SPE-176465-MS

Experimental Investigation of Crude Oil Emulsion Physicochemical

Properties and Demulsifier Dosage Prediction
Osamah Alomair, Kuwait University; Salman Alqabandi, Mariam Malallah, and Amer Alajmi, Kuwait Oil Company

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE/IATMI Asia Pacific Oil & Gas Conference and Exhibition held in Nusa Dua, Bali, Indonesia, 20 –22 October 2015.

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
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Abstract
One of the common methods of reducing or eliminating the emulsion is the use of different chemical
demulsifiers depending on the type of crude oil and water cut. This method is widely used in Kuwait Oil
Company (KOC) at wellheads and gathering centers (GC). However, some wells have practice increases
of demulsifier dosage as a result of increase in water content. Consequentiality, KOC initiated a program
for optimization of chemical consumption for water/oil emulsion separation in the surface facilities at
West Kuwait. As a result, of one year oil field statistical analysis of crude oil emulsion collected data. The
results indicate that there are four oil wells of a different physical property could be very helpful for our
study. Such properties include emulsion viscosity, size of water droplets, surface active materials, resin
to asphaltene ratio (R/As), emulsion temperature. Over and above the demulsifier efficiency and dosages
were evaluating using the calculated emulsion separation index (ESI) and interfacial tension measurement.
As a result the oil field laboratory test indicates that the viscosity of emulsion increases to at least from
12 to17% of its original value based on dry condition. The average droplet size distribution near to (1–10)
␮m was highly effect on emulsion stability. Moreover the emulsion behavior was linked closely to the
film form around the water droplets that are believed to result from the adsorption of high-molecular-
weight polar molecules (asphaltene) and fine inorganic solids. There surface-active behavior that makes
them good emulsifiers. Also it was found there are a consistent relationship between emulsion stability
and relative resin to asphaltene content R/As for all four of the field samples under study. The crude oil
of high emulsified water, near 30%, contains low (R/As, 0.84). However, as resins to asphaltene ratio
increased the emulsion become unstable and emulsified water decrease up 9 %. This relationship could
be used as the method to indicate the more likely oil field areas of strong emulsions and the suitable
practical methods for treatment. Also from the well head operating conditions collected data; emulsion
temperature, well head pressure, salinity of emulsified water and IFT. From the laboratory bottle test and
oilfield crude oil emulsions data. The demulsifiers dosage was predicted using the proposed empirical
model. In addition it could be used as a good tool for the new or the incumbent demulsifier evaluation.
Introduction
Emulsion is a heterogeneous system containing at least immiscible liquid fine dispersed in another with
the form of droplets. In general the emulsion forms in diameter ranging between (0.1–20) ␮m and it is
2 SPE-176465-MS

stabilized by an emulsifying agent, resins, asphaltenes, and finely divided inorganic solids (Kenneth 1988;
Elsharkawy et al. 2008). The dispersion of the first immiscible phase droplets into the other phase will
increase the interfacial surface area and hence a greater interfacial free energy in the system (Pilehvari et
al. 1988, Benayoune 1998, Guo et al. 2006). One of the early emulsion nature observations was conducted
by Finga (1995), who characterized emulsions into three major categories namely; Stable, Meso-stable
and Unstable, depending on the physical appearance, viscosity difference, and elasticity. Naturally, crude
oil emulsions were formed in the oil well, with the presence of natural surfactants that forms a rigid
interfacial film with high interfacial tension that prevents the dispersed phase droplets from coalescence
and forming an independent phase that will separate (Schramm 1992). Emulsions are undesirable due to
many reasons such as; pipeline corrosions, high pumping costs, reducing throughput, and cause high
pressure drop due to their high viscosity (Banerjee, et al. 2009; Chawla et al. 1998). There are some
petroleum industries in which emulsion may be desirable as in the oil-in-water generation used for
transportation and water-in-oil emulsion for gas hydrate inhabitation.
The stability of water-in-oil emulsions depends on the total structure of the molecular matrix of the
interfacial active components (Schramm 1992 and Finga 1995). Therefore, the size of water droplet, crude
oil aromaticity, types of carbonyl functionality, temperature, PH of brine, droplet size and droplet
distribution, and other functional groups in the bulk play an important role in the total stability of
emulsions (Langevin et al. 2004 and Guo, et al. 2006). A number of research groups have investigated the
various mechanisms of water-in-oil emulsion stabilization, a good review of which has been issued El
Gamal et al. (2005). Mikula and Shramm (1992) suggest that the interfacial active agents in the emulsion
had a high impact on emulsion stability, such as asphaltenes, resins, and naphthenic acid. Among these
components, asphaltenes are believed to be the major causes in stabilized the emulsion. This is because
they tend to adsorb at water-in-crude oil interfaces to form a hard film surrounding the water droplets and
protect the interfacial film from rupturing during droplet-droplet collisions (Kennth, 1988).
Generally, various techniques in industries were used to break the emulsions including; destabilizing
(heating, chemicals, or distillation), coalescence (heating chemical, electrostatic field, agitation), and/or
gravity separation. Heat application for emulsion separation considers as one of the common methods, it
results on decrease the density of the oil at a greater rate than that of water and thus allows more rapid
settling of the water. As the results, the rate of water droplets settlement and the mobility of water are
increased and lead to collisions, coalescence, and further increase in the rate of separation. This is because
the difference in densities of the two liquid phases may be increased (Mikula and Shramm 1992). Among
with the most widely used methods are using small amounts of chemicals so-called demulsifiers (De),
(Guo, et al. 2006, and Teklebrhan et al., 2012, 2014). These demulsifier (surface-active molecules) adsorb
at the oil-water interface and accelerate the phase separation. Nowadays, the exact mechanism for
destabilization is however not yet fully understood and the choice of the most efficient demulsifier is a
long and difficult task. Moreover, during the well life, the production conditions (temperature, salinity,
PH, surface-active substances, wellbore pressure, etc.) can change and it is very often necessary to proceed
to the selection of another additive.
Consequently the main objective of our study is to develop a better understanding of the crude oil
emulsion and to come across key factors effecting the stabilization of the crude oil emulsions. The results
will be helpful for evaluating the demulsifier efficiency increment and to develop a model capable to
predict the demulsifier dosages at the most effecting operating conditions. Numbers of demulsifiers
proposed by emulsion breakers chemical company were tested through a ⬙bottle-test⬙ method. The effect
of crude oil viscosity, size of water droplet, salinity, demulsifier dosage, temperature, resins to asphaltene
ratio (R/As), shearing of oil-water mixture, and IFT on separation efficiency were investigated.
From the results of oil field pilot test and the bottle test it was a large amount of information regarding
test conditions (and therefore process conditions), crude oil components that contribute to emulsion
stabilization, and demulsifier properties that counter the factors contributing to emulsion stabilization.
SPE-176465-MS 3

While there is no substitute for field experience, statistical techniques can help identify and sort through
the factors that contribute to emulsion stabilization and the properties of chemical demulsifiers that help
destabilize emulsions. To establish which factors optimize bottle test response and provide the greatest
amount of data variance experimental design is probably the tool of choice.

Experimental Section

Sample preparations
Three sets of four sealed dark bottles each with 2.5 liter capacity were used to collect crude oil samples
from the proposed four wells before demulsifier injection points at well head. All samples were kept on
dry condition and store at 15 °C. One set was mixed with emulsion breaker (commercial grade Nalco
Demulsifier) centrifuged according to ASTM D4007 to calculate the traces of basic sediments and water
cut (BS&W). The second set was simply distilled by heating to 110 °C for completely separation of the
emulsified water only. Each of dry crude oil and the separated water were kept separately in specially
designed screw cap bottles and store on oven at 20 °C, for physicochemical property measurements. The
third set without any further treatment were kept on the cabinet at 20 °C for emulsion stability evaluation
and Demulsifier investigation.

Physical property measurement

For the second set prior to the analysis each sample bottle were shaken vigorously using Lab-Line’s
(model max. Q2000) Open-Air Platform Shakers to achieve homogeneity and all instruments were
calibrated according manufacture specification. As per the test procedures, the density measurements at
25 °C were performed for all samples of dry crude oil and water. The results were averaged and the
estimated uncertainty of the measurements was within 0.5 kg · m-3. Kinematic viscosity ␮, of the four dry
crude oil samples were determined using the Cambridge Electromagnetic viscometer, (model EV 1000)
Vinci technologies France. Triplicate of measurements attained and the averages were used and the
estimated uncertainties in dynamic viscosity measurements were found to be not more than 8.10-3 mPa·s
with confidence interval 95% of all measurements. Also saturates, aromatics, resins, and asphaltenes,
SARA analysis for all dry crude oil samples were conducted using IATROSCAN MK-6sMitsubishi CMC.
Total nitrogen, carbon, hydrogen, and sulfur are determined using a CHNS analyzer, Vario MACRO-Cub
Elements. The crude oil boiling points distribution and carbon numbers of all samples were examined with
a Simulated Distillation (SIMDIS) Analyzer using the ASTM D2887 method for low-temperature tests
and the D6352, D7500, and D7169 methods for high-temperature tests. The SIMDIS analyzer uses a
nonpolar chromatographic column that separates the hydrocarbons in order of their boiling points. These
hydrocarbons are correlated with the retention times through a calibration curve obtained by running a
known mixture of hydrocarbons, typically n-alkanes, under the same conditions and covering the boiling
range expected in the sample. The analysis yielded the initial boiling point (IBP) between 88 –120 °C and
final boiling point (FBP) values ranges 710 to 740 °C (see figure 1). The total carbon numbers from C35
to C100 (50.8, 39.42, 29.26, 20.21, and 73.8 mol %) for Cr-1, Cr-2, Cr-3, Cr-4, and asphaltene,
respectively, as shown in Tables 1 and 2. These analyses indicating that all crude oil samples are contain
asphaltene fractions of a different concentration Cr-1 ⬎ Cr-2 ⬎Cr-3 Cr-4.
4 SPE-176465-MS

Figure 1—Boiling range of 4 dry crude oil samples with mass % distilled using Simdis

Table 1—Physical Properties of Dry Crude Oil Samples

Designation Cr-1 Cr-2 Cr-3 Cr-4

WCT ml at 2500 RPM 30 22 16 9

Sediment (ml) 0.15 0.0225 0.03 0.025
Crude oil assay
Kinematic viscosity,mm2·sec-1 (ASTM- D7042)
@ 20 °C 599.85 425.00 296.00 171.00
@ 25 °C 426.5 343.00 209.0 117.4
@ 30 °C 303.22 241.96 139.8 80.86
@ 40 °C 132.41 89.75 53.197 35.78
Density @ 25°C (gm/cc) 0.9731 0.9454 0.9418 0.9234
Elemental analysis, wt% (ASTM D 5291)
H 9.89 9.5 9.5 8.95
C 81.95 81.63 82.55 80.12
N 1.08 0.89 0.75 1.99
S 4.23 4.96 5.11 6.9
O* 2.85 3.02 2.09 2.05
H/C 1.45 1.4 1.38 1.34
SARA test, colloidal stability index (CII)*, and R/As ratio
Saturate %,S 14.03 11.63 10.76 9.1
Aromatic %, A 64.43 67.64 69.51 68.93
Resin %, R 9.81 10.91 10.7 13.17
Asphaltene %, As 11.73 9.82 9.03 8.8
C II* ⫽(As ⫹S)/(A⫹R) 0.35 0.27 0.25 0.22
R/As 0.84 1.11 1.18 1.5

*
SPE-176465-MS 5

Table 2—GC Analysis by Carbon Number of Cr-1, Cr-2, Cr-3, Cr-4, and As.
Carbon Number Cr-1 Cr-2 Cr-3 Cr-4 Average of extracted (As)

C6-C16 11.29 26.32 37.01 39.9 0

C16-C27 25.09 24.92 23.9 30.03 3.95
C28-C30 5.29 3.96 4.2 5.32 8.76
C31-C34 7.53 5.38 5.63 4.54 13.49
C35-C78 36.89 29.48 24.11 15.92 27.54
C79-C98 11.86 8.93 4.25 3.44 24.95
C99-C100 2.05 1.01 0.9 0.85 21.31

The interfacial tension of emulsified water with crude oil was measured by Spinning Drop Tensiometer
Grace instrument model M6500 USA. Conductivity, TDS, and salinity, for emulsified water were also
measured using VWR Traceable Hand-held meter, turbidly measured by Hach Model 2100P Portable
Turbidimeter. To measure TSS, a water sample is filtered, dried, and weighed. The cation radical of
emulsified water were determined by Dionex ICS-1600 Standard Integrated IC System (isocratic ion
chromatography (IC)) separations using conductivity detection with standard bore (4 mm) and micro bore
(2 mm) columns, Thermo Fisher Scientific USA. The measured experimental physical properties of
emulsified water were tabulated in Tables 3.

Table 3—Physical Properties of Water cut (Emulsified)

Designation Cr-1 Cr-2 Cr-3 Cr-4

Water analysis
TSS(mg/l) 15.2 5.6 2.4 1.777
Salinity (g/l) manual 207 209 209 209
Conductivity (ms/cm) 216 218 216 218
PH at 25°C 5.93 6.06 6.01 6.05
Turbidity (NTU) 10.3 0.82 0.82 0.43
Density (gr/cm3) @ 25 °C 1.1708 1.1693 1.1691 1.17151
Spec. gr. 1.1742 1.1727 1.1726 1.1749
TDS (g/l) calculated 216 249.4 250.9 246.3
Hardness (mg/l) 55775.9 63529.8 64432.8 64912
Resistivity at 25°c (ohms-cm) 4.63 4.587 4.63 4.587
Sulfate as SO4- (mg/l) 320 320 310 310
Bicarbonates (mg/l) 175.44 184.22 158.84 204.72
TDS (g/l) calculated 250.86 249.38 216.01 246.25
Hardness (mg/l) 64432.77 64911.99 63529.8 55775.95
Iron (mg/l) 0.23 0.12 0.07 0
Silicon (mg/l) 4.71 5.08 0.35 0.07
Lithium (mg/l) 9.89 9.13 7.35 8.11
Barium (mg/l) 3.52 3.22 3.07 3.12
Boron (mg/l) 34.53 33.54 31.52 29.79
Strontium (mg/l) 460.69 419.05 420.78 406.29
Chloride (mg/l) 152743.8 151763.3 131032.5 149715.5
Bicarbonate (mg/l) 204.72 184.22 158.84 175.44
Sodium (mg/l) 70112.96 69942 60697.57 68289.22
Mg (mg/l) 3364.56 3333.14 3058.45 3378.4
K (mg/l) 3273.94 3314.28 2916.18 3311.2
Ca (mg/l) 20255.23 20424.22 19945.57 17294.52
6 SPE-176465-MS

Results and Discussion

3-1 Emulsion stability investigation (Main factors)
There are many factors that usually favor emulsion stability but the potent stabilization of the emulsion
is achieved by stabilization of the interface such as high viscosity of the bulk phase and relatively small
volumes of dispersed phase, droplet size distribution, surface active materials and asphaltene to resin ratio.
(Sarbar et al. 1995)
Viscosity The qualitative study is accessible in term of dry crude oil and emulsion viscosity of different
water cut as a function of temperature. The viscosity of the four crude oil emulsions and dried crude oils
were carried out at four temperatures, 20 to 40 °C (see table 4). Generally it could be seen that the higher
percentage of water content (Cr-1) the higher will be its dry viscosity (599.85 mm2.sec-1) and the lower
value (171 mm2·sec-1) will be for (Cr-4) of low water. Also the rate of increase of the viscosity as a
function of water cut is much more pronounced as the temperature is reduced for all the crude oil
emulsions. The viscosity of crude oil emulsion samples are reduced from 3630, 2860, 2070 and 1401
mm2·sec-1 to the values 599.9, 425, 296 and 171 mm2·sec-1 for the four dry crude oil samples respectively,
at the temperature 20 °C. It was noticed as the water cut increase from 9 % to 30 % the viscosity of crude
oil emulsion increase from 12 to 17 percentage of its original value based on dry condition at 20 °C. This
result very well agrees with crude oil emulsion viscosity behavior having water content 28 to 50%
reported by (Benayoune et al. 1998) also with viscosity behavior of water-in-oil emulsions having water
cuts from 10 to 50 wt% studied by El Gamal et al. (2005).

Table 4 —Kinematic Viscosity of Emulsified Crude Oil Samples.

Kinematic Viscosity mm2.sec-1

Cr-1 Cr-2 Cr-3 Cr-4

Temperature (°C) Emulsified Dry Emulsified Dry Emulsified Dry Emulsified Dry

20 3630.0 599.9 2860.0 425.0 2070.0 296.0 1401.0 171.0

25 2800.0 426.5 2120.0 343.0 1490.0 209.0 890.0 117.4
30 2111.0 303.2 1420.0 242.0 980.0 139.9 490.0 80.9
40 1401.0 132.4 890.0 89.8 587.0 53.2 214.0 35.8

Droplet Size Distribution, (DSD) The investigation of physical properties of emulsion (w/o) is neces-
sary to provide some insight about the water droplets phase within the continuous phase of crude oil. The
DSD of an emulsion is one of the most important of its characteristics, because it controls droplet diffusion
in continuous phase, coalescence, and resistance to sedimentation or creaming, as well as rheology. Two
emulsions can have the same mean droplet size but exhibit different behavior because of differences in
their DSDs (Mikula, and, Shramm, 1992; Kenneth 1988; Thompson et al. 1985). Because size distribution
might reflect stability controls, it could also be used as an alternative of stability, if measured as a function
of time (Kenneth 1988). Generally, there are several techniques have been used to characterize w/o
emulsions and their size distribution, in particular (Thompson et al. 1985). Near infrared spectroscopy
(NIR), microscopy as (optical microscopy, transmission electron microscopy, and scanning electron
microscopy), acoustics and electro acoustics, and nuclear magnetic resonance (NMR) are some of the
popular techniques at present (Sjöblom et al. 2003). Each of these techniques offers several advantages
over others and their own biases. Optical microscopy has been used in several studies to determine size
distributions or average size diameters of emulsions to investigate the effect of asphaltenes, waxes, and
fine solid particles on emulsion stability (Thompson et al. 1985; Kenneth 1988; Mikula, and, Shramm,
SPE-176465-MS 7

1992; El Gamal et. al. 2005). The optical microscopy accuracy is sensitive to the sampling procedure and
to the best statistical interpretation, therefore, the size of water droplets distribution in w/o emulsions has
been studied by DLS Malvern Instruments. The apparatus automatically detect the particle size every 5
minutes for up to 200 times. Zeiss optical microscope is used to examine the emulsion characteristics,
droplets distribution, and water-crude oil droplets interaction of, w/o emulsion. The diameter obtained by
this technique is that of a sphere that has the same translational diffusion coefficient as the particle’s
diffusion coefficient. The ranges of estimated droplet size distribution (1–5), (2– 6), (4 – 8), (7–11) ␮m for
emulsified crude oil Cr-1, Cr-2, Cr-3, Cr-4 respectively with an average (1–10)␮m (Figure 2). Also the
emulsion stability can be characterized through the conditions that avoid the coalescence mechanism of
small water droplets; whereas the coalescence will produce larger water droplets and eventually will lead
to unstable w/o emulsion (Mikula and Shramm 1992). Suggest that as there was higher water cut, the
droplet size distribution will exhibit a lower range of particles size and create more stable emulsions.
Norwegian crude oil formed emulsion with water droplets size range of 10 –30 ␮m Kenneth (1988).
However, the average water droplet size of water in the North Sea crude oil emulsion is about 10 ␮m,
Thompson et al. (1985). In general, an emulsifying agent that are available in a crude oil plays an
important characteristic to stabilize the w/o emulsion.

Figure 2—Water droplet size distributions of the four crude oil samples

Surface active materials Surface active materials are the particles that are existing in a crude oil behave
as emulsifying agents to prevent water separation from a given w/o emulsion, Sjöblom et al. (2003).
Surface active material accumulates at the interfacial film between water droplets and crude oil to stabilize
the water droplets and consequently stabilize the emulsion. If the concentration of surface active materials
is reasonably high, the coalescence of water droplets will be avoided (Thompson et al. 1985; Sjöblom et
al. 2003; Yan et al. 1999). Figure 3 shows the effect of solid particles concentration on resolved water after
aging to the maximum steady condition, 80 hours. The calculated percentage of resolved water from crude
oil emulsion Cr-1, Cr-2, Cr-3, and Cr-4 were increase by (2, 9, 19, and 22) vol.% respectively based on
the original volume of water. This indicates that least stable emulsion is Cr-4, and the most stable
emulsion Cr-1, (see table 1, 3). In other words, the general trend observed from this behavior is that
increasing the solid content (inorganic compounds) in crude oil emulsion give rise to less amount of water
resolved from emulsion upon aging under low temperature. Figure 4 shows the non-negative least squares
8 SPE-176465-MS

analysis of the DLS autocorrelation function, which results in solid particles size distribution (SPSD) of
emulsified water throughout the elapse time of 1000 minutes. The peaks are overlapping and having the
highest intensity (85%) for Cr-1 of a lowest average SPSD, 4 nm and low intensity (59%) with heights
value near to 16 nm for Cr-4. Suggest that as the sizes of surface active materials (solid inorganic
compounds) were decrease; the stability of water will be increase. Furthermore higher solid content leads
to higher degree of stability of the emulsion formed (Eley et al. 1967, Gu et al. 1990). Also the presence
of solid particles can add to the stability if the particle sizes are small enough to become interfacially
active, with the adsorption of resins and asphaltene from crude oils, Ghannam (2003). The surface
properties of the particles can be altered by adsorption of the other interfacially active components from
the water or crude oil, Dudášová et al. (2008). Such alterations will affect the tendency of particles to
aggregate, sediment, and form a stabilized emulsion (Dudášová et al. 2009; Dudášová et al. 2009 Part 2;
Simon et al 2010). Ultimately, this may increase the separation difficulties.

Figure 3—Effect of total suspended solid on stability of water in crude oil emulsion for ageing 80 hours at 20 °C.
SPE-176465-MS 9

Figure 4 —Solid particle size distribution in emulsified water for the crude oil samples using non-negative least squares method (NNLS)
within 1000 minutes.

Ali and Alqam (2000) suggest that the chemical composition of the particles in emulsified water
depends on the origin of the solids. Sand and clay particles follow the fluids from the reservoir, while iron
oxide and iron sulfide are typical corrosion products that can be formed along the transport and processing
lines. Changes in process variables such as temperature, pressure, and pH can also lead to precipitation
of scale products like CaCO3 and BaSO4, (Amjad and Koutsoukos 2010), see table 3. Suggest that the
collected oil field operating data and pilot test will be helpful to understand about the main factors
effecting on emulsion stability.
Asphaltene (As), resin(R) and (R/As) ratio Asphaltenes are the crude oil components of a boiling
range, 400 –700 °C, and insoluble in n-heptane but soluble in toluene or benzene (Mc Lean et al. 1997b,
Sarber et al. 1997). Asphaltenes extracted from rude oil samples using (Yarranton et al 2000) and ASTM
methods (2005). The Boiling Range Distribution and carbon number for all samples were examined by
Agilent Simulated Distillation (SIMDIS) Analyzer (Model No 7890 A, USA), comparable to methods
ASTM D2887 for low temperature; and ASTM D6352, D7500 and D7169 for high temperature tests. The
result of analysis, shows the final boiling point near to 720 °C and the average of initial boiling point for
the four crude and asphaltene are range from (77.5 to 100) °C and 410 °C respectively (see figure 1). Also
the averages of total carbon number from C35 to C100 were (50.8, 39.4, 29.26, 20.21, and 73.8) mol %
for crude oil samples Cr-1, Cr-2, Cr-3, Cr-4 and (As) respectively (see table 2). So we can say that the
four crude oil samples contain almost asphaltene fractions as shown in elemental analysis section of
(Table 1).
Resin, (R) is a crude oil fraction and generally believed that resin molecules are composed of a highly
polar end group, which may incorporate sulfur, oxygen or nitrogen, and a long non-polar end group (Gelot
et al. 1984). From the results of the elemental composition of asphaltenes and resin (see table 5); the value
of H/C ratio varies in a ratio 1.55 ⫾ 0.5 of resin compared to asphaltenes, 1.21 ⫾ 0.5. Since a resin has
a much higher H/C ratio, indicating that they are less aromatic than asphaltenes (Gafonova, 2000).
Asphaltenes can form aggregates in solution through intermolecular ␲-␲ and hydrogen bonds between
asphaltene monomers. Resins reduce the tendency for asphaltenes to aggregate by disrupting these
intermolecular interactions. Suggest that (R/As) ratio may play a significant role in stability of crude oil
emulsions. However, the presence of resins in solution can destabilize emulsions via asphaltenes solvation
10 SPE-176465-MS

and/or replacement at the oil/water interface. (Gafonova and Olga 1984) studied the effect of resins on
asphaltene stabilized water-oil emulsions and found that resins tend to destabilize emulsion in most cases.
The same behavior could be seen from the results of this study that the crude oil stability decreases with
the increase of that ratio. So the values of the crude oil emulsified water decrease from (30 to 9) wt% as
the R/As ratio for crude oil emulsion increase gradually Cr-1 ⬍ Cr-2⬍ Cr-3⬍ Cr-4 from (0.8 to1.5) wt/wt
(Tables 1).

Table 5—Elemental analysis of resin and asphaltene extracted from crude oils, wt% ASTM D 5291
R As R As R As R As

Designation Cr-1 Cr-2 Cr-3 Cr-4

H 10.85 8.02 10.48 8.96 10.140 8.80 10.16 9.01

C 79.86 82.11 79.32 81.09 80.120 81.70 79.01 81.59
N 1.02 1.67 1.42 1.53 1.320 1.50 1.48 1.49
S 5.47 7.60 5.77 4.81 6.100 6.30 7.71 5.98
*O 2.80 0.60 3.01 3.61 2.320 1.80 1.64 1.93
H/C 1.63 1.17 1.59 1.33 1.52 1.29 1.54 1.33

*Oxygen by difference

Emulsion destabilization
Emulsion stability evaluation by, (Emulsion Separation Index, ESI) While a standard method ASTM
D4007 is available for determining BS&W, no standard method is available in the literature for
determining the stability of the emulsion. There are a general testing procedures are available to select
appropriate chemicals. These tests include bottle tests, or dynamic simulators and actual plant tests, (oil
field Pilot test from well head to GC. The demulsifier evaluation in our study will use a method developed
at Saudi Aramco (Kokal et al 2000) for measuring the stability and tightness of an emulsion as the
emulsion separation index, or ESI. The 100 ml of the four emulsions was distributed in 100ml graduated
bottle tests. Known amount of demulsifier was then added to each bottle test, which was shaken and
placed in a temperature-controlled bath. The percentage of separated water was then recorded over time.
A given emulsifier was characterized by the fraction of water separated within two hours of settling. The
emulsion separation index was calculated. The index is based on the ease of resolution of the test emulsion
using a proprietary chemical demulsifier. The water separation is determined by the following procedure:
1. Determine the total existing water content of the sample by using the standard BS&W procedure
according to ASTM D 4007.
2. Calculate the amount of water separated after 30 minutes at the test temperature and 5 minutes
centrifuge.
3. Convert the water separated in step, 2 into % of available water for each demulsifier dose using
the equation.
(1)

- The ESI can then be calculated as:

(2)

ESI varies from 0 ⫽ no separation, even with demulsifier addition, to 100 for full separation
SPE-176465-MS 11

Chemical Demulsifiers The demulsifiers are certain chemical compounds are widely used to destabilize
and to assist in coalescence of crude oil emulsions. The chemical counteracts the emulsifying agent,
allowing the dispersed droplets of the emulsion to coalesce into larger drops and settle out of the matrix
(Sjöblom et al. 1990). Table 6 shows the four demulsifiers hydrocarbon groups’ chemical composition as
cyclo-alkane, alkanes, aromatic, with high surface active compound like 2-Butoxyethanol (C6H14O2) have
ability to lower the interfacial tension between two liquids, (Abdel-Azim et al.2010). The active properties
may be derived from any one or a combination of nonionic, cationic, and anionic materials within each
of these types, compositions are used that will confer various degrees of hydrophobic-hydrophilic balance
to the chemical carrier that will make handling easier; this carrier is almost without exception an organic
solvent (Wu, et al. 2003). Therefore, the number of demulsifiers and their combinations must likewise be
numerous to treat the emulsions. According to manufacture specification the four oil soluble demulsifiers
were ranked on the basis of hydrophilic-lipophilic balance (HLP) as follows E⬎ C ⬎ B ⬎ A. Figures 5
shows the performance of the four demulsifiers E, C, B and A, on the same crude oil of high water content,
Cr-1 at the same 50 ppm demulsifier dosage and average well head temperature 50 °C. The results of
calculated values of the emulsion separation index (ESIs) for E, C, B and A, were (90, 75.5, 51, and 35)
% respectively. Also when using the demulsifier E of the high (ESI) under the same operating condition
but with different crude oil samples it gives high values of ESI range 90% to 96% (Figure 6). Suggested
that as the 2-butoxyethanol content increase in the demulsifier under investigation the more effective one
could be used with this type of crude oil under test. Figure 7 shows the comparison between demulsifiers
(E) and (C) behavior on the less stable crude oil emulsion and more water droplet size of the crude oil
sample Cr-4 at the same condition of temperature 50 °C and 50 ppm dosage using DLS, instrument
measuring the particle size every 5 minutes for up to 200 times. The result indicate that the demulsifier
(E) decrease 95% of water content and only 5% with average size 1–3␮m remain in oil but for demulsifier
(C), 16% of water content with an average droplets size 3– 8 ␮m remain (need more treatment on each
GC and desalter units). The ability of the demulsifier (E) on demulsification of the crude oil samples Cr-1,
Cr-2, Cr-3 and Cr-4 of the different water droplet size distribution (1–5), (2– 6), (4 – 8), (7–11) ␮m
respectively (Figures 8–10). In spite of low aromatic content of the demulsifier E (see table1, 6). It shows
signs of the high separation efficiency range from 90 to 96% and the remain with average water droplet
1–3␮m. Suggested that performance could not only depends on the crude oil composition or aromatic
concentration but also the effect of its surfactant composition on decreasing the water oil interface or water
oil interfacial tension. To go insight the water droplets phase within the continuous phase of crude oil. Carl
Zeiss optical microscope GmbH was used to examine the emulsion characteristics, droplets distribution,
and water-crude oil droplets interaction of w/o emulsion. Figure 11 exhibits a photomicrograph at 10x of
a water droplet of emulsified crude oil samples Cr-1, Cr-2, Cr-3 and Cr-4 respectively with an average
water droplet diameter, rang of 1–10 ␮m and 1–3 ␮m before and after demulsification with demulsifier
E respectively. It indicated that the demulsifier molecules were adsorbed on water-oil interfacial film and
replaced the emulsifiers. That replacement decreased both the strength and the life of oil film and film
thickness until it collapsed (Abdel-Azim et al. 2010).
12 SPE-176465-MS

Table 6 —Hydrocarbon Groups in Demulsifier by Weight Percentage

Carbon No. 6 7 8 9 10 11 12ⴙ

Hydrocarbon Groups Weight Percentage

Demulsifier-A cyclo-alkane 2.34 2.22 0.52

alkanes 5.11 35.92 1.23 0.13 3.22
aromatic 0.02 0.02 10.52 35.62 3.13
2-butoxyethanol 0
Demulsifier-B cyclo-alkane
alkanes
aromatic 38.9 53.88 1.02
2-butoxyethanol 6.2
Demulsifier-C Cyclo-alkane
alkanes
aromatic 38.2 53.38 1.02
2-butoxyethanol 7.4
Demulsifier-E cyclo-alkane
alkanes 0.09
aromatic 0.06 20.54 60.26 6.25
2-butoxyethanol 12.8

Figure 5—Effect of different demulsifiers on Cr-1 of the high emulsified water (30%)v/v on water resolved at 50 ppm dosage and
temperature 50 °C.
SPE-176465-MS 13

Figure 6 —Effect of demulsifier, (E) on water resolved for different crude oil samples using 50 ppm dosage at 50 °C

Figure 7—Effect of demulsifier type on Cr-4 demulsification

14 SPE-176465-MS

Figure 8 —Water droplets size distribution of Cr-1 with and without demulsifier, E

Figure 9 —Droplets size distribution of Cr-2 with and without demulsifier, E

Figure 10 —Droplets size distribution of Cr-3 with and without demulsifier, E

SPE-176465-MS 15

Figure 11—Photomicrograph a, b, c, d using optical microscope at 10x of water-in-oil before and after demulsification with demulsifier
E

Demulsifier Dosage and Emulsion Temperature The increased in density difference between the dis-
persed phase (water) and continuous phase (crude oil) enhanced emulsion breakdown (Sjöblom et al.
1992). Also temperature influences many variables such as viscosity of each phase and solubility of the
nonionic surfactant in either phase (Hemmingston et al. 2005). The demulsifiers act by total or partial
displacement of the indigenous stabilizing interfacial film components polar materials around the
emulsion droplets (Hemmingston et al. 2005, Sztukowski et al 2003). This displacement also brings about
a change in properties like interfacial viscosity or elasticity of the protecting film, thus enhancing
destabilization (El Gamal et al. 2005; Shetty et al. 1992). From statistical analysis of 128 experimental
16 SPE-176465-MS

data results, were done on four crude oil samples with four demulsifier and four dosage (20, 30, 40, 50)
ppm, at two temperatures ambient and average emulsion temperature (25, and 50) °C. The optimum
separation efficiency of the demulsifiers under study was found at dosage between 40 and 50 ppm and at
temperature 50 °C. So to avoid discrepancy and interference the experimental data the effect of
demulsifier type on the more stable crude oil emulsion Cr-1 was selected only to exhibits the demulsifier
performance. In addition as the demulsifier dosage increase from 20 to 50 ppm for the more efficient
demulsifier E, the ESIs were increase respectively to the high value of 50 ppm (Figure 12). Also as the
temperature increase from 25 to 50 °C for the same crude oil sample Cr-1 and demulsifier dosage change
from 40 to 50 ppm the calculated value of ESI increase from (13 – 80) % to (26 –95)% respectively (Figure
13). Suggested that the demulsification efficiency was not only depends on the demulsifier dosage but also
on the emulsion temperature. In addition to the concentration of inorganic solid particles on the water/oil
interface, R/As ratios there are other factors likes the salinity, PH and well head pressure. In spite of salts
can have a pronounced effect on the IFT of crude water /oil system, (Bai et al., 2010), and pH significantly
affected the film-forming, oil-wetting and emulsion-stabilizing properties of the polar asphaltene and resin
fractions Okasha, et al. 2009. Unfortunately no considerable difference on the salinity concentration and
PH could be seen for the four crude samples under lab test (see table 1). Suggest that from oil field
statistical analysis of crude oil emulsion collected data the effect of this variable factors and well head
prassur on the process of demulsification will be studied.

Figure 12—Effect of demulsifier, (E) dosage on the resolved water for emulsified crude oil sample Cr-1 of water cut 30%
SPE-176465-MS 17

Figure 13—Effect of temperature and demulsifier (E) dosage on crude oil emulsion Cr-1

Shearing of oil-water mixture The shear is caused by pressure drops in wellbores that lead to gas
release and hence violent agitation. Pressure drops also occur in sub-surface and wellhead valves. The
flow regime in the choke-valve is in general completely turbulent. Other potential sources of shear are
two-phase flow in branch lines, changing flow regimes, and pumping. Shearing of oil-water mixture has
an important effect on emulsion stability. So only these tests do with controlling condition. The three
experiments were conducted at different shears; low, medium and high in which the oil and water were
shaken in the automatic shaker for two minutes. The tested sample of crude oil emulsions were created
by mixing the required volume of dry crude oil and separated emulsified water from the aforementioned
second set to get new emulsion a ratio 30/70, (same w/o ratio of Cr-1), and stirring for 2 min at 650, 1000
and 3500 rpm respectively with an L5M-A laboratory mixer; 500-mL emulsions were there be prepared
and distributed in nine graduated bottle tests. Less than 5 min after the preparation of the emulsion, a 50
ppm of demulsifier E was then added to each bottle test, which was shaken and placed in a temperature-
controlled bath at 50 °C. The percentage of separated water based on original water content was then
recorded with time. The maximum % resolved water was obtained 78, 52 and 18 % at 650, 1500 and 6500
rpm respectively which all less than the original emulsion of Cr-1of resolve water 94% without using any
additional shirring effect (Figures 13 and 14). Consequently keeping all others factors constant, an
increase in shear results in a tighter emulsion. This indicate that event at the same physicochemical
property of crude oil samples and the equivalent demulsifier dosage and temperature the results will be
different if the emulsion treated with the different manner.
18 SPE-176465-MS

Figure 14 —Effect of shear on the separation of Cr-1 emulsion using 50 PPM Demulsifier (E) at temperature 50 °C

Interfacial tension at constant temperature The most common method of emulsion treatment is adding
demulsifiers. These chemicals are designed to neutralize the stabilizing effect of emulsifying agents.
Demulsifiers are surface-active compounds that, when added to the emulsion, migrate to the oil/water
interface, rupture or weaken the rigid film, and enhance water droplet coalescence. The demulsifying
efficiency is related to oil film life time and thickness and water separation efficiency of emulsion (Menon
et al 1986). The more oil film life time is reduced and the quicker the oil film thins, the more efficient
the separation of emulsion (Sarber and Al-jaziri 1995, Abdul-Raouf et al 2011). Suggest that the
emulsifiers at the interfacial film were replaced by demulsifiers. The effect of demulsifier concentration
on interfacial tension between crude oil-water interfaces is shown in Figure 15. The interfacial tension was
decreased with the increase of demulsifier concentration. When the demulsifier concentration reached a
plateau, interfacial tension considerably changed. The water-soluble and oil-soluble demulsifier can
decrease both IFT and the interfacial viscosity (IFV), but the water-soluble demulsifier E, can decrease
them to much lower level. The IFT values undergo an exponential decrease with increasing surfactant
concentration. Badakhshan and Bakes (1990)48 have, however, described this functionality as linear due
to a very narrow range of surfactant concentration used in their experimental program.
SPE-176465-MS 19

Figure 15—Effect of demulsifier concentration on interfacial tensions on crude oil emulsion Cr-1 at 50 °C

3-3-Dynamic study of crude oil emulsion (Oil filed pilot test)

The laboratory bottle test of crude oil emulsions could provides an estimate of some of the operating
variables that can be used for design the operation and evaluating the demulsifier. However, all crude oil
emulsion quality tests were done under static but the production in oil field were under a dynamic
condition. Generally the laboratory test of the crude oil emulsions deviates from field condition (Kokal
et al 2000; Badakhshan and Bakes (1990) Menon et al 1986). Consequently the field optimization of
demulsifier injection dosage should be an on-going task as conditions change over time. From the
statistical analyzes of recorded oilfield production data within one year it could be seen that each well has
its own fingerprint even at the same formation. Suggest that it will be more valuable to spotlight on four
wells dynamic performance of the same formation but with different physicochemical properties. At the
demulsifier injection point of well head the average daily operating conditions; temperatures (°C),
pressures (psi), demulsifier dosage (ppm), oil flow rate (BBL/D) and water salinity (wt%) and IFT
(mN/m) were recorded for each well. Also the efficiency of each proposed demulsifier A, B, C and E were
calculated for the wells under tested at the equal time continually for three shifts up to four days. The daily
bottle tests of collected twelve crude oil emulsions samples for each well were tested in laboratory oilfield
and the other factors were noted: color and appearance of the emulsion, clarity of the water, sediments in
the water and/or solids hanging at the interface. These factors were provided information that will be used
as a tool for demulsifier selection. According to complicated oil field data and the need for determining
the optimum dosage of the demulsifier. So it will be more valuable from economical side to predict an
empirical model correlate the more effective variables related to the demulsifier dosages. Such as
interfacial tension between water-oil phases, emulsion stability factors of oil phases, and demulsifier
dosages. The results indicate the demulsifier dosages (Xde) are performing a nonlinear function with the
measured values of IFT. Also the well head pressure (P), temperature (T), and salt concentration (Ys) in
the aqueous phase values were interrelated linearly to interfacial tension. There are various forms had been
tried and the best equation that can represent the entire data within an acceptable range of average error
was found to be of the form:
20 SPE-176465-MS

(3)

where,
The IFT, Xde, T, P and Ys are the interfacial tension (mN/m), demulsifier dosage (wt%), operating
temperature (°C), well head pressure (psi) and emulsified water salinity (wt%) respectively. The param-
eters of the variables temperature, pressure and salt concentration were, a1, a3, and a4 (-0.19553, 0.24567,
0.01115) respectively and (a2 ⫽1.4543) is constant. It was obtained by fitting the experimental data to the
developed equation using nonlinear least squares regression. To quantify the degree of accuracy of the
approximate functional relation and compare it to the true relation between the variables, a coefficient of
determination (R2) is calculated using the following equation.
(4)

where
Xexp, Xest and are experimental estimated and the average of demulsifier dosage data respectively.
The result of calculated value (R2) was 93% indicated how good the model matches the data and shows
a measure of the utility of the model (Figure 16).

Figure 16 —Comparison between experimental demulsifier dosage (Xde) for Cr-1 with different demulsifier and predicted values using
proposed model

To determine the dispersion of the data the standard deviation (SD) was calculated using equation (5).
The result of this error was near to 7.5 %. This is indicative of a smaller degree of scatter.
(5)
SPE-176465-MS 21

Also to determine the data dispersion around zero the root mean square error (RMSE) was calculated
and the deviation were (0.005– 0.008) using the equation (6).
(6)

Practically because each oil field has its own oil emulsion characterization; it is highly recommended
before using the proposed model to recalculate the parameters (a1, a2, a3, and a4) to get a appropriate
values compatible with the new condition. The accurate calculation depend on using the average Xde at
calculated values of emulsion separation index (ESP) more than 90% and high percentage of resolved
water, ⬎ 97 % (calculated by ASTM 4007). Finally good results could be obtained when root mean square
error near to zero between measured and predicted values of Xde, and a coefficient of determination (R2)
near to one.
Lastly it is recommended that field optimization of demulsifier injection should be a continuing task.
It cannot be expected that the same demulsifier composition or the same demulsifier dosage will be
capable of resolving emulsions when conditions change. Generally because emulsion is a heterogeneous
system the laboratory studies and field-testing of demulsifier must do periodically. Also on all cases of
decay on well head pressure, or in flow rate of the production line, and after the process of well treatments
or for evaluation the new and incumbent demulsifier performance. Furthermore it is recommended to
minimize the shearing of oil-water mixture by control the flow regime in the choke-valve due to its
negative effect on emulsions. Also it should use some suitable inhibitors for inorganic scales, corrosion
products, fine solids, and asphaltene
Conclusion
The selection of a demulsifier is still mainly on trial and error even after some preliminary screening.
There are still many unsolved questions related to the irregular behaviors of emulsions due to oil
compositions from the surface active materials contained in crude oil. These materials cover a large range
of chemical structures, molecular weight and hydrophilic-lipophilic balance that can interact between
themselves and reorganize at the water in oil interface. As a rule of thumb, the smaller the droplets, the
more stable emulsions are provided even if all other conditions are the same. Consequently according to
these study it was found as the water cut increase from 9 % to 30 % the viscosity of crude oil emulsion
increase from 12 to 17 times of its original value based on dry condition at ambient temperature. Also the
solid content (inorganic compounds) in crude oil emulsion give rise to less amount of water could be
resolved from emulsion and the crude oil stability will decreases with the increase of that ratio. Also there
are clear links between asphaltenes and emulsion tightness was noticed. The higher the amount of
asphaltenes in the crude oils the tighter the emulsion. Moreover the values of water cut of crude oil
emulsion decrease from (30 to 9) wt% when the R/As ratio for crude oil emulsion increase gradually from
(0.8 to1.5). Also it could be seen that the stability of crude oil emulsions not only depend on the crude
oil composition or aromatic concentration but also on the effect of its surfactant composition and its
capability on decreasing the water oil interface or water oil interfacial tension. The laboratory experiments
indicate that the IFT values undergo an exponential decrease with increasing surfactant concentration.
Also a promising tool (ESI) can be used for measuring the stability and tightness of an emulsion. The
emulsion stability increases with shear and the impacts on emulsion stability were negatively. Hence there
can be no universal demulsifier could be available, because the type and composition of oil which contains
the emulsions has more influence on how a certain chemical demulsifier will perform. According to the
complicated oil field data and were the need for determining the optimum dosage of the demulsifier. The
best demulsifier is the one that produces the fastest, cleanest separation at the lowest possible cost per unit
barrel of crude. So it will be valuable from economical side to predict an empirical model to correlate the
more effective variables related to the demulsifier dosages.
22 SPE-176465-MS

Acknowledgments
The authors are grateful for the help and support received from the Kuwait University General Facility
Research, Grants GE 01/07, GE 03/08, GS 01, GS 05, and KOC crude oil and water lab.

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