C).
The physical properties of water-in-crude oil emulsion in terms of density,
viscosity, and interfacial tension are measured by Pycnometer, Ostwald
viscometer, and spinning drop tensiometer, respectively. The stability of water-
in-crude oil emulsion is studied for each case in details. This investigation shows
that the presence of the emulsifying agent is necessary for stable emulsion, and
stability gradually decreases with water concentration. The presence of 5% NaCl
or 1,000ppm of Alcoood polymer provides 100% stable emulsion. Emulsion
stability reduces with temperature. Impeller type has a strong effect on the
emulsion stability. S-curved blade impeller provides 100% stable emulsion for
more than 2 days.
Keywords: Alcoood polymer; Mixing; Salt; Surfactant; Water-in-crude oil
emulsion.
INTRODUCTION
When water is present in an immiscible dispersed droplets phase within
the continuous crude oil phase it usually leads to the formation of
Received October 20, 2003; Accepted December 10, 2003
C, kg/m
3
827
Dynamic viscosity @ 25
C, mPas 4.79
Asphaltene content, wt% 0.42
Sulphur content, wt% 1.33
652 Ghannam
Table 2. Physical properties of W/O emulsions
Density Viscosity IFT
W/O emulsion Kg/m
3
mPas mN/m
10/90 833 4.1 43.5
20/80 849 3.7 43.5
30/70 874 3.2 43.5
40/60 893 2.7 43.5
50/50 908 2.3 43.5
used for interfacial tension (IFT) measurements. However, for non-
Newtonian emulsion behavior RheoStress RS100 rheometer is used to
investigate the viscosity behavior of W/O emulsion in the presence of
500 and 1,000ppm Alcoood polymer material of AF1235. Tables 24
show all the physical properties of all the prepared W/O emulsions.
RESULTS AND DISCUSSION
The water-in-crude oil emulsion has great importance in the oil industry,
such as in heavy crude oil transportation, presence of water within
the produced crude oil, and presence of Alcoood polymer solution
within crude oil. The stability of W/O emulsion is investigated under
the inuence of numerous parameters and conditions. These parameters
and conditions are the water concentration, surfactant concentration,
mixing speed, salt concentration, Alcoood polymer concentration, and
temperature.
Water Concentration
Wide range of water concentration is covered in this study over the
range of 1050% by volume. Figure 1 shows the percentage of the water
content within the W/O emulsion versus elapsed time for two samples
Table 3. Physical properties of W/O emulsion in presence of salt
NaCl Density Viscosity IFT
W/O emulsion Conc.% Kg/m
3
mPas mN/m
10/90 1 840 5.1 61
10/90 5 849 5.5 33.5
50/50 1 916 2.4 61
50/50 5 930 2.8 33.5
Water-in-Crude Oil Emulsion Stability Investigation 653
Table 4. Physical properties of W/O emulsion in presence of Triton X-100
Triton X-100 Density Viscosity IFT
W/O emulsion % Kg/m
3
mPas mN/m
10/90 0.1 841 3.65 1.31
0.2 845 3.71 1.29
0.5 851 3.78 1.19
1.0 862 3.90 1.10
50/50 0.1 910 2.5 1.31
0.2 914 2.4 1.29
0.5 917 2.3 1.19
1.0 925 2.2 1.10
of water concentration of 10 and 50% W/O emulsions. These samples
are prepared with no surfactant and mixing speed of 2,000rpm for
30min of mixing period. Figure 1 shows that the percentage of water
content within both emulsions drops very signicantly over 15min only.
The water content drops from almost 100% at 1min to 16% and 4%
after 15min for the 10% and 50% water concentration, respectively.
These samples show strong unstable behavior of water within W/O
emulsion. This conclusion can be attributed to the absence of emulsifying
agents within the emulsion. These samples are prepared without any
addition of surfactant materials. Also, this type of crude oil has a very
limited amount of asphaltene content (i.e., 0.42 wt.%). Several studies
Figure 1. Emulsion behavior without surfactant.
654 Ghannam
reported the importance of asphaltenes in W/O emulsions. Brandvik
and Daling (1991) reported that the presence of asphaltene within the
crude oil enhances strongly the stability of W/O emulsion. Sjoblom
et al. (1990) found that very unstable W/O emulsions are produced if
asphaltene content of the original crude oil is removed.
Figure 2 shows the stability behavior of water content versus elapsed
time when 1% by volume of Triton X-100 surfactant was added as an
emulsier for wide range of water concentrations over 20 to 50% by
volume. Surfactant material accumulates at the interfacial lm between
water droplets dispersed phase and crude oil continuous phase. This role
of surfactant stabilizes the water droplets and avoiding the coalescence
mechanism of water droplets phase (Sherman, 1983). Therefore, the
stability of W/O emulsion is strongly enhanced by the addition of
Triton X-100, as can be concluded from Figure 2. For 20% water
concentration, the percentage of water content drops slightly from 100%
at 10min to 95% after 2 days. Therefore, the function of the Triton
X-100 is to help in the formation of W/O emulsion, stabilize the
water droplet dispersed phase for longer time, and delay the coalescence
and separation mechanism of water. Figure 2 shows that when water
concentration increases for the same conditions of mixing speed and
surfactant concentration, the percentage of water content decreases
gradually with elapsed time. This can be attributed to the coalescence
mechanism that enhances gradually when more water is added. In the
case of water concentration of 50% by volume, the percentage of water
content gradually decreases from 98.4% at a 10min period to 24% after
2 days. Table 5 reports the amount of water separated as a function of
Figure 2. Effect of water concentration on W/O emulsion.
Water-in-Crude Oil Emulsion Stability Investigation 655
Table 5. Water separation performance
Reduction % of water content
Water concentration % 1hr 5hr 48hr
20 0 0 5
30 0.667 1.67 16
40 2.5 14 66.5
50 6 22.8 76.8
reduction percentage of water content in W/O emulsion. It shows that
the reduction percentage in water content of W/O emulsion increases
slightly with water concentration at the beginning of the separation
process. However, it increases signicantly with time. After 48hr, only
5% of water content is separated in the case of 20% water concentration,
however, 76.8% of water content is separated in the case of 50% of water
concentration.
Effect of Surfactant Concentration
The presence of surfactant material in W/O emulsion promotes
and stabilizes the water-in-crude oil emulsion. Surfactant molecules
surround the water droplets with a certain arrangement. The polar
hydrophilic portion of the surfactant molecules resides within the
aqueous phase, whereas the hydrophobic end resides within the crude
oil phase. Mackay et al. (1973) found that the water droplets are
encapsulated with surfactant molecules to prevent coalescence of the
water droplets. Figure 3 shows the effect of Triton X-100 on the stability
performance of W/O emulsion for 50% water concentration over
the surfactant concentration of 0.1 to 1.0% by volume. It shows that
the stability performance increases with surfactant concentration. This
can be attributed to the ability of more surfactant molecules to encap-
sulate more of the water droplets to avoid the coalescence mechanism.
Although the stability performance enhanced with surfactant concen-
tration, however, the W/O emulsion is not stable over time. This issue
will be addressed later in this study. Figure 4 shows the same effect
for 10% water concentration. It shows again, the more the addition of
surfactant the better stability is reported up to 0.2% by volume, which
can be explained due to a lower amount of water available (i.e., 10%
only). The stability of water performance of 96% is achieved for a time
period of 5hr in comparison with much less performance and a shorter
period in the case of 50% water concentration.
656 Ghannam
Figure 3. Effect of surfactant concentration on 50% W/O emulsion.
Mixing Speed Effect
Mechanical mixing is one of the well-known methods to form W/O
emulsions from two immiscible phases. Adding the dispersed phase very
slowly to the continuous phase during the mixing process usually offers
Figure 4. Effect of surfactant concentration on 10% W/O emulsion.
Water-in-Crude Oil Emulsion Stability Investigation 657
a big advantage for the emulsication process. The interface between the
dispersed and continuous phases is deformed to form droplets.
At the beginning of the emulsication process, the droplets are
mostly too large. During the mixing process, these large droplets are
broken down into smaller ones due to the disruption process of the
large droplets. Droplets must be deformed to achieve their disruption,
the deformation behavior is opposed by the high Laplace pressure. The
pressure drop, AP, between the concave side and the convex side of a
curved interface is given by:
AP = 2,R (1)
where is the interfacial tension between crude oil and water, and R
is the droplet radius. To break down the large droplet diameter, such
a pressure must be externally supplied over the droplet radius. The
required pressure gradients are supplied by agitation. Eq. (1) shows that
the smaller the droplet, the more amount of agitation should be supplied.
Figure 5 shows the percentage of the water content within the
emulsion versus elapsed time for 50% W/O emulsion in the presence
of 1% surfactant. A wide range of mixing speed is investigated over
the range of 500 to 2000rpm for 30min of mixing period. Figure 5
shows that the more rpm supplied, the more stability is achieved.
It is clear that by increasing the mixing speed, the droplet diameter
decreases signicantly and consequently enhances the emulsion stability.
However, Figure 5 shows a gradual reduction of water content within
Figure 5. Effect of mixing speed on 50% W/O emulsion.
658 Ghannam
the emulsion over time due to the coalescence mechanism between the
water droplets.
After the formation of W/O emulsion, droplets may recombine
together through a occulation process followed by coalescence to form
bigger droplets in which the emulsion stability will be negatively affected.
During the emulsion preparation, it is difcult to predict whether or
not and how fast the coalescence will occur. When water and crude oil
are agitated within a vessel until the emulsion is formed, the surfactant
concentration is consumed due to the generation of a new droplet
surface area. Therefore, the water droplet size often increases slowly,
which results in a change in the initial droplet size distribution. This
process usually leads to the complete separation of the emulsion into two
immiscible water and crude oil phases. The enhancement of the water
content percentage will be investigated in this study in a later section.
Salt Effect
It is necessary sometimes to form W/O emulsions with salty water,
especially for a heavy crude oil pipeline transportation situation, since
saline water is available and much cheaper than fresh water at oil
industry facilities. Therefore, it is important to investigate the role and
the effect of sodium chloride on the stability of W/O emulsion. Figures 6
and 7 show the effect of NaCl concentration on the stability of 50 and
10% W/O emulsions, respectively. One percent NaCl slightly increases
Figure 6. Behavior of 50% W/O emulsion in the presence of NaCl.
Water-in-Crude Oil Emulsion Stability Investigation 659
Figure 7. Behavior of 10% W/O emulsion in the presence of NaCl.
the water content within the W/O emulsion for both concentrations.
However, the addition of 5% NaCl strongly improves the presence of
water content within the emulsion. The presence of 5% NaCl in both
emulsions, 50 and 10% W/O emulsions, enhances the stability of W/O
emulsion to reach 100% for the whole period of the test.
The same experiment was exactly repeated for 50% W/O emulsion
(with the conditions of 5% NaCl, 2,000rpm, and 30min of mixing
period), but without Triton X-100. Although, this sample has 5%
of NaCl concentration, however, it separated completely into water
and crude oil phases within a few minutes. First, these results clearly
showed that the emulsifying performance of Triton X-100 is enhanced
signicantly in the presence of NaCl. Second, the addition of NaCl
lowers the IFT between crude oil and water signicantly, which enhances
the stability of W/O emulsion. Third, increasing the ionic strength
may reduce the electrostatic attraction between the water droplets
and therefore prevents occulation and coalescence of these droplets.
Therefore, the role of NaCl strongly enhances the stability performance
of W/O emulsion and reaches to 100% stability after 48hr for 5% NaCl
concentration. The improvement performance for the presence of NaCl
within W/O emulsion can be calculated using Eq. (2) as:
Improvement % = |(S)
5%NaCl
(S)
0%NaCl
]
100,|(S)
0%NaCl
] (2)
where (S) is the H
2
O content percent. The results of improvement
percent for the presence of NaCl for 10 and 50% W/O emulsions are
listed in Table 6.
660 Ghannam
Table 6. Improvement percentage for the presence of NaCl
Improvement percent
Time, min 10% W/O emulsion 50% W/O emulsion
10 41.2 0.41
20 84.6 0.81
30 118.2 3.33
60 166.7 6.90
120 242.9 18.10
180 242.9 20.40
240 300.0 24.00
300 300.0 30.53
1,440 300.0 230.67
2,880 300.0 350.91
Table 6 shows that the improvement percent increases with time for
both emulsions. The presence of NaCl is more effective in the rst three
hr for the 10% W/O emulsion, whereas, it reports higher improvement
for the 50% W/O emulsion after ve hr.
Polymer Effect
Alcoood polymer of AF1235, water soluble polymer powder, is used
extensively in the enhanced oil recovery stage to extract some of the
trapped oil in the well. Alcoood polymers provide superior handling
characteristics and solubility to enhance injection properties through
reservoir permeability. The main objectives of using Alcoood polymers
are to improve mobility ratio, sweep efciency, and increase recovery and
oil production rates. Therefore, it is necessary to study the role and effect
of the presence of AF1235 in the aqueous phase on the stability of W/O
emulsion. This study covers two different concentrations of aqueous
solution of 500 and 1,000ppm. The viscosity behavior of AF1235
aqueous solutions is studied using RheoStress RS100 from Haake
of cone and plate sensor (cone diameter is 35mm, cone tip gap is
0.137mm, and cone angle is 4
C. After one hr of
emulsion preparation, temperature shows a signicant inuence on the
emulsion stability. It shows that the higher temperature slightly reduces
the emulsion stability. Although, the solubilization of crude oil in the
aqueous surfactant solution increases, the viscosity of either phase will
reduce signicantly with temperature. Therefore, the droplets of water
phase will acquire more kinetic energy in which the collisions between
Figure 10. Effect of temperature on 50% W/O emulsion.
Water-in-Crude Oil Emulsion Stability Investigation 663
droplets of water phase will be more common. The collision mechanism
between water droplets is enhanced with temperature, therefore, the
interaction between these mechanisms improves the separation between
the crude oil and water phases, (i.e., lower stability).
Enhancement of Stability Behavior
It is necessary to improve the W/O emulsion stability performance. The
presence of 5% NaCl or 1,000ppm of AF1235 enhances the stability of
W/O emulsion to almost 100% over 48hr. However, all other samples
suffer a signicant drawback in the stability behavior. It is important
for this study to investigate the effect of mixer impeller as well. The
impeller with a helical shape diameter of 1.2cm was used in all previous
emulsions. S-curved blade impeller with a diameter of 2.8cm is used to
investigate the stability of 50% W/O emulsion with conditions of 1%
Triton X-100, 2,000rpm mixing speed, and for a wide range of mixing
time (10 to 50min). The 50% W/O emulsion was selected because it
showed the lowest stability behavior among all samples. Table 7 shows
the stability results as a function of the elapsed time over the time
range of 048hr for the S-curved blade impeller mixer. First of all, it is
very necessary to mention that no water was separated from any tested
sample over the recorded time. Therefore, the stability of W/O emulsion
reaches 100% for all samples (no water was separated). However, over
the time, depending upon the mixing period of 10 to 50min, a light
brown emulsion layer formed underneath the main emulsion layer. The
light brown layer increases slightly with time. Therefore, one can say
this technique achieves stable emulsion for the mentioned conditions
over 48hr with no water separated. The values listed in Table 7 are
Table 7. Stability performance percent using S-curved blade impeller
Mixing period, min
Elapsed time, min 10 20 30 40 50
10 100 100 100 100 100
20 100 100 100 100 100
30 97.5 98.5 99 100 100
60 96.5 97.5 98 100 100
120 95 95.5 97 100 100
180 92 93 95 100 100
240 90.5 91 94 100 100
300 88.5 88.5 92.5 100 100
1440 65.5 66.5 67.5 68 100
2880 64 65 66 68 68.5
664 Ghannam
Table 8. Average diameter of the water droplet
Mixing period, min 10 20 30 40 50
D
sv
, m 11.5 11.0 10.3 9.6 8.8
for the stability of the main emulsion w.r.t. the light brown emulsion.
The growth percent of the light brown layer can be obtained from the
subtraction of 100 minus the listed value in Table 7.
The computer image analyzer system is used to observe the W/O
emulsions prepared with a different time of mixing, 1050min. Several
images were analyzed for each sample over the rst 5hr of elapsed time.
For each sample, the image analyzer shows that the average diameter of
the water droplets within W/O emulsion does not change signicantly
with elapsed time. The Sautor mean droplet diameter D
sv
, Eq. (3), is
measured for these emulsions.
D
sv
=
N
i
D
3
i
,
N
i
D
2
i
(3)
where N
i
is the number of droplets and D
i
droplet diameter. Table 8 lists
the average diameter of the water droplets within W/O emulsion for each
mixing period.
Figure 11 shows some examples of water droplets distribution within
different W/O emulsions for different mixing periods with the conditions
of 2,000rpm, 1% Triton X-100, and 50% water concentration. Table 8
and Figure 11 show that the water droplets average diameter decreases
gradually with time of mixing. The droplets average diameters are 11.5,
10.3, and 8.8m for a mixing period of 10, 30, and 50min, respectively.
The degree of emulsion stability enhances signicantly by decreasing the
droplet diameter. Therefore, for the same mixing speed, the more mixing
time supplied the more stable the emulsion will be.
CONCLUSIONS
From the investigation of W/O emulsion behavior, the following points
are found:
1. The W/O emulsions show strong unstable behavior of water within
the emulsion due to the absence of an emulsifying agent.
2. The stability of W/O emulsion enhances signicantly by the addition
of Triton X-100.
3. Stability of W/O emulsion gradually decreases with water
concentration.
Water-in-Crude Oil Emulsion Stability Investigation 665
Figure 11. Photomicrograph for 50% W/O emulsion.
666 Ghannam
4. Stability of W/O emulsion enhances with Triton X-100 concentration.
Concentrations of 0.2% and 1.0% of Triton X-100 achieved better
performance for 10 and 50% W/O emulsions, respectively.
5. Mixing speed improves the W/O emulsion stability, the more rpm
supplied the more stability of the W/O emulsion is achieved.
6. The role of NaCl strongly enhances the stability performance of W/O
emulsion and reaches to 100% stability for 5% NaCl concentration.
7. The presence of AF1235 strongly enhances the stability of W/O
emulsion.
8. High temperature reduces the W/O emulsion stability.
9. The stability of W/O emulsion reaches 100% by using S-curved blade
impeller.
ACKNOWLEDGMENT
The author is very grateful to the nancial support from the United Arab
Emirates University under the grant # 01-02-7-11/04.
REFERENCES
Bobra, M. (1990). In: Proceeding of Arctic and Marine Oil Spill
Program. Minister of Supply and Services Ottawa, Environmental
Canada.
Brandvik, P., Daling, P. (1991). W/O-emulsion formation and W/O-
emulsion stability testingan extended study with eight oil types. IKU
Sintef Group, Trondheim.
Canevari, G. (1987). In: Proceedings of Oil Spill Conference. American
Petroleum Institute, Washington, DC.
Carcoana, A. (1992). Applied Enhanced Oil Recovery. New Jersey:
Prentice-Hall.
Christopher, C. (1993). In: Walker, A., Ducey, D., Gould, J., Nordvik, A.
eds. Formation and Breaking of Water-in-oil Emulsions. Washington,
DC: Marine Spill Response Corporation.
Dalgleish, D. (1996). Food Emulsions. Surfactant Science Series. New
York: Marcel Dekker V61.
Eley, D., Hey, M., Symonds, J., Willison, J. (1976). Electron micrograph
of emulsions of water in crude petroleum. J. Colloid Int. Sci. 54:462.
Fingas, M., Fieldhouse, B., Mullin, J. (1995). In: Proceedings of Oil Spill
Conference. American Petroleum Institute. Washington, DC.
Ghannam, M. (2003). Emulsion ow behavior of crude oilAlcoood
polymers. J. Chem. Eng. Japan 36(1):35.
Mackay, D. (1987). Formation and stability of water-in-oil emulsions.
Environment Canada, Ottawa.
Water-in-Crude Oil Emulsion Stability Investigation 667
Mackay, G., Mclean, A., Betancourt, O., Johnson, B. (1973). The
formation of water-in-oil emulsions subsequent to an oil spill. J.
Institute Pet. 59:164.
Mikula, R. (1992). In: Shramm, L., ed. Emulsion Fundamentals and
Applications in the Petroleum Industry. Washington, DC: American
Chemical Society V231.
Mingyuan, L., Christy, A., Sjoblom, J. (1992). In: Sjoblom, ed.
EmulsionsA Fundamental and Practical Approach. Dordrecht:
Kluwer Academic Publishers V363.
Pilehvari, A., Saadevandi, B., Halvaci, M., Clark, D. (1988). In: Roco,
M. C. ed. Pipeline transportation of heavy crudes as emulsions.
Proceedings 3rd International Symposium Liquid Solid Flows, ASME
V75, New York.
Reichman, D., Garti, N. (1991). In: Dickinson, E., ed. Food Polymers,
Gels and Colloids. Cambridge: Royal Society Chemistry.
Sherman, P. (1983). In: Becher, P., ed. Encyclopedia of Emulsion
Technology. New York: Dekker V1.
Sjoblom, J., Sonderlund, H., Lindblad, S., Johansen, E., Skjarvo, I.
(1990). Water-in-crude oil emulsions from the Norwegian continental
shelf. Part II. Chemial destabilization and interfacial tensions. Colloid
and Polymer Sci. 268:389.
Thompson, D., Taylor, A., Graham, D. (1985). Emulsication and
demulsication related to crude oil production. Colloids and Surfaces
15:175.