SPE 114345

Application of Surfactants with Narrow Equivalent Weight Distribution

and Desirable Structure to Daqing ASP Flooding
Xiaolin Wu, Liping Zong, Jie Chen, Haifeng Wang,Yong Yang, Cunlong Shan, and Jie Geng, Daqing Oilfield
Co., LTD
Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 1923April2008.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not
been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum
Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited.
Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE
copyright.


Abstract
Alkyl benzene surfactants with narrow equivalent weight distribution (NEWD) and desirable structure were prepared by
the alkylation of olefin, sulfonation and neutralization. Due to the favorable composition and molecular structure, they
prove to have exceptionally high activity and oil displacement ability. The laboratory evaluation indicates: (1) ASP
formulation can reduce oil-water interfacial tension IFT to/below 10
-3
mN/m at very low surfactant concentration
(0.05-0.3 wt%) and wide concentration range of alkaline (Na
2
CO
3
, 0.8-1.4 wt%). (2) The addition of Na
2
CO
3
instead of
NaOH reduces the risk of equipment corrosion and severity of produced fluid treatment. (3) Compared with conventional
surfactants, this class of surfactant is much more compatible with Daqing crude oils with different properties. (4) The
effect of surfactant chromatographic fractionation on ASP performance is dramatically reduced due to its narrow
equivalent weight distribution. (5) Laboratory core flooding can achieved about 20 per cent original oil in place (OOIP)
incremental over that for water displacement.
A 75 meter well-spacing ASP flooding field test composed of 3 injectors and 4 producers was conducted in Daqing
Sabei area in October, 2004 and was completed in 2005. Effective response began to be observed for the central
producing well No. 122 at the injection of 0.09 PV. Water cut decreased by 25.1 percent from 95.3 to 70.2 percent at the
injection of 0.378 PV and the period of water cut below 80 percent was maintained for 0.42 PV. The daily oil production
increased from 1 to 4 tons. For another producing well No. 133, water cut decreased by 71.3 percent from 99.0 to 28.7
percent at the injection of 0.575 PV. The final oil recovery amounted to 24.66 percent OOIP over water flooding.

Introduction
Laboratory studies on alkaline/surfactant/polymer (ASP) flooding were conducted since 1980s at Daqing and it proved to
have the favorable attributes of improving both the sweep efficiency and oil displacement efficiency.
1
The following
ASP pilot tests implemented in 1990s confirmed it is an effective oil recovery process with the ability of achieving about
20 percent original oil in place (OOIP) incremental over that for water displacement regardless of the low acid value of
Daqing crude oil (about 0.01 mg KOH/g crude oil).
2,3,4
To make ASP flooding more economically attractive, how to
reduce the cost of chemicals, especially the cost of surfactants, has been the main issue of interest. Various surfactants
including petroleum sulfonates, petroleum carboxylates, lignosulfonates, alkyl benzene sulfonateswere investigated at
2 SPE 114345
Daqing to form an ideal ASP formulation.
5,6,7,8,9
From 2001, alkyl benzene sulfonates with wide equivalent weight
distribution (WEWD) from about 330 to 530 were synthesized from the by-product of dodecyl alkyl benzene, and were
successfully applied in Daqing ASP pilot test.
8,10
However, poor compatibility with crude oils in Daqing different areas
may limit the large-scale application of WEWD surfactants to reservoirs with relatively low permeability and high
mineral content. Additionally, the addition of NaOH in the ASP formulation caused a series of problems such as
equipment corrosion, scaling and emulsion of produced fluid.
11
In this paper, the potential of alkyl benzene sulfonates
with narrow equivalent weight distribution (NEWD) used for EOR surfactants are investigated.

Experiment Section

Main Instruments.
SO
3
falling film reactor, B/R 9600 distillation unit for the alkyl benzene treatment, GC-MS (for the alkyl benzene
analysis), Texas-500 spinning drop interfacial tensiometer, coreflooding apparatus, Daqing sandstone cores with
permeabilitis in around Darcys.

Main Reagents.
Alpha-olefin (98%, purchased from Shell Company), NaOH, Na
2
CO
3
.

Surfactant Synthesis.
Surfactants synthesis procedure is illustrated by Fig. 1. Alkylbenzenes with narrow molecular weight distribution were
first prepared by the reaction of alpha-olefin with aromatics at the presence of catalyst and were further purified by
vacuum distillation to revome the impurities such as unreacted alpha-olefin and aromatic based on the boiling point
difference at the same pressure condition. Compositional difference between two kinds of alkylbenzenes is demonstrated
by Fig. 2. It indicates the content of alkylbenzenes with the same molecular weight amounted up to 98%. Compared with
the by product of dodecyl alkylbenzene, their carbon number is dramatically narrowed from about 13 to almost 1.
Sulfonation with SO
3
carried out in the falling film reactor produces the sulfonic acid and alkylbenzene sulfonates are
prepared by the neutralization with NaOH after the aging and hydrolysis period. Typically, surfactant product is brown in
color and uniformly dispersed containing about 50% activity.

Aromatics
T, Catalyst
Sulfonation with
SO
3
-olefin
Alkylbenzene
sulfonates
Neutralization with
NaOH
Alkylbenzene
Alkylation
Aromatics
T, Catalyst
Sulfonation with
SO
3
-olefin
Alkylbenzene
sulfonates
Neutralization with
NaOH
Alkylbenzene
Alkylation

Fig. 1-The flowchart of surfactant synthesis.
SPE 114345 3
0
5
10
15
20
25
A
b
u
n
d
a
n
c
e

(

)
Molecular weight
0
20
40
60
80
100
Molecular weight
A
b
u
n
d
a
n
c
e

(
%
)
Alkylbenzenes with Narrow molecular
weight distribution
Alkylbenzenes with wide molecular
weight distribution
0
5
10
15
20
25
A
b
u
n
d
a
n
c
e

(

)
Molecular weight
0
20
40
60
80
100
Molecular weight
A
b
u
n
d
a
n
c
e

(
%
)
0
5
10
15
20
25
A
b
u
n
d
a
n
c
e

(

)
Molecular weight
0
20
40
60
80
100
Molecular weight
A
b
u
n
d
a
n
c
e

(
%
)
Alkylbenzenes with Narrow molecular
weight distribution
Alkylbenzenes with wide molecular
weight distribution

Fig. 2-GC-MS analytical result of different kinds of alkylbenzenes.

Surfactant Property Evaluation.
To meet the criterion of enhanced oil recovery (EOR) surfactants, surfactant propertis including interfacial tension,
adsorption onto Daqing sandstone, thermal and chemical stability of IFT and viscosity of ASP solution and oil
displacement efficiency are measured under Daqing reservoir conditions. (1) IFTs between ASP solution and Daqing
crude oils were tested using Texas-500 model interfacial tensiometer at 45 and around 5000 rpm. The ASP solutions
were prepared by dissolving chemicals into Daqing producing water with salinity around 5000 mg/L TDS. (2)
Adsorption of surfactant onto Daqing sand is calculated by determining the surfactant concentrations before and after
immerging clean sands into ASP solution for a sufficient long time or an equilibrium state is considered to be reached.
Two-phase titration for anionic surfactant concentration determination is applied here. (3) Thermal and chemical stability
of ASP solution which is put into an oven at 45 are tested by measureing its IFTs and viscosity periodically over 3
months. (4) Laboratory coreflooding is performed to assess oil-displacement efficiency of ASP system. The core is first
vacuumed and then saturated with Daqing formation water with salinity of 7000 mg/L and Daqing crude oil. Water
flooding is performed to displace oil until water cut is almost 100 per cent. During the chemical flooding period, ASP
solution and polmer solution with a specific slug size are injected followed by water postflush until the effluent is almost
100 per cent water. The final oil recovery could be calculated.

Results and Discussions

Comparison of Molecular Structures between NEWD Surfactants and WEWD Surfactants.
Except for the difference in the molecular distribution, molecular structure difference between these two surfactants is
also illustrated by Fig. 3 (octodecyl alkylbenzene is set an example here). For the NEWD surfactants, only one long
alkyl chain with a carbon number of 18 is attached to the benzene ring. However, for the conventional WEWD alkyl
benzene sulfonates, the alkyl chains attached to benzene ring are usually composed of two parts, one is octadecyl, and the
other is decadecyl.
4 SPE 114345
NEWD alkylbenzene sulfonates WEWD alkylbenzene sulfonates
S
O
3
N
a
S
O
3
N
a
NEWD alkylbenzene sulfonates WEWD alkylbenzene sulfonates
S
O
3
N
a
S
O
3
N
a

Fig. 3-Molecular structure comparison between NEWD and WEWD alkylbenzene surfactants.

Interfacial Tension (IFT) Evaluation.
IFT between Daqing crude oil and ASP system were measured by Texas-500 interfacial tensiometer at 45 , see Fig. 4
and 5. By comparison, the dynamic IFT behavior of conventional WEWD alkylbenzene sulfonates were also provided
here. It demonstrates that within a wide concentration range of surfactant (0.05-0.3 wt%) and alkaline (Na
2
CO
3
, 0.8-1.4
wt%), ultra-low IFTs with a magnitude order of 10
-3
mN/m were achieved. Properties depends on the molecular
structure, therefore, NEWD surfactants tend to orient more vertically and tightly onto the oil/water interface, resulting in
a lower IFT decrease than WEWD surfactants. On the other hand, the more uniform composition are able to achieve a
stable adsorption onto this interface, therefore, IFTs with a magnitude order of 10
-4
mN/m are able to last for more than 5
hours, Nevertheless, for WEWD surfactants, IFTs below 10
-2
mN/m only last for about 3 hours.
10
-4
120 180 240 300
WEWD surfactant
NEWD surfactant
10
-3
10
-2
10
-1
1
0 60
Time, min
I
F
T
,

m
N
/
m
10
-4
120 180 240 300
WEWD surfactant
NEWD surfactant
10
-3
10
-2
10
-1
1
0 60
Time, min
I
F
T
,

m
N
/
m

Fig. 4-Comparison of dynamic IFT behavior of NEWD and WEWD surfactants.
SPE 114345 5
0.6 0.8 1 1.2 1.4 1.6
0.1
0.2
0.3
0.25
0.05
10
-4
mN/ m
10
-2
mN/ m
10
-3
mN/ m
S
u
r
f
a
c
t
a
n
t

c
o
n
c
e
n
t
r
a
t
i
o
n

(
w
t
%
)
4
-
-
Na
2
CO
3
concentration (wt%)
0.6 0.8 1 1.2 1.4 1.6
0.1
0.2
0.3
0.25
0.05
10
-4
mN/ m
10
-2
mN/ m
10
-3
mN/ m
S
u
r
f
a
c
t
a
n
t

c
o
n
c
e
n
t
r
a
t
i
o
n

(
w
t
%
)
4
-
-
Na
2
CO
3
concentration (wt%)

Fig. 5-Activity diagram of NEWD surfactants.
IFT and Viscosity Stability.
ASP solution stabilities are evaluated at 45 . Fig. 6 and 7 illustrate that the IFT and viscosity of ASP formulation
(S=0.2wt%, Na
2
CO
3
=1.2wt%P=1200mg/L) could be kept stable for at least 3 months.
Time( days)
0
20 40 60 80 100
10
-4
10
-1
10
-2
10
-3
1
I
F
T
(
m
N
/
m
)
Fig. 6-IFT stability of ASP formulati on
0
60
0 10 20 30 40 50 60 70 80 90 100
20
40
80
V
i
s
c
o
s
i
t
y

(
c
p
)
Time(days)
Fig. 7-Viscosity stability of ASP formulati on
Time( days)
0
20 40 60 80 100
10
-4
10
-1
10
-2
10
-3
1
I
F
T
(
m
N
/
m
)
Fig. 6-IFT stability of ASP formulati on
Time( days)
0
20 40 60 80 100
10
-4
10
-1
10
-2
10
-3
1
I
F
T
(
m
N
/
m
)
Fig. 6-IFT stability of ASP formulati on
0
60
0 10 20 30 40 50 60 70 80 90 100
20
40
80
V
i
s
c
o
s
i
t
y

(
c
p
)
Time(days)
Fig. 7-Viscosity stability of ASP formulati on
0
60
0 10 20 30 40 50 60 70 80 90 100
20
40
80
V
i
s
c
o
s
i
t
y

(
c
p
)
Time(days)
Fig. 7-Viscosity stability of ASP formulati on


Surfactant Adsorption.
To better understand the effect of surfactant chromatographic fractionation on the ASP performance, the adsorption of
C12, C18 and C20 alkylbenzene sulfonates onto Daqing sand were measured. Fig. 8 demonstrates that the adsorption
increases by about 155%, from 0.47 to 1.20 mg/g sand, with the increase of the surfactant equivalent weight from C12 to
C20 alkylbenzene sulfonates, which proves that higher equivalent weight molecules will cause a higher retention onto the
reservoir. Therefore, the performance of the ASP formulation using a WEWD surfactant will be affected by the
chromatographic fractionation more severely than the use of a NEWD surfactant.
6 SPE 114345
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.1 0.2 0.3 0.4 0.5
Surfactant concentration (wt%)
A
d
s
o
r
p
t
i
o
n

(
m
g
/
g

s
a
n
d
)
C20
C18
C12
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.1 0.2 0.3 0.4 0.5
Surfactant concentration (wt%)
A
d
s
o
r
p
t
i
o
n

(
m
g
/
g

s
a
n
d
)
C20
C18
C12

Fig. 7-Adsorption comparison of surfactants with different equivalent weight.
Laboratory Coreflooding.
Recovery efficiency of ASP system on Daqing sandstone cores (2.5 cm10 cm) could enhance oil recovery about 20
per cent OOIP incremental over that for water displacement, see Table. 1.
Table.1-Laborotory coreflooding results
Core No.
Permeability
10
-3
m
2

Waterflooding
oil recovery
(OOIP) %
ASP oil recovery
(OOIP) %
Total oil recovery
(OOIP) %
Oil Saturation
%
t-04-113 1199 55.0 18.8 73.8
67.6
t-04-22 1056 47.6 22.6 70.2 71.6
t-04-28 1123 44.9 19.0 63.9 71.6
t-04-126 1270 41.7 19.0 60.7
72.0
t-04-10-1 1638 47.8 18.7 66.5
72.5

Compatibility with Daqing Different Crude Oils.
IFTs between ASP formulation and Daqing curde oils which are from different pay zones were measured to test the
performance of the NEWD surfactants. Fig. 9 shows the good compatibility of NEWD alkylbenzene sulfonates with
Daqing different crude oils, which illustrates the great potential of the large-scale application of NEWD surfactants to
Daqing ASP flooding because for those reservoirs with relatively low permeability and high mineral content, an ideal
ASP solutions could still be formulated.
SPE 114345 7
0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
I
F
T

(
m
N
/
m
)
1
Gaotaizi
P
I
S
II12
10
-1
10
-2
10
-3
10
-4
Na
2
CO
3
concentration (wt%)
0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
I
F
T

(
m
N
/
m
)
1
Gaotaizi
P
I
S
II12
Gaotaizi
P
I
S
II12
Gaotaizi
P
I
S
II12
10
-1
10
-2
10
-3
10
-4
Na
2
CO
3
concentration (wt%)

Fig. 9-Compatibility of NEWD surfactant with Daqing different crude oils.
Note: Gaotaizi, P
I
and S
II 12
represent Daqing different pay zones.

ASP Flooding Pilot Test.
The ASP flooding pilot test with 75m well-spacing and 7 wells (3 injectors and 4 producers) was conducted in Daqing
Sabei area in October, 2004 and was completed in 2005. The target zoon is S
II12
and the detailed information is shown in
Table.2.
Table 2-Reservoir characteristics of ASP flooding pilot test
Item Central area Whole area
Sandstone thickness (m) 3.0 2.7
Net thickness (m) 2.2 1.9
Effective permeability ( m
2
) 0.435 0.465
Area (m
2
) 7,944 35,748
Pore volume (m
3
) 4,285 16,207
OOIP (ton) 2,401 9,137

Effectiveness began to be observed for the central producing well No. 122 at the injection of 0.09 PV, see Table. 3.
Water cut decreased by 25.1 from 95.3 to 70.2 percent at the injection of 0.378 PV and the period of water cut below 80
percent was maintained for 0.42 PV. The daily oil production increased from 1 to 4 tons. For another producing well No.
133, water cut decreased by 71.2 from 99.9 to 28.7 per cent at the injection of 0.575 PV. The final oil recovery amounted
to 24.66 percent OOIP over water flooding. Therefore, both laboratory study and field test confirmed surfactants with
narrow equivalent weight distribution and desirable structure are promising in the ASP flooding application in the
Daqing oilfield.


8 SPE 114345
Table 3-Production performance of the ASP flood pilot
The start of ASP injection The maximum water-cut decline
Well No.
Daily fluid
prod
(t/d)
Daily oil
prod
(t/d)
Water
cut
(%)
Daily fluid
prod (t/d)
Daily oil
prod (t/d)
Water cut
(%)
Daily
incremental
Oil
(t/d)
Water-cut
decline (%)
122 26 1 95.3 15 4 70.2 3 25.1
133 8 0 99.9 2 1 28.7 1 71.2
Whole area 49 1 98.0 32 6 79.1 5 18.9

Conclusions
1. Alkyl benzene surfactants with narrow equivalent weight distribution and desirable structure prove to have
exceptionally high activity. Ultra-low IFT with a magnitude of 10
-3
mN/m could be achieved at very low
surfactant concentration (0.05-0.3 wt%) and wide concentration range of alkaline (Na
2
CO
3
, 0.8-1.4 wt%) and
the ASP solution maintains good IFT and viscosity stability over a period of three months.
2. Compared with conventional surfactants, this class of surfactant is much more compatible with Daqing crude
oils with different properties.
3. The effect of surfactant chromatographic fractionation on ASP performance is dramatically reduced due to its
narrow equivalent weight distribution.
4. Both the Laboratory core flooding and pilot test confirmed that ASP formulation using NEWD surfactants can
achieved about 20 per cent original oil in place (OOIP) incremental over that for water displacement.
5. The addition of Na
2
CO
3
instead of NaOH reduces the risk of equipment corrosion and severity of produced fluid
treatment.

References
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SPE/DOE 35383 presented at the 1996 SPE/DOE Symposium on Improved Oil Recovery held in Tulsa, OK, April 21-24.
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at the 1996 SPE Annual Technical Conference and Exhibition held in Denver, Colorado, October 6-9.
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SPE 114345 9
10. Li Hongfu, et al.: Alkaline/Surfactant/Polymer (ASP) Commercial Flooding Test in Central Xing-2 Area of Daqing
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