J181742 DOI: 10.

2118/181742-PA Date: 8-June-16 Stage: Page: 1 Total Pages: 10

Effects of Surfactants and Alkalis on the

Stability of Heavy-Oil-in-Water Emulsions
Nana Sun, State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation–Southwest Petroleum
University and Xi’an Shiyou University; Jiaqiang Jing, State Key Laboratory of Oil and Gas Reservoir Geology
and Exploitation–Southwest Petroleum University and Oil & Gas Fire Protection Key Laboratory of Sichuan
Province, China; Huayi Jiang, Xi’an Shiyou University; Yunpeng An, China Pipeline Petroleum Engineering
Corporation; and Cheng Wu, Sijia Zheng, and Hongyuan Qi, State Key Laboratory of Oil and Gas
Reservoir Geology and Exploitation–Southwest Petroleum University

Summary upgrading (MacWilliams and Eadie 1993), and injection of a

In this work, the effects of combining a surfactant/alkali on the water sheath around the viscous crude. Each of these has logistic,
stability of heavy-oil-in-water emulsions are analyzed by use of technical, or economic drawbacks.
bottle testing, spinning-drop interfacial-tension (IFT) meters, Another favorable pipeline technique is the transport of vis-
microscopes, conductivity meters, zeta-potential analyzer Turbis- cous crude oils as an oil/water emulsion (Simon and Poynter
can laboratory expert stabilizer, and Anton Paar rheometer. The 1970; Ahmed et al. 1999). In this method, with the aid of suitable
experimental results showed that the formulated surfactant (BS- surfactants, the oil phase is dispersed in the water phase to form a
12 and OP-10) had an optimal mass ratio (1:2), and the water-sep- stable oil-in-water emulsion. The use of surfactants and water to
aration rates initially decreased sharply as the concentrations of form stable oil/water emulsions with crude oil is the subject of a
the surfactant increased, before decreasing moderately until series of patents (Titus 1973). The development of adequate tech-
reaching a minimum value. The formulated alkali solution exerted nologies aimed at handling very-viscous hydrocarbons through
a positive synergistic effect in tandem with the surfactant at low emulsification in water has been studied during the past 2 decades
alkali concentrations. In this way, an increasing number of petro- by a number of researchers. Zaki et al. (2001) discovered that a
leum soaps are produced by reactions between the alkali solutions nonionic surfactant had a positive contribution in forming low-
and the active components in heavy crude oil. However, the effect viscosity emulsions by measuring the viscosity and particle-size
was reversed at high alkali concentrations, where the compression distribution. Abdurahaman et al. (2012) revealed that the stability
of the alkali on the electric double layer was more significant. of oil-in-water emulsions stabilized by nonionic surfactant TX-
Images of the emulsions taken with a microscope showed that the 100 was improved as the surfactant concentrations increased.
sizes of the oil droplets were the smallest when the alkali concen- Kundu et al. (2013) researched the effect of anionic surfactant
tration was 0.2% and mass ratio of NaOH and TEA (triethanola- SDBS on the stability of oil/water macroemulsions by making
mine) was 1:1, which indicated that the amount of petroleum soap measurements of the conductivity, zeta-potential, and turbidity of
produced reached the maximum at this point. In addition, TEA, as the emulsions. They discovered that the anionic surfactant SDBS
a type of surface-active molecule, can form cross-multiple adsorp- exhibits polydispersity, which is the main contributor to the
tion and hydrogen-bonding structure with surfactant and petro- phase-inversion temperature.
leum soap at the water/oil interface. When the oil/water ratio was In conclusion, the previous researchers mainly concentrated on
7:3, the water-separation rate reached its lowest point 5.33% for 3 nonionic and anionic surfactants. An amphoteric surfactant is
hours. In addition, the emulsion stabilized by the surfactant and complex: It is positive in an acidic environment; however, it is
the compositional alkali possesses salt tolerance and temperature negative in an alkaline solution. Therefore, there has not been
resistance. When the concentration of the bivalent salt (CaCl2 and much published information on heavy-oil-in-water emulsions that
MgCl2) increased to 0.01molL1, the water-separation rate was are stabilized by amphoteric surfactants. Given this, we analyze
less than 20%, and when the temperature increased from 30 to dodecyl dimethyl betaine (BS-12) in this paper. BS-12 contains
60 C, the growth of back-scattering (BS) value was less than 2%. both amino, which has a positive charge, and ionized carboxyl,
which has a negative charge. The molecular structure is shown in
Introduction Fig. 1. Not only does BS-12 possess great interfacial activity, but
it is water-soluble, capable of emulsifying heavy crude oil, resist-
The International Energy Agency has reported that during the past ant to hard water, and has been widely used in, for example,
20 years, 80% of the world’s nonrenewable energy has come from chemical engineering, food industries, pharmaceuticals, machin-
fossil fuels. In addition, they note that crude oil will still be the ery, and detergents.
most important hydrocarbon resource during the next 5 decades. In addition, heavy crude oils may contain large numbers of
With the contradiction between an increase in global-energy con- asphaltenes, resins, naphthenic acids, and fatty acids. These can
sumption and a decline in conventional oil production, heavy
react with alkali to generate surface-active species known as in-
crude oils have been presented as a relevant hydrocarbon resource situ soap. However, it is difficult to form a stable emulsion with
for use in the future (Lanier 1998). However, the demand for an alkali alone. Therefore, the addition of a surfactant is needed.
heavy and extraheavy oil has been minimal because of their high Bryan and Kantzas (2007, 2008) and Bryan et al. (2008) reported
viscosity and complex composition, which make them difficult to that not only can the synergistic effect between alkalis and surfac-
produce, transport, and refine.
tants reduce the oil/water IFT, but it can also largely improve the
To be suitable for transportation from reservoir to refinery emulsification of oils. Ashrafizadeh et al. (2012) investigated the
with conventional pipelines, several nonconventional methods for effects of Na2CO3 concentrations on the stability, viscosity, and
the transport of heavy oils have been proposed. These include pre- zeta-potential of emulsions. They found that an excess of Naþ
heating the crude oil with subsequent pipeline heating (Saniere ions in the continuous phase could destabilize the emulsified
et al. 2004), dilution with lighter crude oils (Lona 1978), partial
structure caused by the precipitation of carboxylate ions as so-
dium carboxylate. Nedjhiouia et al. (2005) examined the influen-
Copyright V
C 2016 Society of Petroleum Engineers ces of two anionic surfactants and sodium hydroxide on the
Original SPE manuscript received for review 12 December 2015. Revised manuscript
conductivity and IFT of emulsions, and the results indicated that
received for review 1 April 2016. Paper (SPE 181742) peer approved 7 April 2016. the mixture of the different compounds had a synergistic action.

2016 SPE Journal 1

ID: jaganm Time: 21:26 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 2 Total Pages: 10

CH3 Preparation of Heavy-Oil/Water Emulsion. Heavy-oil-in-

water emulsion was prepared by stirring crude oil (mass concen-
tration 70%) and aqueous phase. All samples were stirred with a
C12H25 N+ CH2COO– digital motor blender (Kinematich Company, Switzerland) for 3
minutes at a rotating speed of 1,000 rev/min. The water used in
the experiments was double-distilled water.
CH3
Emulsion-Stability Determination. The emulsion stability was
Fig. 1—Molecular structure of BS-12. followed by test-bottle method. The volume of separated water
reflects the stability of emulsion—the larger the separated water
volume, the lower the stability.
Bai et al. (2014) investigated the IFT between Shengli crude oil After stirring, each sample was poured into a 50-cm3 grad-
and a novel organic alkali (OA). The results showed that the syn- uated tube and placed into a water bath, and the operating temper-
ergy of OA and the anionic surfactant was crucial for the emulsifi- ature was set at 30 C; then, the separated water volume was
cation of crude oil. measured every 30 minutes within 3 hours. Finally, each sample
In addition to the aforementioned studies, it is well-known that was left standing for 24 hours, and then the total volume of emul-
the oil/water ratio plays an important role in the stability of an sion was measured.
emulsion. Domian et al. (2015) found that the stability of emul-
sion was strengthened with increasing the oil/water ratio. At the Oil/Water Equilibrium IFT Measurement. The IFT between
same time, the oil-in-water emulsions may be stabilized by elec- heavy oil and aqueous solution was measured at 30 C with the
trostatic interactions and the adsorption of macromolecules at the spinning-drop IFT meter of Texas-500C (Temco, Loveland, Ohio,
oil/water interface. Therefore, the ionic strength of the continuous USA).
phase has a strong impact on the stability of the emulsion. Tang
et al. (2013) researched the effects of inorganic salts on the stabil-
ity of oil/water and discovered that the alkali can react with Mg2þ Oil-Droplets Dispersion Visualization. A polarizing micro-
and Ca2þ ions, which can lead to scale buildup in the injected sys- scope (XP-300C) by use of 25X objective with 960  1280 image
tem. Yang et al. (2013) interpreted that the salt screening was re- resolution was applied to visualize the dispersed oil droplets in
sponsible for the increased phase separation by phase-boundary water phase. Shapes and sizes of the oil droplets were recorded by
determination and zeta-potential and viscosity measurements. In a digital Sony camera.
addition, they observed that, as the temperature increased, the sta-
bility of the oil/water emulsion decreased. Farah et al. (2005) Conductivity of Surfactant/Alkaline Solutions. The conductiv-
reported that a rise in temperature can reduce the viscosity of the ities of surfactant/alkaline solutions were obtained by DDS-307A
emulsion and strengthen the Brownian movement of the oil drop- conductivity meter (Rex, Shanghai) with DJS-1 conductance sen-
lets at the same time. sor and T-818-B-6 temperature sensor, and the operating tempera-
By analyzing the present research conditions, the influences of ture was set to 30 C.
amphoteric surfactants/ organic/inorganic alkalis on the stability
of heavy-oil-in-water emulsions have not been reported. In addi- Zeta-Potential of Oil Droplets. The zeta-potential of oil droplets
tion, there are few reports discussing the effects of bivalent cati- was measured by a Zetasizer-Nano-ZS (Malvern Instruments UK)
ons and temperature on the stability of emulsions prepared by the at 30 C. A 15-mW helium neon laser was used as the incidental
compounded amphoteric/nonionic surfactants and inorganic/or- beam.
ganic alkalis. Therefore, it is necessary to research these problems
by monitoring the volume of separated water and conductivities
Viscosity Measurement. The Anton Paar viscometer model
of the aqueous solutions, comparing microscopic images of the
Rheolab QC was used for measuring the viscosities of emulsions,
emulsions and analyzing the dynamic stability of the emulsions.
and this device was armed with a waterbath thermostat. In experi-
ments, the shear rates were set from 50 to 300 s1, and the operat-
Materials and Methods ing temperature was kept at 30 C.
Materials. The heavy crude oil was obtained from Tahe oil field
in Xinjiang of China, with a water content of less than 0.1%. The Dynamic Stability of Emulsion Under Different Temperatures.
viscosity of heavy oil is 3921.34 mPas, and its density is equal to The dynamic stability of heavy-oil/water emulsions was moni-
973.5 kgm3, at 30 C. The physical and chemical properties of tored by measuring the transmittance (T) and BS of a pulsed near-
Tahe heavy crude oil are shown in Table 1. infrared light (k ¼ 880 nm) by Turbiscan laboratory expert made
Surfactants nonylphenol polyoxyethylene ether (OP-10), so- in Formulaction (France). The analysis of stability was carried out
dium dodecyl sulfate (SDS), and BS-12 were provided by Chengdu as a variation of BS and T profiles.
Kelon chemical factory in China. Their average molecular weights
are 646.86 gmol1, 288.38 gmol1, and 356.54 gmol1, respec-
tively, and OP-10 has 99.0 mass% active material, SDS has 94 Results and Discussion
mass% active material, and BS-12 has 32 mass% active material. The Effect of Surfactants on Oil/Water Separation. The
They are water-soluble surfactants. Effects of Nonionic, Anionic, and Ampholytic Surfactants on
Sodium hydroxide (NaOH) and sodium carbonate (Na2CO3) Oil/Water Separation. This study analyses how heavy oil-in-
were selected as inorganic alkalis. TEA was used as organic alkali water separation is affected by the nonionic surfactant OP-10, the
in this study, with an average molecular weight of 149.19 gmol1 anionic surfactant SDS, and the ampholytic surfactant BS-12. In
and a 99.0 mass% active content. The three alkaline substances this experiment, the mass concentration of surfactant was 1.5%.
were also provided by Chengdu Kelon chemical factory in China. The results of the experiments are shown in Fig. 2.

Total Acid Number

–1 –3
Resins (wt%) Asphaltenes (wt%) (mg KOH·g ) Sulfur Content (wt%) Water Content (wt%) Density (g·cm )

22.31 14.59 1.35 2.14 0.10 0.98

Table 1—Physical and chemical properties of Tahe heavy crude oil (30º C).

2 2016 SPE Journal

ID: jaganm Time: 21:26 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 3 Total Pages: 10

60 charge and an ionized carboxyl with a negative charge contained

in the same molecule, meaning that an electrostatic attraction

Water Separation Rate (vol%)

would appear between neighboring molecules. All these result in
the close arrangement of amphoteric surfactant molecules, which
40 OP-10 can increase the strength of the interfacial film.
BS-12 The Effect of a Formulated Surfactant on Oil/Water
SDS Separation. This study considers that the nonionic surfactant OP-
10 has a stronger ability to decrease oil/water IFT, as shown in
20 Table 2, and is not easily affected by acid or alkali solutions.
Therefore, in this research, BS-12 and OP-10 were blended, and
the effects of the mass ratios and concentrations of the formulated
surfactant on the stability of heavy oil-in-water emulsion are ana-
0
lyzed independently. The experimental results are shown in Figs.
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 3 and 4.
Time (hours) The mass concentration of the formulated surfactant in Fig. 3
was 1.5%. The water-separation rates increase with the surfactant
Fig. 2—Effects of nonionic/anionic and ampholytic surfactants mass ratio, and the water-separation rate reaches its minimum
on oil/water separation. value (11.3%) after 3 hours, when the mass ratio is 2:1. This phe-
nomenon may be explained in this way: When the mass ratio of
OP-10/BS-12 is above 2:1, large numbers of interfacial locations
The magnitude of the effects of these three surfactants on the are occupied by nonionic surfactants, which render the ampho-
stability of an oil/water emulsion is: BS-12>OP-10>SDS. As a teric surfactant distribution more scattered at the interface. Thus,
result of the amphoteric surfactant, the water-separation rate is the electrostatic attraction forces between adjacent molecules
only 7.4% after 3 hours. By use of OP-10, the water separation become weaker, causing the interfacial film structure to become
rate can reach 38.8% and 55.1% for SDS. looser. At the same time, because the negative-charge density of
The reasons for this phenomenon are: the hydrophilic groups the oil droplets is diluted by the nonionic surfactants, the electro-
of the anionic surfactants are negatively charged, meaning that static repulsion of oil droplets is weakened, which renders the oil-
the arrangement of adjacent surfactants molecules at the interface water emulsion unstable.
is loose because of the electrostatic repulsion. This can reduce the Fig. 4 shows the relationship between the surfactant concentra-
strength of the interfacial film between the heavy oil and aqueous tions and the water-separation rates for a formulated surfactant
phase (Dong et al. 2010). The adsorbed nonionic surfactant mole- with a mass ratio of 2:1 and mass concentrations of 0.5, 1.0, 1.5,
cules mainly provide a steric barrier to prevent the coalescence of 2.5, 3.0, and 3.5%. The water-separation rates decrease sharply
oil droplets (Abdurahaman et al. 2012). However, because the po- first as the surfactant concentrations increase and then decline
lar headgroup of the nonionic surfactant is relatively wide, there moderately until reaching a minimum value.
is a large gap between the adjacent molecules. In addition, the As the surfactant concentrations increase, more surfactant mol-
hydrogen bond between the water molecules and the hydrophilic ecules will adsorb at the interface, resulting in a close interfacial
groups of nonionic surfactants is comparatively weak, which pro- film and a minimized oil-droplet size. The smaller oil droplets can
motes the formation of a thin hydration layer. All these facts con- lead to an augmentation in the ratio between the surfactant-film
tribute to the effect that nonionic surfactants have on the stability thickness and the droplet radius (Tadros et al. 2004). A relatively
of emulsions being less prominent than those using amphoteric thicker interfacial film can provide a greater steric stabilization
surfactants. Amphoteric surfactants do not display apparent ani- against various instability processes, resulting in the emulsion
onic properties under neutral conditions. Therefore, the repulsive being more stable. With further increase to the surfactant concen-
force between the adjacent surfactant molecules is relatively trations, the surfactant molecules will aggregate to form micelles,
weak. In addition, there is a quaternary amine with a positive resulting in the decrease of the ratio of single surfactant molecules

Surfactant OP–10 BS–12 OP-10: BS-12(2:1)

–1
Equilibrium IFT (mN·m ) 0.167 0.445 0.214

Table 2—Equilibrium oil/water IFT in the presence of surfactants (1.5 m%, 30º C).

100
2:1
Water Separation Rate (vol%)

30
Water Separation Rate (vol%)

3:1
4:1
75
24

18 50

12
25

6
0
0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Time (hours) Surfactant Concentrations (%)

Fig. 3—Effect of formulated surfactant mass ratios on oil/water Fig. 4—Effect of the formulated surfactant mass concentrations
separation. on oil/water separation.

2016 SPE Journal 3

ID: jaganm Time: 21:26 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 4 Total Pages: 10

35 Na2 CO3
2Naþ þ CO3 2 . . . . . . . . . . . . . . . . . . . . ð2Þ
Na2CO3
Water Separation Rate (vol%) 28 TEOA CO3 2 þ H2 O
HCO3  þ OH . . . . . . . . . . . . . . . ð3Þ
NaOH þ
R  NH2 þ H2 O
OH þ R  NH3 : . . . . . . . . . . . . ð4Þ
21
As shown in Eqs. 1 through 4, the three alkalis exhibit different
14 ionization characteristics, and the content of ionized hydroxyl
ions in solutions for the same alkali concentration is
NaOH>Na2CO3>TEA. The most interfacial active substances
7
are produced by reactions between the NaOH solution and organic
acids in crude oil. At low alkali concentrations, the weak base can
0 only react with small molecular acids in crude oil. However,
0.1 0.2 0.3 0.4 0.5 strong alkalis can react with long-chain molecules and esters to
Alkali Concentration (%) generate interfacial active substances, which can form a strong
interface film. As a result, when the alkali mass concentration is
Fig. 5—Effects of inorganic/organic alkali mass concentrations less than 0.2%, NaOH has the strongest influence on the stability
on oil/water separation. of the emulsions, and TEA has the weakest.
When the mass concentrations of the alkalis increase, the al-
to the bulk solution, which is not favorable for surfactant adsorp- kali acts as an electrolyte solvent. On one hand, the compression
tion onto the interface. The surfactant micelles can only slightly of the alkali on the electric double layer is strong, but the alkali
increase the viscosity of the aqueous phase, meaning that the renders a more-pronounced hydrophobic effect on the surfactant,
water separation decreases gradually. improving the solubility of the interfacial active substances in the
oil phase. Therefore, the water-separation rates increase as the al-
kali concentration increases. When the concentration exceeds
The Effect of Alkali on Oil/Water Separation. The Effects 0.3%, TEA has the most-prominent impact on the emulsion stabil-
of Inorganic/Organic Alkali on Heavy-Oil-in-Water-Emulsion ity than any of the other alkalis studied here, whereas NaOH has
Separation. Heavy oil contains some active ingredients with po- the least. This phenomenon occurs because TEA and Na2CO3 are
lar functional groups, such as resins, asphaltenes, naphthenics, both weak alkaline substances, and their positive hydrolytic reac-
and fatty acids. The effect of alkalis on the emulsion stability is tions can be promoted by an increase in the alkali concentrations,
usually attributed to the ionization of these interfacial active com- meaning that more active substances will appear on the oil/water
ponents, which induces strong electrostatic repulsive forces to interface. In addition, TEA is a type of surface-active species that
overcome the cohesion of the interfacial film. These ionized com- can form a mosaic adsorption together with the surfactant and pe-
ponents are described as in-situ soap. These active substances not troleum soap molecules to improve the stability of the emulsion
only reduce the IFT sharply but also have a synergistic effect with (Bai et al. 2014).
the surfactants. Therefore, the impacts of inorganic alkali (NaOH/ Conductivity of the Surfactant/Alkali System. The ampho-
Na2CO3) and organic alkali (TEA) on the stability of heavy-oil- teric surfactant BS-12 contains both amino with a positive charge
in-water emulsions are being researched, respectively. and ionized carboxyl with a negative charge and is readily
The correlation between alkali solutions and water-separation affected by alkali. This study presents an analysis of how the al-
rates is illustrated in Fig. 5 for the combination surfactant mass kali types and mass concentrations change the conductivity of the
concentration of 1.5% and alkali mass concentrations of 0.1, 0.15, pure alkali solution and the AS (alkali and surfactant) system. The
0.2, 0.3, 0.4, and 0.5%. experimental results are shown in Fig. 6.
Fig. 5 shows that when the mass concentration of the alkali is Fig. 6 reflects the varying tendencies of the conductivities of
less than 0.2%, the magnitude of the effects from the three alkalis the three pure alkali solutions and the AS systems (composed of
examined on the water separation is TEA>Na2CO3>NaOH. BS-12 and inorganic/organic alkali). (1) Both the pure alkali solu-
When the alkali concentration is greater than 0.3%, the magnitude tions and the AS systems exhibit an increasing conductivity when
is NaOH>Na2CO3>TEA. the alkali mass concentrations increase. (2) The conductive mag-
For above-mentioned results, this is because the order of the nitude of the different bases is NaOH > Na2CO3>TEA. (3) The
pH values of these three alkalis is NaOH>Na2CO3>TEA. The conductivity of the NaOH and surfactant system is less than that
hydrolysis reactions in aqueous solution for these are shown in of the pure NaOH solution (Fig. 6a). In addition, the conductivity
Formulas (1), 2), (3), and (4) (Mercado et al. 2014): of the Na2CO3 and surfactant system is slightly larger than that of
the pure Na2CO3 solution, and these two trend lines are nearly
NaOH ! OH þ Naþ . . . . . . . . . . . . . . . . . . . . . . . ð1Þ parallel (Fig. 6b). However, the conductivity of the TEA and

30 9 1.6
Conductivity (ms·cm–1)

Conductivity (ms·cm )

Conductivity (ms·cm )
–1

–1

TEOA solution
25 NaOH solution Na2CO3 AS system
AS system 1.2
AS system
20 6

15 0.8

10 3
0.4
5

0 0 0.0
0.1 0.2 0.3 0.4 0.5 0.1 0.2 0.3 0.4 0.5 0.1 0.2 0.3 0.4 0.5

Alkali Concentration (%) Alkali Concentration (%) Alkali Concentration (%)

(a) (b) (c)

Fig. 6—Effect of alkali mass concentrations on the conductivity of the alkali solution/AS system NaOH solution and the system of
NaOH and BS-12, (b) Na2CO3 solution and the system of Na2CO3 and BS-12, and (c) TEA solution and the system of TEA and BS-12.

4 2016 SPE Journal

ID: jaganm Time: 21:26 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 5 Total Pages: 10

24 0

Water Separation Rate (vol%)

–2
18

ζ-Potential (mV)
–4

12
–6

–8
6

0.0 0.1 0.2 0.3 0.4 0.5 –10

0.0 0.1 0.2 0.3 0.4 0.5
Alkali Concentration (%)
Alkali Concentration (%)
Fig. 7—Effects of compositional alkali mass concentrations on
oil/water separation. Fig. 8—Effects of compositional alkali concentrations on the
zeta-potential of oil droplets.

surfactant system is considerably greater than that of the pure

TEA solution (Fig. 6c). interactions between the inorganic solution and organic acids in
The alkalinity of the NaOH aqueous solution is the strongest, the crude oil. However, inorganic alkalis can denude the strata,
meaning that the number of hydroxyl ions in the NaOH solution corrode pipelines and equipment, and produce precipitates with
is greatest. All these factors can significantly advance the ioniza- multivalent cations, whereas organic alkalis perform equally well
tion of the carboxyl of BS-12, meaning that a large amount of in both soft and hard brines and have a strong salt tolerance, espe-
hydroxyl ions will be consumed, However, the quantities of ani- cially for calcium and magnesium ions (Tang et al. 2013).
onic charge are far less than the consumed hydroxyl ions in the For these reasons, an inorganic alkali was combined with the
NaOH solution; hence, the AS system is less conductive than the organic alkali in this paper. Because NaOH can stabilize an emul-
pure NaOH solution. sion more effectively than Na2CO3, NaOH was used as the inor-
Na2CO3 is a weak base, and its carbonate ionization is acceler- ganic base during this study. The effects of the compositional
ated by acid/base reactions between BS-12 and Na2CO3, which alkali concentrations and mass ratios on the stability of the emul-
accounts for the compensation of consumed hydroxyl ions by new sions were both examined with the experimental results shown in
ones. There are lone pair electrons carried by the amino nitrogen Figs. 7 through 9.
atom that are contained in the TEA molecules, and the TEA mole- Fig. 7 shows the relationship between the compositional alkali
cules have the ability to accept protons. However, the electronic concentrations and the water-separation rates for a combinational
effect and the solvent effect reaction is insignificant (Bai et al. alkali mass ratio of 1:1 and for alkali mass concentrations in the
2014), which makes the solution take on a slight alkalinity. range of 0 to 0.5%. When the alkali concentration is zero, the
When TEA and BS-12 are mixed together, the electronic effect water-separation rate is 11.3%. As combinational alkali is added,
and the solvent reaction of the TEA molecules are promoted by the water-separation rate decreases until it reaches its lowest point
acid-base neutralization between the hydrogen ions in the car- (5.33%) before increasing as the alkali concentration increases.
boxyl and the hydroxyl ions in the solution. In addition, the ani- An interpretation for this phenomenon is that when the alkali
onic charge density of the BS-12 increases as TEA molecules are concentrations are less than 0.2%, the electronic-effect and the
gradually added. Therefore, the strength of the negative electric solvent-effect reactions of the compositional alkali become stron-
properties of the BS-12 is much larger than that of TEA. ger with increasing alkali concentrations, which lead to the pro-
All these factors illustrate how disparate alkali concentrations duction of more hydroxyl ions. As a result, an increasing amount
result in differences in the stability of emulsions. of petroleum soap is produced, which increases the absolute value
The Effects of Compositional Alkalis on Oil/Water of the zeta potential on the oil-droplet surface (as shown in Fig. 8)
Separation. This study considers that the content of ionized and restricts the collisions of oil droplets.
hydroxyl ions in an inorganic solution is higher than in an organic In addition, TEA is a type of surface-active small molecule
solution for the same mass concentration. Therefore, more interfa- that has lone pair electrons carried by an amino-acid nitrogen
cial active substances with negative charges can be produced by atom. Therefore, it can form a cross-multiple adsorption and
hydrogen-bonding structure with the surfactant and petroleum
soap at the water/oil interface, leading the film of the oil droplet
to become thicker and more rigid.
30
Finally, the hydroxyl ions in solution can promote the ioniza-
Water Separation Rate (vol%)

1:1 tion of the carboxyl in BS-12, which results in the increase of the
3:1 absolute zeta-potential of the oil droplets (as shown in Fig. 8).
1:3 When the mass concentration exceeds 0.2%, the role of the com-
20 positional alkali as the electrolyte is more significant, which
reduces the absolute zeta-potential of the oil droplets (as shown in
Fig. 8). This effect should be attributed to the precipitation of
some of the carboxylate ions that are adsorbed on the surface of
10 the oil droplets (Ashrafizadeh et al. 2012). However, increasing
amounts of interfacial spaces are occupied by the TEA molecules,
decreasing the electrostatic attraction forces between the adjacent
interfacial molecules.
0 The effects of the combination alkali mass ratios on the water-
0.5 1.0 1.5 2.0 2.5 3.0 separation rates were studied when the alkali mass concentration
Time (hours) is 0.2%, as shown in Fig. 9. The water-separation rate reaches its
minimum value (5.33%) after 3 hours when the mass ratio of 1:1.
Fig. 9—Effects of compositional alkali mass ratios on oil/water Whenever the mass ratio deviates from 1:1, the water-separation
separation. rates increase. This phenomenon demonstrates that the emulsion

2016 SPE Journal 5

ID: jaganm Time: 21:26 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 6 Total Pages: 10

(a) (b) (c) (d)

(e) (f) (g) (h)

Fig. 10—Microscopic images of the emulsions at different compositional alkali concentrations.

is most stable at a mass ratio of 1:1. When the mass ratio is lower, an increasing amounts of organic alkali molecules act as surfac-
there are not enough ionized hydroxyl ions to react with all the tants and adsorb on the interface of the oil droplets. With the
acids in the heavy crude oil. When the mass ratio is higher, there increase in the “surfactant” concentrations, the interfacial area
are fewer TEA molecules adsorbed at the interface, which will between the dispersed (oil) phase and continuous (water) phase
weaken the synergistic effect between the TEA molecules and increases, producing a larger number of small-sized oil droplets
the surfactants. (Kundu et al. 2013), making them difficult to approach and coa-
lesce to each other. However, when the alkali mass concentration
exceeds 0.2%, the sizes of oil droplets increase. This is caused by
The Effects of the Compositional Alkali on the Size of Oil the compositional alkali molecules that act as an “electrolyte” and
Droplets. To further research the effects of the compositional al- reduce the negative electrical-charge density and increase the
kali concentrations on the size of the oil droplets, microscopic “hydrophobic effect” of the surfactant, resulting in a decrease of
images of the emulsions with alkali mass concentrations from 0 to the emulsion stability.
0.5% were performed and shown in Fig. 10.
The alkali mass concentrations in Samples (a) through (h) are:
0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, and 0.5%, respectively. The Effects of Oil/Water Ratios on the Emulsion Stability. It
As seen in Fig. 10, when the mass concentration of the alkali is well-known that the greater the oil/water ratios, the higher the
composition is less than 0.2%, the sizes of oil droplets decrease as pipeline-transporting efficiency. However, when the oil/water ra-
the alkali concentrations increase. And when the alkali mass con- tio is too high, the emulsion may be unstable. To research the
centration exceeds 0.2%, the sizes of oil droplets become larger effects of oil-water ratios on the stability of emulsions, the oil/
with increasing the alkali concentrations. water ratio was increased from 5:5 to 9:1. However, when the oil/
These aforementioned results should be explained that, as the water ratio was equal to 9:1, a phase inversion from oil/water
concentrations of the alkali increase, the negative charged surfac- emulsion to water/oil emulsion could be obtained, and the rest of
tants increase from the reactions between the hydroxyl ions in the experimental results were shown in Fig. 11.
alkali solution and acidic components in the crude oil. In addition, As seen in Fig. 11, the water-separation rates decrease initially
as the oil-water ratios enlarge and then increase. And when the
oil-water ratio is 7:3, the water-separation rate reaches its lowest
70 point (5.33%) after 3 hours.
5:5
Water Separation Rate (vol%)

6:4 These reasons for aforementioned results may be demonstrated

56 7:3 that as the ratios of oil/water increase, the interfacial area between
8:2 the oil phase and water phase increases, producing a larger num-
ber of small-sized oil droplets (Kundu et al. 2013). At the same
42 time, decreasing the size of the oil droplets results in the thinning
of the liquid films between the oil droplets, which leads to an
28 increase in the viscosity of emulsions (as shown in Fig. 12), and
then makes droplets difficult to approach and coalesce to each
other. However, with further increasing the oil/water ratios, there
14
will be fewer surfactant molecules adsorbed at the new interface,
causing the interfacial film structure to become looser. Therefore,
0 the coalescence of small oil droplets gets promoted, which renders
0.0 0.5 1.0 1.5 2.0 2.5 3.0 a decrease in viscosity (as shown in Fig. 12) and an increase in
Time (hours) water-separation rate of the emulsions.
As shown in Figs. 11 and 12, the water-separation rate is
Fig. 11—Effects of oil/water ratios on oil/water separation. higher at the oil/water ratio of 8:2, but the difference in the

6 2016 SPE Journal

ID: jaganm Time: 21:26 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 7 Total Pages: 10

200 rates and the MgCl2 or CaCl2 molar concentrations is similar, and
5:5 the stability of the emulsion is improved through the addition of
6:4 organic alkali. (4) For the emulsions stabilized by the com-
160 7:3 pounded alkali/surfactant, the effect that the Mg2þ ions has on the

Viscosity (mPa·s)
8:2
water-separation rates is greater than that of the Ca2þ ions.
120 The reasons for the former two results are demonstrated as fol-
lows. (1) Mg2þ and Ca2þ ions can strongly compress the diffused
80 electric double layer and lower the negative-electrical charge den-
sity, resulting in a high-collision efficiency for the oil droplets
in water. (2) The Mg2þ and Ca2þ ions can form complexes
40 within petroleum soap adsorbed at the oil/water interface. (3) Large
amounts of OH ions in solution can be consumed by the
0 Mg2þ and Ca2þ ions, leading to the production of less petroleum
50 100 150 200 250 300 soap to stabilize the interfacial film. (4) Mg(OH)2 is insoluble in
Shear Rate (s–1) an aqueous solution, but Ca(OH)2 is slightly soluble. The loga-
rithm of the solubility product of Mg(OH)2 or Ca(OH)2 is shown
Fig. 12—Dependence of heavy-oil-in-water emulsion viscosities in Eq. 5 (Harris 1991):
on oil/water ratios.
Pksp ¼ log10 ðkspÞ: . . . . . . . . . . . . . . . . . . . . . . . . . ð5Þ
viscosity is not obvious between the oil/water ratio of 7:3 and 8:2.
Therefore, the classic oil/water ratio of 7:3 was selected. The Pksp values of Mg(OH)2 and Ca(OH)2 are 10.74 and 5.26,
respectively (Harris 1991). The larger the Pksp value, the smaller
the solubility of the precipitate. Therefore, there are fewer free
The Effects of Bivalent Salts on the Emulsion Stability. Under
hydroxyl ions in the MgCl2 solution than in the CaCl2 solution. In
the same molar concentrations, the pH values of the NaOH solu-
addition, considering the hydrated ionic radius of Mg2þ and Ca2þ
tions are higher than those of the TEA solutions. Therefore, more
[i.e., 0.428 and 0.412 nm (Kiriukhim and Collins 2002)], the
interfacial active substances known as petroleum soap can be pro-
smaller the radius of hydration, the more easily electrons travel
duced by the acid/base reactions in the emulsions. However,
into the electric double layer, making the aggregation of oil drop-
NaOH may cause strata denudation and corrosion of pipelines/
lets easier (Feng et al. 2012). These two effects are in competi-
equipment, and organic alkalis can relieve these problems.
tion, and the influence of the Mg2þ ions on the water-separation
Another important aspect is that organic alkalis have a strong salt
rates is greater than that of the Ca2þ ions at low molar concentra-
tolerance (Zhao et al. 2013). Assuming that the produced water
tions. However, this result is reversed at high concentrations.
contains Mg2þ and Ca2þ ions, the compatibility of the different
The reasons for the latter two results may be because the TEA
alkalis containing MgCl2 and CaCl2 solutions is shown in Fig. 13.
molecule has lone pair electrons carried by the amino-nitrogen
Fig. 13c shows that the organic alkali TEA possesses great
atoms. TEA molecules have the ability to provide electron pairs
compatibility with MgCl2 and CaCl2 solutions. Therefore, the or-
to form a coordinate bond with the Mg2þ and Ca2þ ions, which
ganic alkali was compounded with the inorganic alkali in this
can both decrease the consumption of the hydroxyl ions in the so-
study. To compare the hard-water resistance of the compounded
lution and lower the compression between the Mg2þ/Ca2þ ions
alkali with that of NaOH, the mass concentrations of NaOH and
and the diffused-electrical double layer. Furthermore, the stability
the alkali combinations were held constant at 0.2%, and the mass
constant of the complex is proportional to the square of the charge
concentrations of the surfactant were kept at 1.5%. The effects of
and is inversely proportional to the ionic radius (Allred 1961).
the MgCl2 and CaCl2 molar concentrations on the stability of vari-
Therefore, the produced complex from the reaction between
ous emulsions were studied, and the experimental results are
MgCl2 and TEA is more-stable, resulting in a higher water-sepa-
shown in Fig. 14.
ration rate.
Four experimental results are observed. (1) Regardless of
whether the emulsions stabilized by the NaOH or compounded al-
kali, the water-separation rates increase with the increase of both Dynamic Stability of Emulsion Under Different Temperatures.
the MgCl2 and CaCl2 molar concentrations. (2) For the emulsions Turbiscan lab equipment was used to analyze the dynamic stabil-
stabilized with NaOH, the effect of the Mg2þ ions on the water- ity of the emulsion under different temperatures by means of
separation rate is greater than that of Ca2þ ions at low molar con- transmission and BS detectors. Because the positive or negative
centrations, but less than at high molar concentrations. (3) For the variations in the transmission and BS profiles are not correlated
compounded alkali, the relationship between the water-separation with destabilization processes for sample heights of 2 mm and

(a) (b) (c)

Fig. 13—Compatibility studies of the different alkalis containing MgCl2 and CaCl2 solutions: (a) NaOH 1 CaCl2, (b) NaOH 1 MgCl2,
and (c) TEA 1 MgCl2/CaCl2.

2016 SPE Journal 7

ID: jaganm Time: 21:27 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 8 Total Pages: 10

40 ples are 6.0, 9.5, and 11.5 mm at 30, 50, and 60 C, respectively,
NaOH+CaCl2 and that the distances between the profile curves become larger as
Water Separation Rate (vol%) NaOH+TEOA+CaCl2 the temperature increases.
30 The aforementioned results can demonstrate that the BS is pro-
NaOH+MgCl2
portional to ð/=dÞ1=2 on the basis of the principle of the Turbiscan
NaOH+TEOA+MgCl2 laboratory, where / is the volume fraction of the dispersed phase
20 and d is the average size of the oil droplets (Kang et al. 2012). In
the bottom of the emulsion samples, as time passes, an increasing
number of large droplets migrate to the upper layer. At the same
10 time, there is a reduction in the average droplet size and a
decrease in the dispersed phase concentrations. The competition
of these two effects leads to an increase in the BS. Higher temper-
atures make the flocculation and coalescence of oil droplets faster
0
0.000 0.002 0.004 0.006 0.008 0.010 and easier, which results in smaller sizes of oil droplets left, larger
BS, and a higher unstable range. After a period of time, a reduc-
Molar Concentration (mol·L–1)
tion in BS is observed at 50 and 60 C, which is attributed to the
reduction in the concentrations of small droplets or a little oil
Fig. 14—Effect of the molar concentrations of MgCl2 and CaCl2
on the stability of the emulsions. remaining in the water phase (Nguyen and Balsamo 2013). The
average size of the oil droplets changes a little. This is mainly
caused by the rigid film at the oil/water interface and because the
more than 42 mm, both values are determined in enclosed air in dispersed droplets do not completely flocculate or coalescence. In
the bottom and on the top of a cylindrical glass tube, respectively the middle and top emulsion samples, the BS decreases with time
(Kang et al. 2011). In this study, the height range of the samples because of more and more oil droplets coalescing into bigger
was set at 2 to 39 mm, the formulated surfactant mass concentra- droplets, leading to a decrease in BS.
tion was 1.5%, and the alkali-combination mass concentration On the basis of these results, the BS values are relatively low.
was 0.2%. An image was taken of the glass cell after 3 hours of This shows that the emulsions stabilized with a formulated surfac-
measuring. Because the transmission values are nearly zero over tant containing BS-12 and OP-10 and a composition alkali con-
this range, the analyses for all the samples were carried out with taining NaOH and TEA have a temperature resistance.
BS profiles, as shown in Fig. 15.
As seen in Fig. 15, when the bottom of the emulsion sample
heights ranges from 2 to 12 mm, the relationship between the BS Conclusions
and time is positive at 30 C, and the BS increases with time ini- • The effect of BS-12 on the stability of heavy-oil-in-water emul-
tially and then decreases at 50 or 60 C. However, in the middle sions is greater than that of OP-10. However, OP-10 can obtain
and top of the emulsion samples, the BS changes a little at 30 C, a lower equilibrium IFT between the heavy crude oil and water.
and the BS decreases with time at higher temperatures. It is also The formulated surfactant of BS-12 and OP-10 has an optimal
seen that the unstable heights at the bottom of the emulsion sam- mass ratio of 1:1, and the water-separation rate decreases

0:00:00 0:00:00
0:00:15 0:00:15
0:00:25 7% 0:00:25
5% 0:00:40 0:00:40
0:00:50 6% 0:00:50
0:01:05 0:01:05
4% 0:01:15 5% 0:01:15
0:01:25 0:01:25
0:01:40 4% 0:01:40
3% 0:01:50 0:01:50
0:02:05 0:02:05
3%
0:02:15 0:02:15
2% 0:02:30
2% 0:02:30
0:02:40 0:02:40
0:02:50 0:02:50
1% 0:03:00 1%
0 mm 20 mm 40 mm 0:03:00
0 mm 20 mm 40 mm
a (30°C) b (50°C)

6:07:37
6:07:52
7% 6:08:02
6:08:17
6% 6:08:27
6:08:37
5% 6:08:52
6:09:02
4% 6:09:17
6:09:27
6:09:37
3% 6:09:52
6:10:02
2% 6:10:12
6:10:27
1% 6:10:37
0 mm 20 mm 40 mm
c (60°C)

Fig. 15—Backscattering variation for heavy-oil/water emulsions at different temperatures.

8 2016 SPE Journal

ID: jaganm Time: 21:27 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 9 Total Pages: 10

sharply with the increase in surfactant concentrations, before Bryan, J., Mai, A., and Kantzas, A. 2008. Investigation Into the Processes
moderately decreasing to minimum value. Responsible for Heavy Oil Recovery by Alkali-Surfactant Flooding.
• The water-separation rate decreases until it reaches the lowest Presented at the SPE Symposium on Improved Oil Recovery, Tulsa,
point and then increases with the alkali concentration. When 20–23 April. SPE-113993-MS. http://dx.doi.org/10.2118/113993-MS.
the mass concentration of the alkali is less than 0.2%, the mag- Bryan, J. and Kantzas, A. 2008. Potential for Alkali-Surfactant Flooding
nitude of the effects of these three alkalis on the stability of the in Heavy Oil Reservoirs Through Oil-in-Water Emulsification. J Can
emulsions is NaOH>Na2CO3>TEA. When the alkali mass con- Pet Technol 48 (2): 37–46. PETSOC-09-02-37. http://dx.doi.org/
centration is more than 0.3%, the magnitudes is as follows: 10.2118/09-02-37.
TEA > Na2CO3 > NaOH. Domian, E., Brynda-Kopytowska, A., and Oleksza, K. 2015. Rheological
• When the formulated alkali of NaOH and TEA mass concentra- Properties and Physical Stability of O/W Emulsions Stabilized by
tion is 0.2% and mass ratio is 1:1, the oil/water emulsion is the OSA Starch With Trehalose. Food Hydrocolloids 44: 49–58. http://
most stable because the quantity of produced petroleum soap dx.doi.org/10.1016/j.foodhyd.2014.08.020.
adsorbed at the interface is the maximized. In addition, TEA Dong, Z., Lin, M., Wang, H. et al. 2010. Influence of Surfactants Used in
molecules, as surface-active substances, exert a synergistic Surfactant-Polymer Flooding on the Stability of Gudong Crude Oil
effect in tandem with the surfactants and petroleum soap at the Emulsion. Petrol. Sci. 7 (2): 263–267. http://dx.doi.org/10.1007/
water/oil interface. s12182-010-0031-y.
• The sizes of the oil droplets become smaller with the increase Farah, M. A., Oliveira, R. C., Caldas, J. N. et al. 2005. Viscosity of
of the alkali concentrations until the mass concentration reaches Water–in–Oil Emulsions: Variation With Temperature and Water Vol-
0.2%, and then the sizes become larger with further increase of ume Fraction. J. Petrol. Sci. Eng. 48: 169–184. http://dx.doi.org/
the alkali concentrations. 10.1016/j.petrol.2005.05.014.
• As the ratios of oil/water increase, the water-separation rates Feng, J. G., Zhang, X. J., Fan, T. F. et al. 2012. Effects of pH Value,
decrease initially and then increase. Emulsification Temperature and Electrolytical Ions on the Stability of
• Regardless of the pure alkali solution or the AS system, their Metolachlor Emulsion in Water. Chem. J. of Chinese Universities 33
conductivities increase when the alkali mass concentrations (11): 2521–2525. http://dx.doi.org/10.7503/cjcu20120156.
increase. The conductivity of the NaOH and BS-12 system is Harris, D. C. 1991. Quantitative Chemical Analysis, third edition,
less than that of the pure NaOH solution. The conductivity of 123–125. New York: W. H. Freeman and Company.
the Na2CO3 and BS-12 system is slightly larger than that of the
Kang, W., Xu, B., Wang, Y. et al. 2011. Stability Mechanism of W/O
pure Na2CO3 solution. Finally, the conductivity of the TEA and
Crude Oil Emulsion Stabilized by Polymer and Surfactant. Colloids
BS-12 system is considerably more pronounced than that of the
Surf. A: Physicochemical. Eng. Aspects 384 (1–3): 555–560. http://
pure TEA solution.
dx.doi.org/10.1016/j.colsurfa.2011.05.017.
• Whether the emulsion is stabilized by NaOH or the com-
pounded alkali, the water-separation rates increase as the molar Kang, W., Guo, L., Fan, H. et al. 2012. Flocculation, Coalescence and
concentrations of MgCl2 and CaCl2 increase, and the stability is Migration of Dispersed Phase Droplets and Oil–Water Separation in
improved by adding the organic alkali TEA. Heavy Oil Emulsion. J. Petrol. Sci. Eng. 81: 177–181. http://
• An increase in temperature is helpful for oil/water separation in dx.doi.org/10.1016/j.petrol.2011.12.011.
emulsions. However, the emulsions stabilized by the formulated Kiriukhim, M. Y. and Collins, K. D. 2002. Dynamic Hydration Numbers
surfactants and compositional alkalis exhibit a temperature for Biologically Important Ions. Biophys. Chem. 99 (2): 155–168.
resistance. http://dx.doi.org/10.1016/S0301-4622(02)00153-9.
Kundu, P., Agrawal, A., Mateen, H. et al. 2013. Stability of Oil-in-Water
Macro-Emulsion With Anionic Surfactant: Effect of Electrolytes and
Acknowledgment Temperature. J. Chem. Eng. Sci. 102: 176–185. http://dx.doi.org/
This work was supported by the Natural Science Foundation of 10.1016/j.ces.2013.07.050.
China (Grant No. 51074136) and the Research Fund for the Doc- Lanier, D. 1998. Heavy Oil—A Major Energy Source for the 21st Century.
toral Program of Higher Education of China (Grant No. Proc., the 7th Unitar International Conference on Heavy Crude & Tar
20115121110004) and the Graduate Student Innovation Fund and Sands, Beijing, 27–30 October. No. 039,361.
the “change cup” breeding project, Southwest University Lona, M. 1978. Process for Producing Low-Density Low Sulfur Crude
(CXJJ2015030). The researchers who contributed to this paper are Oil. US Patent No. 4,092,238.
acknowledged greatly for participating in parts of this study.
MacWilliams, M. A. and Eadie, W. 1993. Process and Apparatus for Par-
tial Upgrading. Canadian Patent No. 1,313,639.
References Mercado, R. A., Salager, J. L., Sadtler, V. et al. 2014. Breaking of a Cati-
onic Amine Oil-in-Water Emulsion by pH Increasing: Rheological
Abdurahaman, N. H., Rosli, Y. M., Azhari, N. H. et al. 2012. Pipeline
Monitoring To Modelize Asphalt Emulsion Rupture. Colloids Surf. A:
Transportation of Viscous Crudes as Concentrated Oil-in-Water Emul-
Physicochem. Eng. Aspects 458: 63–68. http://dx.doi.org/10.1016/
sions. J. Petrol. Sci. Eng. 90–91: 139–144. http://dx.doi.org/10.1016/
j.colsurfa/2014.03.109.
j.petrol.2012.04.025.
Nedjhiouia, M., Moulai-Mostefa, N., Morsli, A. et al. 2005. Combined
Ahmed, N. S., Nassar, A. M., Zaki, N. N. et al. 1999. Formation of Fluid
Effects of Polymer/Surfactant/Oil/Alkali on Physical Chemical Prop-
Heavy Oil-in-Water Emulsions for Pipeline Transportation. Fuel 78
erties. Desalination 185 (1–3): 543–550. http://dx.doi.org/10.1016/
(5): 593–600. http://dx.doi.org/10.1016/S0016-2361(98)00157-4.
j.desal.2005.05.013.
Allred, A. L. 1961. Electronegativity Values From Thermochemical Data.
J. Inorg. Nucl. Chem. 17 (3–4): 215–221. http://dx.doi.org/10.1016/ Nguyen, D. and Balsamo, V. 2013. Emulsification of Heavy Oil in Aque-
0022-1902(61)80142-5. ous Solutions of Poly(vinyl alcohol): A Method for Reducing Appa-
Ashrafizadeh, S. N., Motaee, E., and Hoshyargar, V. 2012. Emulsification rent Viscosity of Production Fluids. Energy & Fuels 27 (4):
of Heavy Crude Oil in Water by Natural Surfactants. J. Petrol. Sci. 1736–1747. http://dx.doi.org/10.1021/ef3014986.
Eng. 86–87: 137–143. http://dx.doi.org/10.1016/j.petrol.2012.03.026. Saniere, A., Henaut, I., and Argillier, J. F. 2004. Pipeline Transportation
Bai, Y. R., Shang, X. S., Zhao, X. T. et al. 2014. Effects of a Novel Or- of Heavy Oils, a Strategic, Economic and Technological Challenge.
ganic Alkali on the Interfacial Tension and Emulsification Behaviors Oil & Gas Science and Technol-Rev. IFP 59 (5): 455–466. http://
Between Crude Oil and Water. J. Dispers. Sci. Technol. 35: dx.doi.org/10.2516/ogst:2004031.
1126–1134. http://dx.doi.org/10.1080/01932691.2013.833483. Simon, R. and Poynter, W. G. 1970. Pipelining Oil/Water Mixtures. US
Bryan, J. and Kantzas, A. 2007. Enhanced Heavy-Oil Recovery by Alkali- Patent No. 3,519,006.
Surfactant Flooding. Presented at the SPE Annual Technical Confer- Tadros, T., Izquierdo, P., Esquena, J. et al. 2004. Formation and Stability
ence and Exhibition, Anaheim, California, 11–14 November. SPE- of Nano-Emulsions. J. Advances in Colloid and Interface Sci.
110738-MS. http://dx.doi.org/10.2118/110738-MS. 108–109: 303–318. http://dx.doi.org/10.1016/j.cis.2003.10.023.

2016 SPE Journal 9

ID: jaganm Time: 21:28 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069

 J181742 DOI: 10.2118/181742-PA Date: 8-June-16 Stage: Page: 10 Total Pages: 10

Tang, M. G., Zhang, G. C., Ge, J. J. et al. 2013. Investigation Into the tion. He has authored more than 110 academic papers and
Mechanisms of Heavy Oil Recovery by Novel Alkali Flooding. Col- holds five patents. Jing earned a PhD degree in oil-and-gas
loids Surf. A: Physicochem. Eng. Aspects 421: 91–100. http:// engineering from SWPU.
dx.doi.org/10.1016/j.colsurfa.2012.12.055. Huayi Jiang is an associate professor in Xi’an Shiyou University.
Titus, P. E. 1973. Pipeline Transportation of Waxy Products. US Patent He has been with the university for more than 20 years. Jiang’s
No. 3,776,248. research interests are microwaves and rheology of crude oil.
Yang, Q. Q., Ke, D., Yang, M. L. et al. 2013. Effect of Salt Concentration He has published more than 15 academic papers and holds
on the Phase Separation of Bitumen Emulsions. Colloids Surf. A: two patents. Jiang earned a PhD degree in oil-and-gas engi-
Physicochem. Eng. Aspects 425: 1–5. http://dx.doi.org/10.1016/ neering from SWPU in 2002.
j.colsurfa.2013.02.041. Yunpeng An is an assistant engineer in China Petroleum Pipe-
Zaki, N., Butz, T., and Kessel, D. 2001. Rheology Particle Size Distribu- line Engineering Corporation. He is engaged in engineering
tion, and Asphaltere Deposition of Viscous Asphaltic Crude Oil-in- design of long distance oil-and-gas pipelines. He has authored
Water Emulsions for Pipeline Transportation. J. Pet. Sci. Technol. 19 or coauthored eight academic papers. He holds an MS
(3–4): 425–435. http://dx.doi.org/10.1081/LFT-100000774. degree in oil-and-gas storage and transportation engineering
Zhao, X., Bai, Y., Wang, Z. et al. 2013. Low Interfacial Tension Behavior from SWPU.
Between Organic Alkali/Surfactant/Polymer System and Crude Oil. J. Cheng Wu is a master’s degree candidate of SWPU. His
Dispers. Sci. Technol. 34 (6): 756–763. http://dx.doi.org/10.1080/ research interests include flow assurance and improvement of
01932691.2012.686252. heavy crude oil. Wu has authored or coauthored three aca-
demic papers.
Nana Sun holds a PhD degree in oil and gas engineering from Sijia Zheng holds a PhD degree in oil and gas engineering
Southwest Petroleum University (SWPU). Her research interests from SWPU. He earned an MS degree in oil-and-gas storage
are emulsification and demulsification of heavy crude oil. Sun and transportation engineering from Xi’an Petroleum Univer-
has authored or coauthored more than 10 academic papers. sity in 2011, and now conducts research in the field of sand
She also holds an MS degree in oil and gas storage and trans- erosion and erosion monitoring.
portation engineering from Xi’an Shiyou University.
Hongyuan Qi is a PhD degree candidate at SWPU. Her
Jiaqiang Jing is a professor at SWPU. He has worked for 25 research interests are in pipeline wettability and frictional re-
years as a teacher for SWPU. Jing’s research interests include sistance. Qi holds an MS degree in oil-and-gas storage and
technology and theory of oil-and-gas storage and transporta- transportation engineering from Xi’an Shiyou University.

10 2016 SPE Journal

ID: jaganm Time: 21:28 I Path: S:/J###/Vol00000/160069/Comp/APPFile/SA-J###160069