Colloids and Surfaces A: Physicochem. Eng.

Aspects 290 (2006) 164–171

Characterization and demulsification of produced liquid

from weak base ASP flooding
Zhang Ruiquan a,b , Liang Chenghao a , Wu Di b , Deng Shubo c,∗
aSchool of Chemical Engineering, Dalian University of Technology, Dalian 116012, China
b Daqing Oilfield Engineering Co. Ltd., Daqing 163712, China
c Department of Environmental Science & Engineering, Tsinghua University, Beijing 100084, PR China

Received 22 January 2006; received in revised form 11 May 2006; accepted 22 May 2006
Available online 27 May 2006

Abstract
Weak base alkali-surfactant-polymer (ASP) flooding technology has been applied in Daqing oilfield to enhance oil recovery. The effects of ASP
on the characteristics of oil droplets in produced liquid were investigated. Surfactant can decrease interfacial tension (IFT) and zeta potential,
making main contribution to the stability of oil droplets. Weak alkali (Na2 CO3 ) can decrease IFT and polymer can decrease zeta potential, resulting
in stable oil droplets in produced liquid. The produced liquid from weak base ASP flooding is easier to treat than that from strong base ASP
flooding. A mixed demulsifier GFD410-8 was prepared and used to enhance oil–water separation in produced liquid. When the demulsifier dose
of 50 mg/kg was used to demulsify the simulated produced liquid with the concentrations of alkali 2000 mg/kg, surfactant 600 mg/kg and polymer
600 mg/kg, water volume and water content after 30 min settling were less than 30% and 1000 mg/L, respectively. The demulsifier also greatly
decreased water content in oil phase and oil concentration in water phase for actual produced liquid from oil well. The demulsification mechanism
was also investigated in terms of IFT and zeta potential.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Produced liquid; Weak base ASP flooding; Interfacial property; Demulsifier; Oil–water separation

1. Introduction
Daqing oilfield is one of the biggest oilfield in the world, and
its oil production reached over 4.5 × 107 tonnes per year in the
past over 20 years [1]. Alkali-surfactant-polymer (ASP) flooding
technology, as an important technology of tertiary oil extraction,
has been found to enhance oil recovery by over 20% and hence
has been used in full-scale in the Daqing oilfield, which is the
most successful case of ASP flooding in the world [2–8]. At first,
the imported surfactant ORS-41 (major component of alkylben-
zene sulphonate) from Witco Company and NaOH were used
as surfactant and alkali, respectively, in Daqing Oilfield [9]. In
consideration of the expensive cost of imported surfactant and
strong alkalinity of NaOH causing the stratum corrosion and
scale formation in the ground systems, a local produced surfac-
tant and weak base (Na2 CO3 ) are being applied and the field
∗ Corresponding author. Tel.: +86 10 62773519-602; fax: +86 10 62794006.
E-mail address: dengshubo@tsinghua.edu.cn (S.B. Deng).
tests have been conducted in Daqing oilfield. To the best of our
knowledge, no field tests of weak base ASP flooding technology
have been carried out in other oilfields and few researchers have
studied the produced liquid (mixture of oil and water from oil
wells). As the different chemicals are adopted in oil extraction,
it is necessary to investigate the characteristics of produced liq-
uid from the weak base ASP flooding and enhance the oil–water
separation through demulsification.
Due to the use of alkali, surfactant and polymer in the
injected water in ASP flooding technology, the oil–water inter-
facial properties are changed and the oil droplets become stable
[10]. Some researchers [1,6,11] studied the effects of strong
alkali/surfactant/polymer on interfacial tension (IFT) between
water and crude oil during oil extraction and found that those
chemicals could greatly decrease the IFT between water and
oil droplets. Kang et al. [6] investigated the effects of strong
alkali/surfactant/ polymer on w/o emulsion stability in produced
liquid from strong base ASP flooding and showed that the IFT
and interfacial film strength affected emulsion stability. Our pre-
vious study showed that surfactant ORS-41 mainly dominated

0927-7757/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.05.023
 R. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 290 (2006) 164–171
the stability of oil droplets in the produced water from strong
alkali ASP flooding (surfactant ORS-41, alkali NaOH), and it
decreased IFT and zeta potential and made oil droplets difficult
to approach and coalesce in produced water [1]. However, the
stability of produced liquid from the weak base ASP flooding
has not been reported.
Demulsification is an important technology for oil–water sep-
aration in the treatment of produced liquid in oilfield, especially
for the produced liquid in Daqing oilfield as water content in
produced liquid has exceeded 85% [10,12]. Effective demulsi-
fiers can accelerate the oil–water separation and reduce the oil
concentration in water phase and water in oil phase [13–15].
Addition of demulsifiers alters the oil–water interfacial prop-
erties and destabilizes the oil droplets in produced liquid. Due
to the different properties of produced liquid from different oil
fields, the effective demulsifier is normally different. In our pre-
liminary experiments, the effective demulsifiers for the produced
liquid from strong alkali ASP flooding and polymer flooding are
not effective for the produced liquid from weak base ASP flood-
ing.
In this study, the simulated produced liquid from weak base
ASP flooding was prepared and the effects of ASP on the stabil-
ity of oil droplets in terms of interfacial tension and zeta potential
were investigated. An effective mixed demulsifier was prepared
and used to demulsify the simulated and actual produced liquid
from weak base ASP flooding, and the demulsification mecha-
nism was also discussed.
2. Materials and methods
2.1. Materials
The crude oil obtained from the local oilfield in Daqing has
water content of less than 0.5%, and density and viscosity of
850 kg m−3 and 60.89 mPa s (at 45 ◦ C), respectively. The poly-
mer (partly hydrolyzed polyacrylamide, HPAM) has an average
molecular weight (MW) of 1 × 107 and a degree of hydrolysis
of about 25%. A surfactant compound with a major component
of alkylbenzene sulphonate with a long side chain (C16 –C24 )
used in this study was supplied by a local company, and its
active content is 50 wt%. The alkali used in this study was
Na2 CO3 . About 50 nonionic and anionic demulsifiers were pro-
vided by Shandong Binzhou Chemical Company and Nanjing
Jinling Chemical Company in China.
2.2. Preparation of simulated produced liquid for its
stability tests
According to the underground water qualities in the Daqing
oilfield, brine was prepared, and salts contained in the brine were
as follows (mg/L), NaCl 1167.2, NaHCO3 2442.9, Na2 SO4 6.8,
CaCl2 59.7, MgCl2 ·6H2 O 53.1. The method for preparing pro-
duced liquid from ASP flooding and the stability tests were as
follows: (1) 70 g of brine with different concentration of ASP
was added to a 150 mL flask. The mixture was then heated to
45 ◦ C. Thirty grams of crude oil at 45 ◦ C was added consecu-
tively; (2) the mixture was heated to 45 ◦ C in a water bath for
165
30 min, and then shaken in a back-and-forth shaker with a fre-
quency of 5 Hz for 5 min to produce the simulated produced
liquid [16]; (3) the mixture was allowed to settle for 30 min at
45 ◦ C in a water bath. Water sample was taken from the bot-
tom of the bottle using a syringe and the oil concentrations were
measured; (4) the water content in oil phase was calculated from
the water volume after 30 min settling.
2.3. Size determination of oil droplets
A laser particle size analyzer 1064L (CILAS Company,
France) was used to determine the size of the oil droplets. The
method for preparing produced liquid from ASP flooding for
size determination in the lab was as follows: (1) 30 g of crude
oil was added to 70 g of brine with different concentrations of
ASP in a 150 mL jar; (2) the mixture was then heated to 45 ◦ C
for 18 h; (3) the mixture was emulsified for 2 min at 20,000 rpm
with a PT3000 emulsifier (Kinematich Company, Switzerland)
to obtain a oil–water mixture; (4) 0.3 mL of the oil–water mix-
ture was added to 500 mL DI water at 45 ◦ C and stirred gently
with a glass rod, and transferred to a cuvette. The median diam-
eter of oil droplets was then measured.
2.4. Oil–water IFT measurement
Two hundred and eighty grams of the simulated produced
water and 120 g of the crude oil were added to a 500 mL jar
and maintained at 45 ◦ C in a constant temperature device for
180 h. The mixture was then cooled down to 10 ◦ C to separate
oil and water. The separated oil and water were used as test
materials. A K12 tensiometer (Kruss Company, Germany) was
used to determine the oil–water interfacial tension at an operat-
ing temperature of 45 ◦ C. The balance time was 30 min before
the determination.
2.5. Determination of zeta potential of oil droplets
The zeta potential measurement was conducted on a Zeta-
plus zeta apparatus (Brookhaven Company, USA). Hundred
milliliters of produced liquid was allowed to settle for 2 h at
45 ◦ C, and then 10 mL sample was taken out from the bottom
of the jar and added to the test utensil of the zeta apparatus for
zeta potential measurement.
2.6. Demulsification tests
To obtain a stable produced liquid in the demulsification
tests, the method for preparing produced liquid was similar
to that described in Section 2.3. The mixture contained alkali
2000 mg/kg, surfactant 600 mg/kg, polymer 600 mg/kg. A 0.5 g
of 1% demulsifier solution was added to 100 g of the pro-
duced liquid. After being intensively shaken for 1 min to pro-
duce a uniform solution, the mixture was allowed to settle for
30 min in a water bath of 45 ◦ C. The water volume and oil
concentration in water phase were measured at 30 min, while
the water content in oil phase was calculated from the known
data.
166 R. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 290 (2006) 164–171

3. Results and discussion
3.1. Oil–water separation properties of simulated produced
liquid
Table 1 shows the effects of alkali, surfactant and polymer on
the oil–water separation in the simulated produced liquid. With
each of the ASP chemicals in water (alkali 0–3000 mg/kg, sur-
factant 0–600 mg/kg, polymer 0–600 mg/kg), it can be seen that
both alkali and surfactant make oil–water separation difficult.
When the alkali concentration changed from 0 to 3000 mg/kg,
the water content in oil phase increased from 3.2% to 37.55%
and the oil concentration in water phase enhanced from 253 to
1803 mg/L. The similar result was observed when the surfactant
concentrations increased from 0 to 600 mg/kg. For the polymer
concentrations ranging from 0 to 600 mg/kg, the water content
in oil phase increases with increasing polymer concentrations,
but the oil concentrations in water phase fall at first, and then
rise, which is attributed to the flocculating ability of the poly-
mer [1]. Among three chemicals, the effect of surfactant on oil
concentration in water phase is the most significant, while the
water content in oil phase is mostly affected by the alkali con-
centration.
Table 1 also shows the oil–water separation when the three
chemicals exist simultaneously in the produced liquid. The sim-
ilar results are observed compared to that obtained for the sole
chemical. The water content and oil concentration increase with
the increase of alkali and surfactant concentrations, while the
oil concentrations and water content decrease initially, and then
increase with increasing polymer concentrations when the con-
centrations of alkali and surfactant are 2000 and 600 mg/kg,
respectively. The minimum water content and oil concentration
are obtained at 200 mg/kg polymer in the effect of polymer on
oil–water separation. According to the above results, oil–water
separation is the most difficult with the concentrations of alkali,
surfactant and polymer at 2000, 600 and 600 mg/kg, respectively,
and the produced liquid with the specific ASP concentrations
was used in the demulsification tests.
3.2. Oil–water interfacial properties
The stability of oil droplets is associated with the oil–water
interfacial properties such as interfacial tension, zeta potential,
interfacial rheology, etc., which are affected by the ASP con-
centrations in the produced liquid [17,18]. The produced liquid
from ASP flooding is normally quite stable due to the presence
of some ASP and the coalescence of oil droplets becomes dif-
ficult, resulting in the high water content in oil phase and oil
concentration in water phase. Interfacial tension and zeta poten-
tial are two important factors affecting the coalescence of oil
droplets and were investigated in this study.
3.2.1. Effects of ASP on oil–water interfacial tension
With each of the ASP chemicals in water (surfactant
0–800 mg/kg, alkali 0–800 mg/kg, polymer 0–800 mg/kg), the
effects of chemical concentrations on IFT are shown in Fig. 1.
It can be seen that the effect of surfactant on IFT is most sig-
nificant. When the surfactant concentrations increase from 0 to
800 mg/kg, the IFT decreases from 23.4 to 0.86 mN/m. When the
imported surfactant ORS-41 was used, the IFT value was lower
[1], indicating that the surfactant used in this study is less effec-
tive in lowering IFT. IFT also decreases slowly with the increase
of alkali concentration because the added weak alkali can react
with the acidic components of the crude oil and some surfac-
tants may be produced and lower the IFT. The effect of polymer
concentrations on the IFT can be negligible. It is well known

Table 1
Effects of ASP on the oil–water separation of the simulated produced liquid
No. Concentration (mg/kg) Water volume (mL) Water content (%) Oil concentration (mg/L)

A S P

1 0 0 0 69 3.2 253
2 1000 0 0 64 16.7 886
3 2000 0 0 58 28.6 1338
4 3000 0 0 52 37.5 1803
5 0 200 0 68 6.3 3207
6 0 400 0 65 14.3 4202
7 0 600 0 62 21.1 4879
8 0 0 200 68 6.3 166
9 0 0 400 65 14.3 1563
10 0 0 600 63 19.0 3407
11 0 600 600 55 33.3 990
12 1000 600 600 52 37.5 3141
13 2000 600 600 50 40 3214
14 3000 600 600 51 38.8 2908
15 2000 0 600 69 3.2 1722
16 2000 200 600 65 14.3 3241
17 2000 400 600 56 31.8 3828
18 2000 600 0 60 25 3509
19 2000 600 200 55 33.3 2162
20 2000 600 400 52 37.5 2804
 R. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 290 (2006) 164–171
Fig. 1. Effects of ASP on the IFT at their sole presence in the produced liquid.
that the lower the IFT is, the more stable the oil droplets are [7].
Therefore, the surfactant can reduce oil–water IFT greatly and
make oil droplets stable.
When the ASP chemicals co-exist in the produced liquid,
the effects of alkali and surfactant on IFT are shown in Fig. 2
when polymer concentration was fixed at 400 mg/kg. It can be
seen that the IFT decreases significantly with increasing sur-
factant concentration in the range of 0–400 mg/kg and deceases
gradually when the surfactant concentrations exceed 400 mg/kg.
The IFT also decreases with increasing alkali concentration in
the range of 0–2000 mg/kg at the same surfactant concentra-
tion. The IFT is 0.51 mN/m when the concentrations of alkali,
surfactant and polymer are 2000, 600 and 400 mg/kg, respec-
tively. In our previous study, the ultra-low IFT of 0.03 mN/m
was obtained when the concentrations of alkali (NaOH), surfac-
tant (ORS-41) and polymer were 1000, 600 and 500 mg/L [1].
As the alkali used in this study is a weak base (Na2 CO3 ) and
the surfactant is a domestic product, their synergetic effects on
IFT are not obvious. The formation of ultra-low IFT is depen-
Fig. 2. Synergetic effects of surfactant and alkali concentrations on oil–water
IFT (polymer concentration 400 mg/kg).
167
dent on many factors such as surfactant, alkali, and crude oil
properties. The domestic surfactant used is sodium salt of alkyl-
benzene sulphonate with a C16 –C24 side chain similar to the
imported surfactant ORS-41, but it has a longer hydrophobic
carbon chain than ORS-41. When the molecular weight and car-
bon chain of surfactant match that of crude oil, the ultra-low IFT
can form in the ASP system [6]. The sole presence of surfactant
cannot form an ultra-low IFT. When alkali reacts with the acidic
components of crude oil, some new surfactants can be produced
and have synergetic effects on IFT. As Na2 CO3 is a weak base,
it may decrease the synergetic effects. The crude oil in Daqing
oilfield has low content of acidic components, and crude oil from
different zones has different properties. From the viewpoint of
IFT, the oil droplets in produced liquid from weak base ASP
flooding are less stable than that from strong base ASP flooding.
In ASP flooding technology, an ultra-low oil–water IFT can be
obtained by using suitable surfactant and alkali [19].
Further experiments show that the IFT increased a little with
the increase of polymer concentration when both alkali and sur-
factant were present in the produced liquid (data not shown). As
the polymer may adsorb on the oil–water interface and form a
complex film with some surfactants, the amount of the adsorbed
surfactant on oil–water interface may decrease, resulting in an
increase of IFT.
3.2.2. Effect on zeta potential
Fig. 3 shows the effects of alkali (0–1000 mg/kg), polymer
(0–600 mg/kg) and surfactant (0–600 mg/kg) on the zeta poten-
tials of oil droplets when other two chemicals were unchanged.
It can be seen that the zeta potentials decrease gradually with
increasing polymer concentration; the zeta potential values
decrease initially, and then increase for both surfactant and
alkali.
The effects of ASP on the zeta potentials are associated
with the characteristics of the three chemicals. Alkali, surfac-
tant and polymer in produced liquid can adsorb on the surface
of oil droplets and change the zeta potentials. As the polymer
used in this study is the partly hydrolyzed polyacrylamide, the
Fig. 3. Effects of alkali, polymer and surfactant on the zeta potentials of oil
droplets.
168 R. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 290 (2006) 164–171
adsorption of polymer on the oil droplets enhances the den-
sity of negative electric charge on the surface of oil droplets.
The zeta potentials decrease at surfactant concentrations below
300 mg/kg, which is attributed to the anionic alkylbenzene
sulphonate surfactant adsorbed on the surface of oil droplets.
The long hydrophobic carbon chains of the surfactant may enter
into oil phase, while the hydrophilic sulphonate groups stay
on the surface of oil droplets. Therefore, the negative charge
increases with increasing surfactant concentrations. It is strange
to find an increase of zeta potential with increasing surfactant
concentrations in the range of 300–600 mg/kg. As the surfac-
tant used in this study is a mixture and contains some nonionic
surfactant and unsulfonated alkylbenzene besides the main com-
ponent of alkylbenzene sulphonate, they may replace the anionic
surfactant on the oil–water interface at high surfactant concen-
trations, resulting in an increase of zeta potential. The profile of
the zeta potentials with increasing alkali concentrations exhibits
a V-shape. The zeta potential decreased from an initial value
of −58.6 mV to a critical minimal value of −63.7 mV when
the alkali concentration increased from 0 to 500 mg/kg, which
may be related to the newly formed surfactant between alkali
and organic acid in crude oil adsorbed on the surface of oil
droplets [20]. With the further increase of alkali concentration,
the zeta potentials increase. Although alkali may increase the
negative electric charge through the formation of new surfac-
tant, it can also compress the diffuse double layer on the surface
of oil droplets to enhance the zeta potential [1]. The overall effect
is an increase of zeta potentials at high alkali concentrations.
3.2.3. Effect on size of oil droplets
As the size of oil droplets directly affects the oil–water sepa-
ration of produced liquid (smaller the oil droplets, more difficult
the oil–water separation), the diameters of oil droplets at differ-
ent ASP concentrations were investigated. The synergetic effects
of ASP on the median diameter of oil droplets are shown in
Fig. 4. It can be seen that the sizes of oil droplets decrease with
increasing surfactant and polymer concentrations ranging from
Fig. 4. Effects of alkali, surfactant and polymer on the median diameter of oil
droplets.
0 to 600 mg/kg, while alkali has little effect on the size of oil
droplets in the range of 0–2000 mg/kg. Among three chemicals,
the effect of surfactant on the size of oil droplets is most signifi-
cant. With the concentrations of alkali and polymer at 1000 and
200 mg/kg, respectively, the median diameters of oil droplets
decreased from 8.64 to 2.95 ␮m when surfactant concentration
increased from 0 to 600 mg/kg. As the concentrations of polymer
and surfactant are 200 and 400 mg/kg, respectively, the effect of
alkali concentration on the size of oil droplets is not obvious and
only a little decrease is observed within the alkali concentrations
studied.
3.3. Demulsifier-screening tests
As the residual anionic polyacrylamide in the produced liq-
uid can react with some cationic flocculants and demulsifiers,
some viscous sediments can form and cause some problems such
as high volume of extra sediments, the fouling of the filtration
medium and short filtration period in the subsequent process
[12]. Therefore, some anionic and nonionic demulsifiers were
adopted in our study to demulsify the produced liquid from weak
base ASP flooding.
About 50 demulsifiers were used in the screening tests. It
was found that most demulsifiers did not decrease the final oil
concentration in water phase and water content in oil phase
compared with that in the reference sample where demulsifiers
were not added, and a few effective demulsifiers were selected
(data not shown). Among them, four demulsifiers were the most
effective and used in the preparation of mixed demulsifiers.
According to the uniform-design method, 10 demulsifiers were
prepared and used to demulsify the simulated produced liquid
with the concentrations of 2000 mg/kg alkali, 600 mg/kg sur-
factant and 600 mg/kg polymer. As shown in Fig. 5, the blank
sample without adding demulsifier has higher water content in
oil phase compared to that in the stability test as the preparation
methods of produced liquid are different. It can be found that the
10 demulsifiers all can enhance oil–water separation. Among 10
demulsifiers, the demulsifier GFD410-8 was the most effective
Fig. 5. Demulsification of the simulated produced fluid from ASP flooding using
different demulsifiers. Conditions: 45 ◦ C, settling time 30 min, demulsifier dose
50 mg/kg.
 R. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 290 (2006) 164–171
Fig. 6. Effect of demulsifier GFD410-8 dose on the demulsification of produced
liquid.
in the demulsification of the produced liquid. The water vol-
ume, water content in oil phase and oil concentration in water
phase after the demulsification using demulsifier GFD410-8
were 61 mL, 23% and 799.6 mg/L, respectively. This demulsifier
is water soluble and mainly composed of ethylene oxide, ethy-
lene oxide copolymer, polypropylene acid ramification, ethanol
and water. Water soluble demulsifiers are more popular for the
demulsification of produced liquid in oilfield due to easy use
and operation compared with oil-soluble demulsifiers [21].
3.4. Effect of demulsifier dose
The demulsifier GFD410-8 was used to demulsify the
simulated produced liquid with the concentrations of alkali
2000 mg/kg, surfactant 600 mg/kg and polymer 600 mg/kg.
Fig. 6 shows the effect of demulsifier dose on the demulsifi-
cation of the simulated produced liquid. When the demulsifier
dose increased from 0 to 60 mg/kg, the water content in oil phase
decreased and the water volume increased gradually, while the
oil concentrations in water phase decreased initially, and then
increased slowly till 40 mg/kg, and finally decreased gradually.
The increase of oil concentrations in the demulsifier dose range
of 10–40 mg/kg may be due to the aggregated oil droplets in
water phase which was not demulsified completely and did not
separate within 30 min settling. During the experiments, some
obvious aggregated oil droplets were observed in the water
phase. When the emulsifier dose exceeded 50 mg/kg, the aggre-
gated oil droplets disappeared. When the demulsifier dose was
60 mg/kg, the oil concentration, water volume and water content
were 773 mg/L, 62 mL and 21.7%, respectively.
In Daqing oilfield, oil concentration in water phase is required
to be less than 3000 mg/L before entering the system of wastew-
ater treatment, while water content in oil phase is less than 30%
before entering the electrical dewaterer. As shown in Fig. 6,
the oil concentration is below 3000 mg/L when the demulsifier
dose is above10 mg/kg, but the water content exceeds 30% at the
demulsifier dose of less than 40 mg/kg. Both water content and
oil concentration met the requirement when a dose of 50 mg/kg
demulsifier was added to the produced liquid.
169
Table 2
Comparison of the interfacial properties of oil droplets before and after
demulsification
Parameter No demulsifier 50 mg/kg ASP concentration
demulsifier (mg/kg)
IFT (mN/m) 2.37 2.69 A 500, S 400, P 400
Zeta potential −58.7 −46.2 A 1000, S 400, P 100
(mV)
Median diameter 4.02 4.95 A 500, S 400, P 200
(␮m)
3.5. Effect of demulsifier on interfacial properties
To investigate the demulsification mechanism, the interfacial
properties of oil droplets before and after demulsification were
measured. As shown in Table 2, when a dose of 50 mg/kg demul-
sifier was used to demulsify the produced liquid, the interfacial
tension increased from 2.37 to 2.69 mN/m and zeta potential
enhanced from −58.7 to −46.2 mV, indicating that the demulsi-
fier molecules can adsorb on the oil–water interface and replace
the surfactants on the surface of oil droplets. Surfactants in the
produced liquid including the residual surfactant and some sur-
factant produced by the reaction of organic acids in crude oil
with alkali can adsorb on the oil–water interface and stabilize
the oil droplets. During demulsification, effective demulsifiers
can replace the surfactants adsorbed on the oil–water interface
and adsorb on the surface of oil droplets [12,22]. As the anionic
charge on the surface of oil droplets decreased and IFT increased,
the stability of oil droplets decreased. The decrease in electro-
static repulsion facilitates the approach and coalescence of oil
droplets. It can be verified by the increased median diameter of
oil droplets from 4.02 to 4.95 ␮m in the presence of the demul-
sifier (see Table 2).
3.6. Evaluation of demulsifier for actual produced liquid
To evaluate the efficiency of the demulsifier GFD410-8 for
actual produced liquid from weak base ASP flooding, the in
situ produced liquid from a well (no.: North 2-6-501) with a
water content of 83%, polymer concentration of 905.1 mg/L,
surfactant concentration of 10.2 mg/L and alkali concentration
of 2870 mg/L in water phase was tested. Fig. 7 shows the water
content in oil phase and oil concentration in water phase with a
function of settling time with/without adding demulsifier. It can
be seen that the water content and oil concentration decrease
obviously after adding the demulsifier. The water content and oil
concentration without adding demulsifier after 30 min settling
are 30.5% and 1623 mg/L, respectively, while they decrease to
7.6% and 530 mg/L when 30 mg/kg demulsifier GFD410-8 was
used. As the surfactant concentration in the produced liquid is
relatively low, the oil–water separation is not difficult and only
30 mg/kg of the demulsifier can achieve the better oil–water
separation after 30 min settling.
As a large amount of ASP is resolved in the injected water
in ASP flooding technology, both produced liquid and produced
water contain some residual ASP and the oil–water separation
170 R. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 290 (2006) 164–171
Fig. 7. Water content in oil (a) and oil concentration in water (b) at different
settling time with/without demulsifier for actual produced liquid from north
2-6-501 well in Daqing oilfield.
in these processes becomes more difficult to treat than that from
water flooding and polymer flooding. As a consequence, the
existing treatment systems cannot meet the requirement of the
treatment of produced liquid and produced water from ASP
flooding. As oil–water separation is not efficient in the dewa-
tering process of produced liquid, oil concentration in produced
Fig. 8. Schematic diagram of the addition site of the demulsifier in the treatment
system of produced liquid and produced water.
water is high, increasing the difficulty of wastewater treatment.
We propose that the addition point of the demulsifier should be
set before the conventional demulsification process (see Fig. 8).
As the oil–water separation efficiency can be enhanced with the
help of the demulsifier in the dissociated water dewaterter, the
residual oil droplets in produced water can be removed success-
fully using the existing system (two settling processes and one
filtration process). This method has been proved to be the most
cost-effective for oil–water separation of produced liquid from
strong base ASP flooding in Daqing oilfield.
4. Conclusions
The surfactant and polymer decreased the size of oil droplets
in the produced liquid from weak base ASP flooding, and
made oil–water separation difficult. Moreover, ASP made the
oil droplets stable in the produced liquid and enhanced the
difficulty of oil–water separation. The surfactant contributed sig-
nificantly to the stability of oil droplets in produced liquid. It
can easily adsorb on the oil–water interface and decrease IFT
and zeta potential. Although alkali (Na2 CO3 ) can decrease IFT,
the ultra-low IFT was not obtained when ASP were present
in the produced liquid simultaneously. A water-soluble mixed
demulsifier GFD410-8 was prepared and used to treat the pro-
duced liquid from weak base ASP flooding successfully. The
demulsifier increased the zeta potential and IFT and made oil
droplets in the produced liquid instable. When the demulsifier
was used to treat the actual produced liquid in Daqing oilfield
at a dose of 50 mg/kg, the water content and oil concentration
after 30 min settling decreased to 7.6% and 530 mg/L, respec-
tively. This effective demulsifier can be added to the produced
liquid before the dewaterer to solve the problem of oil–water
separation.
Acknowledgements
This research was supported by Daqing Oilfield Limited
Company. Some researchers of Daqing Oilfield Engineering Co.
Ltd., including Qiao Liyan, Sun Fuxiang and Zhao Fengling, and
Liu Gang from School of Chemical Engineering, Dalian Univer-
sity of Technology, are acknowledged greatly for participating
in parts of this research.
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