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Synthesis and Preliminary Demulsification Efficiency

Evaluation of New Demulsifiers Based on Fatty Oils
a a b
Rasha A. El-Ghazawy , Ahmed M. Al-Sabagh , Nadia G. Kandile & Mahmoud R. Noor El-
a
Din
a
Egyptian Petroleum Research Institute, Nasr City, Egypt
b
Chemistry Department, Faculty of Women, Ain Shams University, Heliopolis, Cairo, Egypt

Version of record first published: 17 Sep 2010.

To cite this article: Rasha A. El-Ghazawy, Ahmed M. Al-Sabagh, Nadia G. Kandile & Mahmoud R. Noor El-Din (2010): Synthesis
and Preliminary Demulsification Efficiency Evaluation of New Demulsifiers Based on Fatty Oils, Journal of Dispersion Science
and Technology, 31:10, 1423-1431

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 Journal of Dispersion Science and Technology, 31:1423–1431, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932690903223534

Synthesis and Preliminary Demulsification Efficiency

Evaluation of New Demulsifiers Based on Fatty Oils
Rasha A. El-Ghazawy,1 Ahmed M. Al-Sabagh,1 Nadia G. Kandile,2 and
Mahmoud R. Noor El-Din1
1
Egyptian Petroleum Research Institute, Nasr City, Egypt
2
Chemistry Department, Faculty of Women, Ain Shams University, Heliopolis, Cairo, Egypt

Three raw fatty oils were used as precursors for demulsifiers. The hydrolyzed form of each oil was
adducted with maleic anhydride then modified by esterification with polyethylene glycols or
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ethyleneoxide-propyleneoxide block copolymers. The demulsfication efficiency, coalescence rate,

some surface active, thermodynamic properties, and partition coefficient of a selected demulsifier
were investigated. The best demulsifier shows 100% demulsification after 19 minutes at 300 ppm.
A correlation between demulsification efficiency and rheological properties of the investigated
demulsifier was investigated. Also, emulsification kinetics were followed by microscopic photo-
graphy. A mechanism following coalescence and flocculation of water droplets is proposed.
Keywords Demulsification mechanism, photomicroscopy, rheological properties

INTRODUCTION Generally, oil with a high viscosity has the ability to

The increased problem of crude oil fields that are now
producing both crude oil and water pushes researchers to
develop more economically chemical demulsifiers. Such
demulsifiers alter the oil-water interfacial properties and
water droplets size. Attempts have been made to correlate
demulsifier performance and some properties like molecu-
lar structure, hydrophilic-lipophilic balance (HLB), interfa-
cial tension, interfacial viscosity, partition coefficient,
dynamic interfacial tension and relative solubility num-
ber,[1–9] but no generalized conclusions have been determ-
ined. The selection of the suitable demulsifier for a
certain oil emulsion stills a practical art. The high molecu-
lar weight components of petroleum crude oil especially
asphaltenes and resins (with misusing name natural surfac-
tants) are responsible for crude oil emulsion stability. They
do not develop very high surface pressure but the steric sta-
bilization in combination with small particle stabilization is
the most plausible mechanism of stabilization of such
emulsions. On adding good demulsifier, an acceleration
of flocculation and film rupture processes are performed
as the demulsifier molecules which lower interfacial tension
much more than the natural surfactants could replace the
latter.[10] On the other hand, the enhancement of the rheo-
logical properties of the emulsion upon adding the demul-
sifier is one of the important factors that should be studied.
Received 14 April 2009; accepted 14 May 2009.
Address correspondence to Rasha A. El-Ghazawy, Egyptian
Petroleum Research Institute, I-Ahmed El Zomer St., Nasr
City 11727, Egypt. E-mail: basharosh_00@yahoo.com
hold up more and larger water droplets than oil with lower
viscosity. Thus, lowering the viscosity increases both the
rate at which water droplets settle and the mobility of
water droplets and thereby leads to collisions, coalescence
and a further increase in the rate of separation.
The main goals of this study were to prepare demulsi-
fiers based on locally available raw materials (soybean,
linseed, and castor oils) and to follow the mechanism of
demulsification through studying the kinetics and using
microscopic photography. Fatty oils are the main local
raw materials that are subjected to hydrolysis and esterifi-
cation. The produced demulsifiers are evaluated through
the conventional bottle test using a stable crude oil emul-
sion containing 7.14% asphaltene. The best demulsifier
was then subjected to further analysis as: effect of water
and asphaltene content, some surface active properties,
rheological properties, kinetic and photomicroscopic stu-
dies.
EXPERIMENTAL
Materials
The following chemicals were used: soybean oil (S)
[byproduct of Egyptian Extracted Oils Co., Egypt], linseed
oil (L), castor oil (C) [Al-Nasr Co., Egypt], potassium
hydroxide [Merck, Germany], maleic anhydride [Prolabo,
France], polyethylene glycol (PEG, Mn ¼ 2000 and
4000 mol
1) [May & Baker Ltd., UK], poly(ethyleneoxide)-
poly(propyleneoxide)-poly(ethyleneoxide) block copolymers

1423
 1424 R. A. EL-GHAZAWY ET AL.

TABLE 1 selected to resemble the real working temperature used in

Physicochemical properties of crude oils the offshore processes.
Results Rheology Measurements
Specification Method Type I Type II Type III A Haake viscometer model Rotovisco RV12 was uti-
lized to measure the dynamic viscosity for untreated and
Specific gravity IP 160 0.793 0.874 0.811 treated emulsions with a selected demulsifier at different
(60=60 F) concentrations, viz., 50, 100, and 200 ppm at 30, 40, 50,
API gravity at IP 160 36.29 40.955 42.6 and 60 C. Yield point and apparent viscosity values were
60 F determined.
Kinematic viscosity IP 71 294.97 222.87 9.2
at 40 C (C.St) Surface Tension Measurements
Asphaltene content IP 143 9.45 7.14 0.723 Surface tension of the prepared surfactants was evaluated
(wt.%) using Lecomte De Nouy tensiometer [Kruss K6–Germany]
Paraffin wax (wt.%) UOP 46 2.86 3.1 16.1 at 25 C using distilled water. The surface tension – concen-
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Water content (%) IP 74=70 0.5 0.5 0.4
(BP, Mn ¼ 3000, 6400 & 14500 mol
1) [Stephan, USA],
Crude oil were submitted from SUCO oil Co., Egypt. The
physicochemical properties of the used crude oils are
illustrated in Table 1. All chemicals were used as supplied.
Synthesis of Demulsifier
Soybean, linseed, and castor oils were hydrolyzed separ-
ately using KOH.[11] The produced fatty acids were indi-
vidually adducted with MA[12] using equimolar ratios.
1 mole of each adduct was esterified with 1 mole of PEG
400, PEG 6000, BP 3000, BP 6400, and BP 14500 using
xylene as a solvent and 1% p-toluene sulphonic acid as a
catalyst. The reaction was continued until the theoretical
amount of water was collected azeotropically. The reaction
was followed up using FTIR spectroscopy [ATI Mattson-
Genesis Series]. Samples code is XYn, where X: represents
the name of the hydrolyzed oil (S, L, or C), Y: represents
PEG or BP (P or B, respectively) and n: represents the mol-
ecular weight of PEG or BP (viz., 2 for 2000, 3 for 3000, 4
for 4000, 6 for 6400, and 14 for 14500 mol
1).
Emulsion Preparation
The demulsifiers were evaluated using different emulsion
of asphaltenic crude oil (O): sea water (W) prepared using a
mixer homogenizer at 350 rpm for 5 minutes. Emulsion
with different ratios namely 30:70, 50:50, and 70:30 (o:w)
were used through this investigation. A commercial sample
submitted from Backer Petrolite Co., Egypt, was used for
efficiency comparison.
Bottle Test (Sani Glass)
Conventional graduated bottle test was used to measure
demulsifiers performance. After adding the demulsifier to
the prepared emulsions the bottles were shacked 60 times
and kept in a water bath at 60 C, where the amount of
separated water was observed. This high temperature was
tration isotherms (SVC) were plotted for the prepared sur-
factants at different temperatures and the critical micelle
concentration (CMC) values were determined from the
abrupt change on these curves. Spinning drop Interfacial
Tensiometer [Kruss Site-04] was used for measuring the
interfacial tension between crude oil and demulsifier. The
demulsifiser was dissolved in sea-water and the denser phase
(oil phase) was injected by means of microliter syringe to a
spinning capillary tube. As the oil drop is elongated, its
diameter was measured by an occulometer. The interfacial
tension was calculated by the following equation
c ¼ 3:427  10
7  ð0:7dÞ3  n3  Dq;
where: d is the diameter of the drop (mm); n is the speed of
rotation (rpm); and Dq is the density difference between the
oil phase and the surfactant aqueous solution (g =cm3).
Microscopic Photography
Also, a photography and kinetic study for the best
demulsifier were carried out for the prepared synthetic
emulsions with 30:70 w:o ratio (tough emulsion). The emul-
sions were kept overnight at room temperature to assure
stability of the emulsion without treatment and the photo-
graphic microscopy studies were carried out at 60 C. The
slides were photographed under a microscope (Binucular
Olympus Microscope, Ltd., Tokyo, Japan) and the droplets
were counted with the help of a Digitat 5050-R [13].
RESULTS AND DISCUSSION
The Fourier transform infrared (FTIR) spectroscopy of
3,6-diene 9,10-succinic anhydride 18-poly(ethyleneoxide)-
poly(propyleneoxide)-poly(ethyleneoxide) octadecanoate
(LB6) as a representative sample showed: broad band at
3126 cm
1 characteristic for carboxylic hydroxyl group
(-OH); two stretching bands at 2928 and 2855 cm-1 for
aliphatic CH2 and CH3; out of plane bands at 1458
and 1384 cm
1 assigned for CH2 and CH3, respectively;
 EFFICIENCY EVALUATION OF NEW DEMULSIFIERS
FIG. 1. Demulsification of hydrolyzed soybean oil based demulsifiers
at 300 ppm for 30% water content of type II oil emulsion at 60 C.

1
stretching band at 1705 cm for C=O of carbonyl group
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of anhydride ring and a stretching band at 1739 cm
1 noted
for the ester group with the block polymer.
Separation time required for complete demulsification
of the prepared demulsifiers based on both soybean (S)
and linseed (L) oils at 300 ppm for 30% water of Type II
emulsion are shown in Figures 1 and 2, from which it is
obvious that the demulsifiers containing only ethylene
oxide groups (PEG) as a hydrophilic moiety are less effec-
tive than those containing both EO and PO groups (BP).
This is probably because of the hydrophilic hydrophobic
nature of the block copolymer (BP) assumes its ability to
link more than one water droplet along each polymer chain
compared with the hydrophilic nature of EO, which is able
to be partitioned at one water droplet interface. This BP
structure may give the chance for dispersed water droplets
to form clusters more or even readily open water channels.
This droplet growth forms clusters then channels facilitates
the role of demulsification. A sketch for the proposed
demulsification mechanism is presented in Sketch 1.
Also, it can be seen that the increasing in (EO) content
is accompanied by an increase in the demulsification
efficiency. This behavior may be due to the demulsifier
molecule will have more suitable amphiphilic structure that
permits better partitioning at w=o interface and hence more
effective adsorption. As a result of efficient adsorption,
FIG. 2. Demulsification of hydrolyzed linseed oil based demulsifiers at
300 ppm for 30% water content of Type II oil emulsion at 60 C.
1425
SKETCH 1. Proposed demulsification for block polymer based
demulsifiers.
better demulsification performance is expected. This
observation runs in harmony with that reported by.[14] that
is, good performance demulsifiers is related to high
percentage of hydrophilic content. On the other hand,
increasing the molecular weight of BP in the demulsifier
molecule from 3000 to 6400 as in LB3 and LB6, respectively
shows an increase in the demulsification efficiency. This
may be due to the increasing probability of water droplet
numbers coalescence forming the channels and finishing
demulsification of the emulsified water. While further
increase in the BP molecular weight up to 14500 as in
LB14 causes a decrease in the demulsification efficiency.
This is probably due to the high increase in the BP molecu-
lar weight causes more coiling of the polymer chain. This
will lead to a decrease in surface concentration and thus
lower efficiency of the demulsification. It is important to
mention that LB6 gives 100% efficiency at 300 ppm in
19 minutes. This fast demulsification at reasonable
concentration is considered as a good step in preparing
an effective demulsifier based on local materials.
Figure 3 shows the demulsification process of the demul-
sifiers based on castor oil (C). It reveals that these demulsi-
fiers show the same trend in performance as those based
on S and L. This similarity is due to similar structures.
Comparing the time required for complete demulsification
FIG. 3. Demulsification of hydrolyzed castor oil based demulsifiers at
300 ppm for 30% water content of type II oil emulsion at 60 C.
 1426 R. A. EL-GHAZAWY ET AL.

(Figures 1–3), C-based demulsifiers are less effective than TABLE 2

the rest. This behavior is explained on the basis of aqueous Effect of water content on the demulsification efficiency of
solubility, function group and its polarity. The polarity is LB6 demulsifier for type II emulsions at 60 C
an important parameter affecting the adsorption of surfac-
tants at the interface. The polar functional groups (here, Water LB6 Coalescence Separation Demulsifier
the hydroxyl group of the castor oil backbone) should content concn. rate constant, Time Efficiency
aid adsorption at the interface since the adsorption (%) (ppm) (ml=min) (min) (%)
phenomenon is mainly electronic. Taking in mind that this 30 25 0.4745 61 100
effect may be counteracted by the fact that: increasing 50 0.5301 53 100
the polarity of the molecule generally increases its water 100 0.7817 37 100
solubility. The net result of these competing effects can 200 1.1266 24 100
only be determined experimentally. Here, through this 50 25 1.3426 40 100
series the water solubility may alter the surfactant transfer 50 1.6119 29 100
to the interface, which in turn affects dragging of asphal- 100 2.2419 21 100
tenes away from the interface. The asphaltene dragging 200 2.5931 17 100
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process is responsible for film thinning, rupture, coalesc- 70 25 2.2091 34 100

ence and finally demulsification. Although C based demul- 50 3.5696 21 100
sifiers are of low activity, the CB6 shows a fast 100% 100 4.0799 16 100
demulsification at 300 ppm after 26 minutes, that is, 200 4.5135 14 100
efficient demulsifier that can be applied practically.

Effect of Water Content
Water content in w=o emulsion is one of the important
factors affecting the demulsification efficiency or the stab-
ility of an emulsion in general. The tough emulsions are
not only depending on asphaltene, resin and paraffin but
also on water content.[3] However, at low water content,
the external pressure of the continuous phase (oil) is greater
than the internal pressure of water droplets.[15] This leads
to an increase in the mechanical stability of the interface
film, so that breaking of this strong interface film will need
a high temperature and strong demulsifier. On the other
hand, at increasing water content, the external pressure
of water phase becomes less than the internal pressure.[15]
This leads to an increase in the interface film thinning, so
that the drawing of water droplets will be increased. In a
regular w=o emulsion, the maximum stability of an emul-
sion will occur at a set ratio of water to oil. Typically, this
maximum is found at low water contents as water droplets
have a small chance of colliding and coalescing with each
other. Increasing the water percentage may destroy the
stability of an emulsion. This behavior is evident upon
investigating a selected demulsifier namely, LB6 with 30,
50, and 70% water to oil ratio. Values of separation rate
constant, time for maximum separation and demulsifier
efficiency in presence of different demulsifiers concentra-
tions of LB6 at the selected water contents are listed in
Table 2. These results indicate that the time taken for com-
plete water separation and the required demulsifier doses
generally decreased with increasing the water content for
all demulsifiers. For example, 100% demulsification
efficiency was exhibited after 37, 21, and 16 minutes with
30, 50, and 70% water contents, respectively, at 100 ppm.
Whereas the same performance was obtained at 53, 29,
and 21 minutes with 30, 50, and 70% water contents,
respectively at 50 ppm. This may be explained by the
reduction of the interfacial film pressure in presence of
the demulsifier or at least the film is no longer as rigid as
in absence of it.
Effect of Asphaltene Content
The stability of the emulsion is controlled by type and
amount of indigenous surfactants and=or finally divided
solids which act as emulsifying agents. These emulsifiers
form interfacial films around the droplets of the dispersed
phase and create a barrier that slows down or prevent
coalescence of the droplets. The displacement of the
asphaltenic film at the w=o interface by the demulsifier, is
an important factor of destabilizing this film.
The effect of asphaltene content (9.8, 7.14 and 1.8%) on
the stability of w=o emulsion in absence and presence of
LB6 is illustrated in Table 3. The data indicate that the time
taken for complete water separation increases with increas-
ing the asphaltene content. Generally, the hydrodynamic
force between the water droplets and asphaltene content
on the emulsion governs the eventual rupture of w=o emul-
sion. The asphaltene is responsible for increasing the stab-
ility of emulsion by forming this stable mechanical
interface and decreasing the hydrodynamic force between
water droplets and asphaltene.[16] Subsequently the ability
of demulsifier to migrate through oil phase to adsorb on
the water droplet interface will be hindered.
Accordingly, the rupture of interface and draining of
water become more difficult. Interestingly, one can notice
that crudes with low asphaltene content generally have a
lower viscosity Table 1. Wax does have a large impact on
 EFFICIENCY EVALUATION OF NEW DEMULSIFIERS 1427

TABLE 3
Effect of asphaltene content on the demulsification efficiency for LB6 demulsifier (type ii oil emulsion with 30% water
content) at 60 C
Asphaltene Concn. Coalescence rate Separation Demulsifier
Demulsifier content (%) (ppm) constant (min=ml) Time (min) efficiency (%)

Control 0 – 74a 81
LB6 9.8 100 0.3843 91 100
200 0.5515 61 100
300 0.4923 57 100
Control 0 – 43a 30
LB6 7.18 100 0.7817 37 100
200 1.1266 24 100
300 1.3025 19 100
Control 0 0.2295 115a 90
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LB6 1.8 10 0.5516 30 80

20 0.9171 19 86.6
50 1.3638 10 93.3
a
Separation time: days.

the solution viscosity, but it has a rather low melting point.
Thus working at this high temperature through the demul-
sification (60 C) would cancel the effect of wax content on
viscosity. However, the increase in viscosity of the oil phase
upon using crudes with higher asphaltene content would
subsequently be hindered.
Surface Active Parameters
The surface active properties of the applied demulsifier
determine how fast the surfactant would orient itself at
the interfaces, which is an important factor in determining
its effectiveness. Some surface active properties (CMC,
IFT, Kp, DGmic, DGad) of LB6 are listed in Table 4. The
value of CMC together with surface tension versus the bulk
concentration were utilized to calculate Gibb’s free energy
of micellization (DGmic) and adsorption (DGad) for LB6
(Table 4). It is noticed that this demulsifier favours adsorp-
tion to micellization (more negative DGad compared with
DGmic). This behavior supports its efficiency as a demulsi-
fier that is able to displace the nature at the interface. Also,
there is a significant reduction in IFT of crude oil=water
TABLE 4
Some surface active properties of LB6
Property Value
CMC (mol dm
3) 4.01  10
5
IFT (mNm
1) 3  10
3
Partition Coefficient 0.61176
DGmic (kJ mol
1)
25.08
DGad (kJ mol
1)
25.783
emulsion by adding 100 ppm of LB6 reaching 3  10
3
mNm
1 (see Table 4). This low IFT leads to a decrease
in the stability of the interfacial film. Consequently, the
drainage of water would be easier and hence promoting
coalescence. The partition coefficient (Kp) for the investi-
gated demulsifiers approaching unity are hypotheorized
by Berger et al.[17] to optimize demulsifier performance.
The good demulsification results are supported by the
value of partition coefficient (Kp). LB6 shows Kp of 0.611
a value near unity (Table 4). This value indicates the ability
of the demulsifier to partitionate well at w=o interface.
Rheological Properties in Relation to Demulsification
Efficiency
For certain asphaltene content (7.14%), the effect of
bulk viscosity of the emulsion on the emulsion stability
was also studied using different concentrations of LB6.
Oil with a high viscosity has the ability to hold up more
and larger water droplets than oil with lower viscosity.
Lowering the viscosity by adding demulsifier increases both
the rate at which water droplets settle and the mobility of
water droplets and thereby leads to favorable collision,
coalescence, and thus increasing the rate of separation.
Table 5 shows yield value (sb), apparent viscosity (gapp)
and dynamic viscosity (gd) for 30% w=o emulsion at differ-
ent concentrations of LB6 at varied temperature. These
data show that apparent viscosity (gapp) and dynamic vis-
cosity (gd) are affected strongly by temperature i.e., they
decrease with increasing temperature. The decrease in the
emulsion viscosity is mainly due to a decrease in the
continuous phase viscosity. By treating the emulsions with
different concentrations of LB6 it was found that sb, gapp
 1428 R. A. EL-GHAZAWY ET AL.

TABLE 5
Rheological parameters for type II crude oil and its 30%
w=o emulsion at 60 C without and with different
concentrations of LB6
Temp. Concn.
Sample ( C) (ppm) sb gap gd

Control 30 – 16.4 111 0.7944

40 10.6 71.67 0.522
50 6.76 45 0.327
60 4.18 26 0.172
Emulsion 30 – 56 350.0 2.048
40 32 203.1 1.312
50 19 125.9 0.88
60 17 50.6 0.403
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LB6 30 100 13.52 179.49 0.135

40 7.406 97.747 0.105
50 4.733 59.777 0.099
60 2.898 37.436 0.047
30 200 10.62 138.67 0.346
40 7.019 91.188 0.204
50 4.347 54.711 0.124 SKETCH 2. Demulsification effect on emulsion rheology.
60 1.867 24.716 0.143
30 300 10.30 134.37 0.588 was followed up and the mechanism of demulsification was
40 6.214 80.407 0.206 suggested using the following first order rate equation:[13]
50 4.121 52.598 0.085
60 2.576 34.282 0.022 logðSÞ ¼
Kt þ C;

where K is the rate constant, t is time, and C is a constant.

and gd decrease with increasing the concentration of the
added demulsifier. This decrease in the viscosity may be
explained on the basis of droplet size of the dispersed phase
(water).[18,19] In other words, it will depend on the viscosity
of dispersion medium.
The mechanism of decreasing the continuous phase vis-
cosity is related to demulsifier treatment as shown in
Sketch 2. By following up Sketch 2: in Phase 1 (the emul-
sion 50% w=o at zero time of treatment) the droplets size
are nearly equal, by the time progresses water droplets
coalesce to reach coalescence step (Phase 2). By dynamic
rotation the dragging of water droplets occurred which is
accompanied by a decrease in the dynamic viscosity and
thus the yield value. This behavior continues till the water
clusters form (Phase 3). Clusters combine to form channel
and complete phase separation occurs (Phase 4). At this
point the viscosity of the phase drops to the original dry
crude oil viscosity.
Kinetics and Mechanism of Demulsification Process
Coalescences parameters of 30% w=o emulsion
(untreated and treated emulsions with 200 ppm of MCB14
and LB6) were investigated using microscopic photography
of samples at different time intervals. The relation between
interfacial area per gram of the dispersed phase (S) and time
Micrograph of the control emulsion sample (Figure 4)
shows a little bit growth of water droplets throughout 35
days. This observation runs in harmony with the demulsi-
fication efficiency data obtained using the bottle test
(Figures 1–3). Figures 5 and 6 demonstrate the micro-
graphs 200 ppm dosed emulsion samples of CB14 and
LB6, respectively. This may be due to the mechanical stab-
ility character of asphaltenes and resins on the interface
film that hinders the drainage of the neighboring water dro-
plets. For CB14 (Figure 5), the radius of water droplets
starts generally to increase after 30 minutes whereas the
good LB6 demulsifier shows a fast increase in the water
droplet radius from 3 to 6 minutes It can be also mentioned
that a non distinct water separation was observed for CB14
after 80 minutes (Figure 5), which actually shows 100%
efficiency after 100 minutes at 200 ppm dose. On the other
hand, a significant water separation is shown by LB6 after
24 minutes, a result that is comparable with that obtained
by the bottle test (Figure 2).
Plot of log (S) versus time of demulsification for 30%
water emulsions of a control sample and that treated with
200 ppm of CB14 and LB6 are shown in Figures 7–9. The
plateau in these figures can be divided into three parts A,
B, and C to describe the demulsification mechanism. Each
part is treated kinetically as a first order rate of a certain
 EFFICIENCY EVALUATION OF NEW DEMULSIFIERS 1429
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FIG. 4. Microscopic photography of demulsification process for control sample at 30% water of type II oil emulsions at 60 C (photo=5 days).

FIG. 5. Microscopic photography of demulsification process for CB14 sample at 30% water of type II oil emulsions at 60 C (photo=10 minutes).

FIG. 6. Microscopic photography of demulsification process for LB6 sample at 30% water of type II oil emulsions at 60 C (photo=3 minutes).
 1430 R. A. EL-GHAZAWY ET AL.
FIG. 7. Demulsification mechanism for blank sample (30% water type
II oil emulsions at 60 C).
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FIG. 8. Demulsification mechanism for 200 ppm of CB14 (30% water
type II oil emulsions at 60 C).
process. Part A points to the rate of coalescence, but Part B
indicates the rate of cluster formation, and Part C denotes
to water channel formation where at the end of this step
complete water separation occurs. This mechanism can
be also observed by following the increase in the volume
of water droplet throughout the micrographs.
FIG. 9. Demulsification mechanism for 200 ppm of LB6 (30% water
type II oil emulsions at 60 C).
TABLE 6
Rate constants of demulsification process for control,
CB14, and LB6 using 30% water of type II oil emulsions
at 60 C
Rate constants
Coalescence Cluster Channel
Sample step (A) step (B) formation (C)
Control 3.1  10
4 3.9  10
3 3.6  10
3
CB14 2.4  10
3 3  10
2 1  10
2
LB6 1.5  10
2 1.2  10
The values of rate constants (k) for each step (viz.
coalescence, cluster and channel formation) are listed in
Table 6. The control emulsion sample exhibited very slow
rates of coalescence (3.1  10
4), cluster formation
(3.9  10
3) and channel formation (3.6  10
3) after 35
day incubation period at 60 C compared with the treated
samples. Treated sample with CB14 shows an increase in
the rate constants of the three steps with a magnitude in
the order of 102. LB6 sample shows only two parts for clus-
ter and channel formation. In this instance, the coalescence
and cluster formation overlapped in one fast step. This may
be attributed to the efficient demulsification power of LB6.
These observations can be translated into application in oil
fields. It implies that treated such an emulsion system no
long mixing periods are essential for the required complete
demulsification. In other words, the distance between the
injection points and processing or transportation sites
could be short enough in the order of 25 minutes or more.
CONCLUSIONS
The conclusions of this work can be drawn as follows:
1. Efficient demulsifiers for Egyptian crude oil in water
emulsions can be prepared with utilizing local raw mate-
rials and available technique.
2. The increase in water content of the emulsion leads to
fast demulsification and only low doses of the demulsi-
fier are required.
3. The increase in the asphaltene content of the emulsion is
one of the factors that are responsible for the stability of
the w=o emulsion.
4. Low interfacial tension and Gibb’s free energy of
adsorption are required for good demulsifier.
5. The addition of the demulsifier may cause a decrease in
the viscosity of the emulsion.
6. Kinetics of the demulsification process can be followed
up by using photomicroscopy of the samples.
7. The demulsification process can be divided into three
steps: coalescence, cluster and channel formation.
 EFFICIENCY EVALUATION OF NEW DEMULSIFIERS
REFERENCES
[1] Sharma, I.C., Haque, I., and Srivastava, S.N. (1982) Colloid
Polym. Sci., 260: 616.
[2] Bhardwaj, A. and Hartland, S. (1993) J. Dispersion Sci. Tech-
nol., 14 (5): 541.
[3] Al-Sabagh, A.M. and Zaki, N.N. (1997) Tenside Surf. Det.,
34: 12.
[4] Al-Sabagh, A.M., Nehal, S.A., Amal, M.N., and Gabr, A.M.
(2002) Polym. Adv. Technol., 13: 346.
[5] Al-Sabagh, A.M., Badawi, A.M. and Noor El-Din, M.R.
(2002) Petrol. Sci. Technol., 20: 887.
[6] Al-Sabagh, A.M., Nehal, S.A., Amal, M.N., and Gabr, A.M.
(2003) Colloids Surfaces A: Physicochem. Eng. Aspects, 216: 9.
[7] Al-Sabagh, A.M., Noor El-Din, M.R., and Mohamed, H.
(2006) Egypt. J. Petrol., 15 (1): 49.
[8] Al-Sabagh, A.M., Maysour, N.E., Naser, M.N., and
Downloaded by [Fondren Library, Rice University ] at 09:03 26 September 2012
Noor El-Din, M.R. (2007) J. Dispersion Sci. Technol., 28: 537.
[9] Al-Sabagh, A.M., Maysour, N.E., and Noor El-Din, M.R.
(2007) J. Disersion Sci. Technol., 28: 547.
[10] Al-Sabagh, A.M., Noor El-Din, M.R., Morsi, R.E., and
Elsadee, M.Z. (2008) J. Appl. Polym. Sci., 108: 2301.
1431
[11] Furniss, B.S., Hannaford, A.J., Smiths, P.W.G., and
Tatchell, A.R. (1989) Vogel’s Textbook of Practical Organic
Chemistry; 5th Ed.; New York: Longman.
[12] Rheimeck, A.E. and Khoe, T.H. (1969) Fette Seifen
Anstrichm, 71: 644.
[13] Anil, B. and Hartland, S. (1994) J. Dispersion Sci.
Technology, 15(2): 133.
[14] Shetty, C.S., Nikolvo, A.D., and Wasan, D.T. (1992)
J. Dispersion Sci. Technol., 13: 121.
[15] Young, H.K. and Drash, T.W. (1996) Ind. Eng. Chem. Res.,
35: 1141.
[16] Mark, A.K., Darsh, T.W., and Chandashekar, S.S. (1991)
Ind. Eng. Chem. Res., 30 (2): 367.
[17] Berger, P.D., Hsu, C., and Arendell, J.P. (1987) Designing and
selecting demulsifier for optimum field performance based on
production fluid characteristics. Society of Petroleum
Engineers, Dallas, TX, pp. 522–526.
[18] Chong, J.S., Christiansen, E.B., and Bear, A.D. (2007)
J. Appl. Polym. Sci., 15: 2007.
[19] Metzner, A.B. (1985) J. Rheol., 29: 739.