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DOI 10.1007/s13202-014-0141-y
ORIGINALPAPER-PRODUCTIONENGINEERING
Received: 3 March 2014 / Accepted: 18 September 2014 / Published online: 1 October 2014
The Author(s) 2014. This article is published with open access at Springerlink.com
Abstract A series of novel alkyl-hydroxyl-sulfobetaine responsible for surfactant EOR is to increase the capillary
zwitterionic surfactants (CnHSB, n = 12, 14, 16 or 18) number by reducing the interfacial tension (IFT) between
were synthesized and their applicability for chemical crude oil and water. The primary surfactant used for SP
enhanced oil recovery was studied. The interfacial tension flooding is petroleum sulfonate (PS). To reach ultra-low
measurements between CnHSB and Shengli crude oils IFT, PS is often mixed with complementary surfactants of
from four different blocks indicated that C16HSB and different types. The combined surfactant system has been
C18HSB are adapted to high-temperature and high-salinity widely used and succeeded at relatively ideal reservoirs
reser-voirs conditions. The interfacial activity was also with low temperature and low salinity. However, with the
main-tained high after interacting with sand. Furthermore, progress of oil field development, the future SP flooding
C16HSB and C18HSB are compatible with partially projects have to face more challenging reservoir conditions
hydrolyzed polyacrylamide (HPAM). Physical simulation with high temperature and high salinity. Ultra-low IFT is
experiment showed that the oil recovery of surfactant/ no longer available by currently used surfactants under
polymer flooding (0.3 wt% C18HSB ? 0.15 wt% HPAM) severe reservoir conditions and the performance of SP
can be improved by 18.6 % over water flooding. flooding will be affected accordingly. Great efforts have
been focused on the development of heat-resistant and salt-
Keywords High-temperature and high-salinity reservoir tolerant EOR surfactant.
Alkyl-hydroxyl-sulfobetaine Surfactant/polymer flooding Zwitterionic surfactants are interesting in several
Enhanced oil recovery Interfacial tension respects. Depending on the nature of the polar groups, the
zwitterionic surfactants often display excellent interfacial
activity, and are known to be less irritating to human’s skin
Introduction than many ionic surfactants. Also, changes in temperature,
pH, and added electrolyte have minimal effects on zwit-
Chemical flood is one of the most important enhanced oil terionic surfactants. Compared with conventional anionic,
recovery (EOR) techniques for oil production. Field cationic and nonionic surfactants, zwitterionic surfactants
applications have demonstrated that chemical flooding have better temperature resistance and salt tolerance.
technologies, especially surfactant-polymer (SP) flooding Hence, many researches on zwitterionic surfactants for oil
can achieve good performance in terms of water cut extraction field have been reported in recent years (Harri-
decreasing and oil production increasing (Austan 1995; son et al. 1998; Danov et al. 2004; El-Aila 2005). The
Sun et al. 2007; Wang et al. 2009). The mechanism betaine zwitterionic surfactants have usually acted as
complementary surfactants in chemical flooding. Very few
SP trials have been carried out using solely betaine and
S. Guo (&) H. Wang J. Shi B. Pan Y. Cheng hydrolyzed polyacrylamide (HPAM). It is mainly due to
Geological Scientific Research, Institute of Shengli Oilfield
Company, SINOPEC, Liaocheng Rd 3, Dongying 257015, the great adsorption loss of betaine surfactants in the for-
People’s Republic of China mation which presents a major challenge for their appli-
e-mail: sfguo513@163.com cations in chemical flooding.
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322 J Petrol Explor Prod Technol (2015) 5:321–326
CnHSB were synthesized in our laboratory with purity Physica MCR 301 rotational rheometer was used to mea-
greater than 99 %. Epichlorokydrin, sodium bisulfite and sure the viscosity of chemical solutions.
tertiary amine were analytically pure, purchased from
Shanghai reagent company. HPAM provided by Hengju IFT after adsorption
Corporation, relative viscosity-average molecular weight
of 22,000,000 and hydrolysis degree of 24.4 %. The adsorption experiment is described here: mix 90 g of
0.3 wt% CnHSB solution with 30 g of sand; after shaking
Synthesis at a speed of 170 r/min in a water bath at formation tem-
perature for 24 h, the supernatant was centrifuged for IFT
The synthesis of CnHSB consists of two steps. First, epi- measurement.
chlorokydrin was added slowly into dissolved sodium
bisulfite with continuous stirring. The reaction may con- Compatibility with polymer
tinue for 7 h at 40 LC. After recrystallizing with alcohol
and drying, the white crystal of 3-chloro-2-hydroxyl pro- The experiment was carried out as follows: first prepare 0.5
panesulfonate intermediate was obtained. The reaction wt% HPAM stock solution with plain water; dissolve 0.3 g
equation of the intermediate is shown as follows: CnHSB into 70 g saline solution with formation water and
OH
O
Cl NaHSO3 ClCH2CHCH2SO3Na ð1Þ
Second, the intermediate was mixed with tertiaryamine keep stirring for 15 min; then add 30 g HPAM stock
(n = 12, 14, 16, or 18) at 1:1 mass ratio. The product was solution into the prepared surfactant solution and keep
then concentrated by spinning evaporation. The equation stirring the binary system for at least 30 min. By doing so,
of quaternary ammonium salt forming reaction is shown as the concentrations of CnHSB and HPAM in the binary
follows: system are 0.3 and 0.15 wt%, respectively. The viscosity
OH
-
N N
+ CH2CHCH2SO3
C H CH
n 2n+1 + ClCH2 CHCH2SO3Na n 2n+1 ð2Þ
OH
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J Petrol Explor Prod Technol (2015) 5:321–326 323
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324 J Petrol Explor Prod Technol (2015) 5:321–326
10 10
EGD EGD
CGD CGD
ST 1 ST
IFT (mN/m)
IFT (mN/m)
1
0.1
0.1
0.01
0 20 40 60 80 100
t (min) 0 20 40 60 80 100 120
t (min)
(a) (b)
0.1
0.01
IFT (mN/m)
IFT (mN/m)
0 10 20 30 40 50 60 70
t (min)
1E-3
(d)
0 5 10 15 20 25 30 35 40
t (min)
(c)
Fig. 2 Dynamic IFT between C12HSB (a), C14HSB (b), C16HSB (c) and C18HSB (d) solutions and crude oil from different blocks
of binary system increased but still remained in the ultra-
IFT after adsorption low range which is demanded by surfactant EOR. Nor-
mally, surfactant as salt can promote polymer hydrolysis
The interaction between surfactant and rock might affect
the activity of surfactant. The ability to maintain high
interfacial activity after interacting with the reservoir sand
is very important for oil displacement.
The dynamic IFTs before and after adsorption are
shown in Fig. 3. It can be seen that IFT increased but still
reached ultra-low after adsorption, indicating that the
interaction of C16HSB and C18HSB with sand has no
impact on its activity.
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J Petrol Explor Prod Technol (2015) 5:321–326 325
0.1 1
Aqueous phase: 0.3% C16HSB
Oil phase: ST Crude oil Oil phase: ST Crude oil
before adsorption Aqueous phase:
after adsorption
0.3% C16HSB
Oil phase: CGD Crude oil
before adsorption 0.1 0.3% C16HSB+0.15% HPAM
IFT(mN/m)
(mN/m)
after adsorption Oil phase: CGD Crude oil
0.01 Aqueous phase:
0.3% C16HSB
0.3% C16HSB+0.15% HPAM
IFT
0.01
1E-3
0 10 20 30 40
1E-3
t (min) 0 10 20 30 40 50 60
(a) t (min)
0.1 (a)
Aqueous phase: 0.3% C18HSB 1
Oil phase: ST Crude oil
Oil phase: ST Crude oil
before adsorption
Aqueous phase:
after adsorption
Oil phase: CGD Crude oil 0.3% C18HSB
before adsorption 0.3% C18HSB+0.15% HPAM
IFT(mN/m)
(mN/m)
0.01
1E-3
0 10 20 30 40
t (min) 1E-3
0 10 20 30 40 50 60 70
(b)
t (min)
Fig. 3 Dynamic IFT between 0.3 % C16HSB (a) and C18HSB (b) (b)
solutions for crude oil before and after adsorption
Fig. 4 Effect of HPAM on the IFT of 0.3 % C16HSB (a) and C18HSB
(b) solutions for Shengli crude oil
Table 2 The viscosity of different chemical systems
IFT(mN/m)
0.01 0.3% C18HSB
1E-3
0 10 20 30 40 50
t (d)
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326 J Petrol Explor Prod Technol (2015) 5:321–326
Table 3 Displacement efficiency of different chemical systems over water flooding. Our study suggests that C 18HSB has
Injected system Recovery Improved the potential as new opportunity for high-temperature and
factor (%) recovery (%) high-salinity reservoirs.
Water 48.6 – Acknowledgments The authors thank financial support from the
0.15 % HPAM 55.7 7.1 National Science & Technology Major Project of China
0.3 % C16HSB ? 0.15 % HPAM (2011ZX05011-004).
65.1 16.5
0.3 % C18HSB ? 0.15 % HPAM 67.2 18.6 Open Access This article is distributed under the terms of the
Creative Commons Attribution License which permits any use, dis-
tribution, and reproduction in any medium, provided the original
C18HSB ? 0.15 wt% HPAM) reached 67.2 %, increased by author(s) and the source are credited.
18.6 % for over water flooding and 10.5 % over poly-mer
flooding. The high recovery efficiency is the syner-gistic
result of swept efficiency improvement by polymer and
good displacement efficiency by zwitterionic surfac-tant. References
Our results indicate that C 18HSB is the most favorable
surfactant for oil displacement. Austan T (1995) Chemical flooding of oil reservoirs 3. Dissociative
surfactant-polymer interaction with a positive effect on oil
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