Alkyl

Benzene Sulfonates Used in Oil Recovery

H. Wang, D. Zhang, Y. Su, H. Gang, S. Yang, R. Ye & B. Mu

To cite this article: H. Wang, D. Zhang, Y. Su, H. Gang, S. Yang, R. Ye & B. Mu (2015) The
Composition and Interfacial Activity of Alkyl Benzene Sulfonates Used in Oil Recovery, Petroleum
Science and Technology, 33:3, 287-293, DOI: 10.1080/10916466.2013.872124

To link to this article: https://doi.org/10.1080/10916466.2013.872124

Published online: 14 Jan 2015.

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Petroleum Science and Technology, 33:287–293, 2015
Copyright 
C Taylor & Francis Group, LLC
ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2013.872124

The Composition and Interfacial Activity of Alkyl Benzene

Sulfonates Used in Oil Recovery

H. Wang,1 D. Zhang,2 Y. Su,2 H. Gang,1 S. Yang,1 R. Ye,1 and B. Mu1

1
State Key Laboratory of Bioreactor Engineering and Institute of Applied Chemistry, East China
University of Science and Technology, Shanghai, China
2
The Fourth Oil Production Company of Daqing Oilfield Limited Company, PetroChina, Daqing,
Heilongjiang, China

The composition of heavy alkyl benzene sulfonates (HABS) was determined and the HABS was separated
by a preparative HPLC. The surface and interfacial tensions of the components were measured. The results
show that the HABS is a mixture of homologues, Cn ABS, with different alkyl carbon numbers ranging
from 12 to 25 on phenyl group. The CMC of six components, C12 ABS, C13 ABS, C16 ABS, C17 ABS,
C18 ABS, and C19 ABS are 0.401–0.030 g·L−1. The C16 ABS has the strongest interfacial activities. There
occurred synergism between C16 ABS and ionized organic acids in the crude oil produced by Na2 CO3 .

Keywords: alkyl benzene sulfonates, separation, HPLC, mass spectrometry, interfacial activity, synergism

1. INTRODUCTION

In recent years, many researches of enhanced oil recovery (EOR) focus on chemical flooding system.
In chemical flooding, surfactants play an important role in EOR because their ability to reduce the
interfacial tension (IFT). It is believed that producing ultra-low (<10−2 mN·m−1) IFT is one of the
most important mechanisms for oil recovery with respect to chemical flooding (Zhao et al, 2010).
Heavy alkyl benzene sulfonates (HABS) has been widely applied for tertiary oil recovery in China.
The industrial product HABS is synthesized by sulfonation of heavy alkyl benzene which is one
of rectifying by-product of dodecylbenzene. HABS from different manufactures are different in
composition and properties due to the raw material, alkylation process, and catalytic system. In
order to produce a preferable HABS, it is necessary to make clear that which components the HABS
consists of and which one plays a key role or is more efficient in EOR.
Recently, many researches on analysis of linear alkyl benzene sulfonates (LAS) homologues
in environmental water sample have been reported. Reversed-phase high performance liquid chro-
matography (RP-HPLC) with a C18 or C8 column (Wangkarn et al., 2005; Lunar et al., 2006)
provides a good separation of LAS mixtures. It has been reported that the short hydrophobic chain
homologues C10 -C13 LAS could be separate easily under appropriate mobile phase (CH3 OH/H2 O
or CH3 CN/H2 O), and the separation of isomers of C10 -C13 LAS also has been done (Akyuz and
Roberts, 2002; del Olmo et al., 2004). In this work, a sample of HABS that was from Daqing Oil
Refinery has been studied on its composition and interfacial activities.

Address correspondence to B. Mu, State Key Laboratory of Bioreactor Engineering and Institute of Applied Chemistry,
East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China. E-mail: bzmu@ecust.edu.cn

287
288 H. WANG ET AL.

TABLE 1
Composition of the Simulated Formation Water

Inorganic Salts Content, mg·L−1

NaCl 1582.0
NaHCO3 3175.2
Na2 CO3 381.6
Na2 SO4 17.0
CaCl2 112.9
MgCl2 43.6

2. EXPERIMENTAL

2.1 Materials

The HABS was from Daqing Oil Refinery. Each component in HABS is prepared by HPLC. Cmix ABS
used in the measurements of IFT was a mixture of all ABS components prepared with fractioned
according their content in the HABS. The crude oil from Daqing Oilfield was dehydrated and
degassed, with a density of 0.84 g·cm−3. Methanol used was of HPLC grade. Doubly distilled water
was used for solution preparation. All other reagents were of analytical grade. The composition of
simulated formation water is shown in Table 1 and the total dissolved solid is 5312.3 mg·L−1.

2.2 Methods

2.2.1 Separation and Determination of HABS

The HABS sample was dried at 105◦ C for 5 h and dissolved in 1:1 methanol-water solution
(v/v) before HPLC analysis. Analytical RP-HPLC was performed using a 4.6 mm × 25 cm ODS-A
column. The mobile-phase system was (A) methanol and (B) water, and the elution conditions:
50% methanol (v/v), linear gradient of methanol concentration from 50% to 100% in 90 min. All
chromatographic elution were carried out at 30◦ C. An electron spray ionization-mass spectrometry
(ESI-MS) was used under negative electrospray ionization mode for the determination of the HABS.

2.2.2 Preparation of the Components from HABS

A 20 mm × 25 cm YMC-Pack ODS-A column was used to collect the components in HABS. The
mobile phase was (A) methanol and (B) water, and the elution conditions: 50% methanol (v/v), linear
gradient of methanol concentration from 50% to 100% in 90 min at a flow rate of 12.0 mL·min−1.
Each component separated from HABS sample was obtained after evaporation and drying.

2.2.3 Measurements of Critical Micelle Concentration (CMC)

The CMC values of the samples were determined by obtaining the surface tensions of desired mass
concentration of surfactants, using a DCAT 21 tensiometer (Dataphysics, Germany) with the plate
method. The samples were dissolved in doubly distilled water and the temperature was controlled
at 25.0 ± 0.1◦ C.
 THE COMPOSITION AND INTERFACIAL ACTIVITIES OF HABS 289

FIGURE 1 Chromatograms of HABS obtained using a linear gradient of methanol in water and the methanol
content was increased from 50% to 100% in 90 min.

2.2.4 Measurements of Dynamic Interfacial Tension (DIT) at Oil/Water Interface

A spinning-drop tensiometer (Dataphysics, Germany) was used to determine the interfacial

tensions between Daqing crude oil and surfactant solutions. The volumetric ratio of water to oil
in the spinning-drop tensiometer is about 2000. Samples were assumed to be equilibrated when
measured values of DIT remained unchanged for half an hour. All experiments of DIT measurement
were performed at 50.0 ± 0.1◦ C.

3. RESULTS AND DISCUSSION

3.1 Composition of the HABS

The chromatogram of HABS eluted from the HPLC column is presented in Figure 1. It reveals
several, different sized peaks, arranged in groups of singles and multiples. According to the molecular
weight obtained by LC-MS, 12 ABS components were separated from the HABS sample, and the
components are numbered in Figure 1. The ESI-MS information of all the 12 groups of peaks is
shown in Table 2. It is found that the HABS is a complex mixture of homologues with different alkyl
carbon numbers ranging from 12 to 25 on phenyl group but with almost no C14 ABS and C15 ABS
content. The multiple peaks indicate the existence of isomers.
Twelve components of homologues with different molecular weight (C12 , C13 , C16 , C17 , C18 , C19
C20 , C21 , C22 C23 , C24 , C25 ABS) were collected by a preparative HPLC. The composition of the
HABS is shown in Table 2. C13 ABS shows the highest content among all components. The content
of all ABS is 75.5 mass% of the HABS sample, and C12 -C18 ABS have a mass content of 86.5% of
the total ABS.

3.2 Surface and Interfacial Activities of ABS

3.2.1 Surface Activity of ABS

Figure 2 shows the relationship of surface tension and concentration of six components, C12 ABS,
C13 ABS, C16 ABS, C17 ABS, C18 ABS, and C19 ABS, and the mixture solution, Cmix ABS. The CMC
290 H. WANG ET AL.

TABLE 2
Composition of the HABS Obtained by LC-MS and Their CMC as Well as γ CMC

No. Surfactant m/z Mass Content of Total ABS, % CMC, g·L−1 γ CMC , mN·m−1

1 C12 ABS 325.2 23.4 4.01 × 10−1 28.6

2 C13 ABS 339.3 28.5 1.23 × 10−1 28.7
3 C16 ABS 381.3 9.9 7.04 × 10−2 29.0
4 C17 ABS 395.3 16.0 5.47 × 10−2 29.2
5 C18 ABS 409.3 8.7 4.30 × 10−2 29.4
6 C19 ABS 423.4 2.9 2.97 × 10−2 30.8
7 C20 ABS 437.3 1.8 — —
8 C21 ABS 451.4 2.0 — —
9 C22 ABS 465.4 2.3 — —
10 C23 ABS 479.4 2.1 — —
11 C24 ABS 493.4 2.0 — —
12 C25 ABS 507.4 0.4 — —

of each component is listed in Table 2. It is observed that the longer the hydrophobic carbon chain of
the ABS, the lower the CMC values of them. The CMC of six components are 0.401–0.030 g·L−1.
As the samples of C20 -C25 ABS were almost insoluble in water their surface tension data was not
obtained. All samples show good surface activity and the surface tensions at CMC (γ CMC ) are
28.6–30.8 mN·m−1.

3.2.2 The Interfacial Activity of ABS

The interfacial activity of the homologous components separated from HABS was measured.
Figure 3 shows the values of equilibrium interfacial tension (IFTeq ) between crude oil and ABS
solutions prepared with doubly distilled water. It is found that there exists a minimum in all curves

FIGURE 2 Surface tensions as a function of concentration of ABS in doubly distilled water.

 THE COMPOSITION AND INTERFACIAL ACTIVITIES OF HABS 291

FIGURE 3 IFTeq of ABS solutions against crude oil as a function of concentration of ABS in doubly distilled water.

and C16 ABS shows the lowest IFTeq . Nevertheless, the IFT of C16 ABS can only be reduced to
10−1 mN·m−1 level. Cmix ABS shows a IFT reduction less than C12 ABS-C16 ABS but greater than
C18 ABS and C19 ABS. According to Davies and Rideal (1963), the interfacial surfactant concentration
depends upon the desorption energy of the surfactant molecule, which is mainly determined by the
hydrophilic-lipophilic (HLB) ability of the surfactant. Good IFT reduction is shown only by those
surfactants that have an appreciable but limited solubility in both oil and aqueous phases (Zhao et al.,
2010). In the present study, among the 12 components C16 ABS has the most appropriate HLB value
so as it can make the greatest IFT reduction in this oil / water system.

FIGURE 4 IFTeq of ABS solutions against crude oil as a function of concentration of ABS in simulated formation
water.
292 H. WANG ET AL.

FIGURE 5 Dynamic IFT behavior of ABS solutions against crude oil. All the ABS solutions were prepared with
simulated formation water at a concentration of 0.2 g·L−1.

Figure 4 shows the values of equilibrium interfacial tension (IFTeq ) between crude oil and ABS
solutions prepared with simulated formation water. It has the similar phenomenon with the results
of Figure 4, C16 ABS also shows the greatest IFT reduction. But in difference, each component can
reach the lowest IFTeq value at a much lower concentration and reach lower IFTeq values especially
C16 ABS, it can reach ultra-low IFT at the concentration of 0.2 g·L−1. Cmix ABS also shows low IFT
maybe due to the effect of C16 ABS. Obviously, the addition of inorganic salts makes effect on the
IFT behavior. The formation water mainly contains a large amount of Na+, some Ca2+ and Mg2+.
For an anionic surfactant as ABS, the double layer can be compressed and the repulsion can be
screened by these cationic ions. Consequently, the intermolecular distance at the interface can be
shortened and the interfacial tension can be reduced (Yang et al, 2005). The another reason can be
effect of alkaline. The pH of the simulated formation water is about 9 for the existence of Na2 CO3 .
It has been proved that the acidic present in crude oil can react with alkaline solution to produce in
situ surfactant (ionized acids), which can interact with surfactant so as to reach a lower dynamic IFT
(Taylor and Schramm, 1990). In the six components, there may occur greatest synergism between
C16 ABS and ionized acids in the crude oil. Figure 5 shows the dynamic IFT of each surfactant at the
concentration 0.2 g·L−1, and it is found that there is a minimum in the dynamic IFT curve of C16 ABS.
It can be explained as follows: initially, the surfactant molecules start to aggregate at interface. At
the same time, Na2 CO3 in the solution and the organic acidic in the oil react at the interface and
produce surface-active species (ionized acids). The IFT decreases with the aggregation of surfactant
molecules and the ionized acids at the interface. In the process of adsorption/desorption of surfactant
molecular at the interface, the IFT reaches a minimum when greatest synergism between the two
surfactant occurs. Then the IFT increase appreciably and reach a stable value after reaching an
adsorption/desorption equilibrium at the interface.

4. CONCLUSION

The HABS from Daqing Oil Refinery was determined and separated by RP-HPLC. The alkyl carbon
number of HABS ranges from 12 to 25 on phenyl group but with almost no C14 ABS and C15 ABS
 THE COMPOSITION AND INTERFACIAL ACTIVITIES OF HABS 293

content. C12 -C18 ABS have a mass content of 86.5% of the total ABS. The longer the hydrophobic
carbon chain of the ABS, the lower the CMC values, but the higher the surface tensions. The C16 ABS
exhibits the strongest interfacial activity and can reach ultra-low IFT at the surfactant concentration
of 0.2 g·L−1 in the crude oil/simulated formation water system. There may occur synergism between
surfactant and ionized organic acids in the crude oil produced by Na2 CO3 . The results provide a basis
for producing a preferable HABS with stronger interfacial activities—maybe C16 ABS for EOR.

FUNDING

This work was supported by the National Natural Science Foundation of China (No. 21203063)
and the Fundamental Research Funds for the Central Universities of China (No. WK1213003,
WJ1214066).

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