ORIGINAL ARTICLE

Water pH and surfactant addition eects on the stability

of an Algerian crude oil emulsion
Mortada Daaou
a,
*
, Dalila Bendedouch
b
a
Department of Industrial Chemistry, Faculty of Sciences, University of Sciences and Technology of Oran, P.O. Box 1505,
El mnaouer, Oran 31000, Algeria
b
Laboratory of Macromolecular Physical Chemistry, Faculty of Sciences, University of Oran (Es-senia), Oran 31000, Algeria
Received 25 January 2011; accepted 29 May 2011
Available online 1 July 2011
KEYWORDS
Emulsion stability;
Test-bottle;
Optical microscopy;
pH;
Crude oil;
Surfactant
Abstract In many oil production sites water injection is used as a piston to push the crude out of
the well. As the age of the eld progresses, the ratio of water to oil produced increases. Agitation of
a water and crude oil mixture may give stable water-in-oil emulsion in which the water remains dis-
persed for a long period of time. These emulsions can cause severe problems in production and
transport processes since they normally possess high stability and viscosity. The most important
water properties which may contribute to the emulsion stability include pH and additive content.
In this study, we report on the effect of both, water pH and the presence of surfactant molecules
(anionic, cationic or non-ionic) on the stability of an Algerian crude oil (Haoudh el Hamra well)
aqueous emulsion prepared by a mechanical agitation procedure. The stability was followed by
the test-bottle method to measure the resolved water separated from the emulsion, and optical
microscopy to visualize the dispersed water droplets in the oil phase. The results of the effects of
varying the aqueous-phase pH suggest that the neutral medium is more efcient than acidic or basic
environment for stabilizing the emulsions. The addition of non-ionic surfactants has a better poten-
tial to improve crude oil emulsion stability with respect to both cationic and anionic surfactants
which do not show any improvement in the oil/water phase compatibility.
2011 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.
1. Introduction
Water in oil emulsion formation occurs at many stages in the
production and treatment of crude oil. Water is used as a pis-
ton to push the crude out of the well during the process of oil
production and to remove species such as chloride salts which
poison renery catalysts and enhance corrosion problems dur-
ing renery treatment. Agitation of a water and crude oil mix-
ture may yield stable water-in-oil emulsion in which water
remains dispersed for a long period of time. These emulsions
can cause severe problems in production, transport and
*
Corresponding author. Tel.: +213 550444965.
E-mail address: daaou_mortada@yahoo.fr (M. Daaou).
1319-6103 2011 King Saud University. Production and hosting by
Elsevier B.V. All rights reserved.
Peer review under responsibility of King Saud University.
doi:10.1016/j.jscs.2011.05.015
Production and hosting by Elsevier
Journal of Saudi Chemical Society (2012) 16, 333337
King Saud University
Journal of Saudi Chemical Society
www.ksu.edu.sa
www.sciencedirect.com
treatment processes since they normally possess high stability
and viscosity. Water can form gas hydrates and is also respon-
sible for corrosion problems. Thus, for other reasons too, it is
of interest to dehydrate the crude oils. An understanding of the
stabilization mechanism and knowledge of the factors which
affect this stabilization is a major concern of several authors
(Mingyuan et al., 1992; McLean and Kilpatrick, 1997b;
Gafonova and Yarranton, 2001; Li et al., 2002; Havre and
Sjo blom, 2003; Ese and Kilpatrick, 2004). It is shown (McLean
and Kilpatrick, 1997a,b; Yarranton et al., 2000) that the stabil-
ity of water in crude oil emulsion depends mainly on a rigid
protective lm encapsulating the water droplets. It is believed
that this interfacial lm is composed predominantly by natural
surfactants contained in crude oil i.e. asphaltenes, resins and
fatty acids (Sjo blom et al., 1992; Spiecker and Kilpatrick,
2004). These substances may accumulate at the wateroil inter-
face and hinder the droplets to coalesce and phase separate.
Among these components, asphaltenes are believed to be the
major ones stabilizing the emulsion. Indeed, most of the time,
the other two components, cannot alone produce stable emul-
sions (Lee, 1999). Moreover, they may in some cases associate
to asphaltene molecules and affect emulsion stability. In par-
ticular, resins could solubilize asphaltenes in oil by the way
preventing them from associating in order to form the interfa-
cial lm and, therefore, lower the emulsion stability. The
asphaltenes represent the heaviest and most polar fraction of
the crude oil and their representative molecule contains mainly
a sheet of more or less condensed aromatic rings with aliphatic
side chains and various functional groups (Strausz et al., 1992;
Daaou et al., 2006; Bouhadda et al., 2007; Daaou et al., 2009).
With these structural characteristics, asphaltenes exhibit sur-
face activity and act as natural emulsiers (see Fig. 1; Taylor,
1992; Sheu et al., 1995; Schildbreg et al., 1995; McLean and
Kilpatrick, 1997a,b; Sztukowski et al., 2003). However, they
do not operate as individual molecules, but through an aggre-
gated state (McLean and Kilpatrick, 1997a). The interfacial
lm is not monomolecular but is constituted by asphaltene
aggregates which accumulate at the surface of the water drop-
lets. Consequently, the propensity of asphaltenes to occulate
in crude oil enhances the water-in-oil emulsion stability
(Sztukowski et al., 2003). This is the case of the Algerian crude
oil from the Haoudh El Hamra well in the Hassi Messaoud oil
eld whose production is continuously perturbed by the aggre-
gation and deposition of asphaltenes (Daaou et al., 2009).
Therefore, it appeared of some interest to study the stability
of aqueous emulsions containing this particular oil.
The interfacial lm and hence the emulsion stability can be
affected by many factors like water-pH and additive content
(Schramm, 1992; Poteau et al., 2005; Fortuny et al., 2007). Lit-
erature reports a multitude of pH and chemical addition effects
on crude oil/water systems which show different behaviors for
different oil origins (Strassner, 1968; Pathak and Kumar, 1995;
McLean and Kilpatrick, 1997a; Goldszal et al., 2002). For in-
stance, Poteau et al.(2005), show that pH has a strong inuence
on interfacial properties of asphaltenes at the Venezuelan
crude oil/water interface and that at high or low pH, asphalt-
enes functional groups become charged, enhancing their sur-
face activity. Recently, Fortuny et al. (2007) studied the
effects of salinity, temperature, water content and pH on the
stability of crude oil emulsions upon microwave treatment
and found that the demulsication process was achieved with
high efciencies for emulsions containing high water contents
except when high pH and salt contents were simultaneously
involved.
Emulsion destabilization occurs in several steps (Graham
et al., 2008): occulation, coalescence, and nally phase sepa-
ration or sedimentation. The occulation of water droplets in
water-in-oil emulsions involves their aggregation in order to
form clusters. During the coalescence step, the clusters fuse
to form larger droplets, this process can eventually lead to
phase separation or sedimentation under the inuence of grav-
ity. Emulsion stability may be determined by a number of
methods, such as the bottle test and electrical methods (Wang
and Alvarado, 2009). The most common method in the lab-
scale is the simple bottle test: varied amounts of potential
demulsiers are added into a series of tubes or bottles contain-
ing each the same amount of an emulsion to be broken (Mat,
2006). More recently, Moradi et al. (2011) studied the effect of
salinity on water-in-crude oil emulsion through the measure of
droplet-size distribution visualized by an optical microscopy
method. They indicate that emulsions are more stable at lower
ionic strength of the aqueous phase, a result consistent with
those obtained by electrorheology and bottle tests (Wang
et al., 2010).
The present work investigates the inuence of both water
pH and the addition of surfactants (cationic, anionic and
non ionic) on the stability of a model emulsion made of
40 vol.% of the Algerian Haoudh El Hamra crude oil and
60 vol.% of water. It is designed as an attempt to contribute
to the understanding of this water-in-oil emulsion behavior
in order to provide ultimately technologic responses to some
oil production problems specic to this crude. Sodium dodecyl
sulfate (SDS), dodecyl triphenylphosphonium bromide
(DTPB) and decyl-tri-oxyethylene alcohol (C
10
E
3
) are selected
since they are well known compounds representative of each
surfactant type. The optical microscopy is used to conrm
Figure 1 Mechanism of emulsion stabilization: asphaltenic thin
lm formation at the oil/water interface (McLean and Kilpatrick,
1997a,b).
334 M. Daaou, D. Bendedouch
the water-in-oil emulsion type and the bottle test method is
employed to evaluate the emulsion stability.
2. Experimental
2.1. Chemicals
The oil is from Haoudh el Hamra well of the Algerian Hassi-
Messaoud eld. Its general specications are given in Table 1
as determined by the Renery Company laboratory.
The different chemicals used in this work were purchased
from Sigma products Company with a nominal purity of 98%.
2.2. Emulsion preparation
2.2.1. Water pH effect
The aqueous solutions of different pH were prepared by mix-
ing adequate amounts of NH
4
OH in demineralized distilled
water for basic solutions (pH: 813), whereas acidic medium
(pH: 26) was prepared with HCl in water. The pH value for
each solution was controlled by a digital pH meter Model
IN-112 apparatus.
Sixty milliliters of the aqueous phase at different pH was
added to 40 ml of the crude oil. The mixture was then homog-
enized by mechanical agitation (Ultra Turrax T 25 basic, IKA-
Werke) at 2500 rpm during 15 min at 20 C.
2.2.2. Surfactant addition effect
Sixty milliliters of brine water containing 3.5 wt% of NaCl and
100 ppm of one of the surfactants were added to 40 ml of crude
oil and homogenized as described in the previous section. The
operation was repeated for each surfactant. An aliquot of each
sample was immediately poured into a 10 ml graduated bottle
which was left to stand at 20 C up to 24 h until water sepa-
rated (Daaou et al., 2005a,b).
2.3. Emulsion stability determination
The stability was monitored by measuring the volume of sep-
arated water from the emulsion by the test bottle method. In-
deed, the lower the emulsion stability, the larger the water
partition. The amount of separated water is directly correlated
to the instability of the emulsion since destruction of the inter-
facial lm and subsequent water droplet coalescence is the
determinant step in the demulsication process (McLean and
Kilpatrick, 1997a).
2.4. Water droplet dispersion visualization
An Axiostar optical microscope (Carl Zeiss) using a 40 objec-
tive with 0.45 lm resolution is used to visualize dispersed water
droplets in the oil phase to conrm the existence of water in oil
(w/o) type emulsion (Balinov et al., 1994; Nandi et al., 2003;
Zhang et al., 2009; Moradi et al., 2011). The sample images
corresponding to a stable emulsion are taken with a digital
Sony camera.
3. Results and discussion
3.1. Effect of water pH
The emulsion samples left to stand are observed and the results
are depicted in Fig. 2a. Obviously, aqueous-phase pH affects
the emulsion stability. For acidic medium, the separated water
volume varies from 3 vol.% to 36 vol.% as water pH varies
from 1 to 6. The largest volume (36%) is reached at pH = 6.
In the basic medium (pH = 813), separated water is com-
prised between 2 vol.% and 15 vol.%. The least stable emul-
sion occurs for weakly acid environment. At pH = 7, the
emulsion is the most stable since no water separates and the
w/o emulsion type is conrmed by optical microscopy which
visualizes the dispersion of water droplets in the oil phase
(Fig. 2b). The system is also relatively stable at very low and
moderately basic pH. These results are comparable to those
obtained by Strassner (1968) who studied crude oil emulsions
at different pH values and found that Venezuelan crude oil
Table 1 General characteristics of Hassi-Messaoud crude oil.
Density d
20
4
0.83
Total acid number (mg KOH/1 g) 0.28
Asphaltenes (wt%) 0.60
Resins (wt%) 6.50
Resins/asphaltenes 10.80
Figure 2 (a) Separated water volume for various water pH. (b)
Water droplet dispersion in the crude oil at pH = 7 (optical
microscopy).
Water pH and surfactant addition effects on the stability of an Algerian crude oil emulsion 335
emulsions at pH < 6 are highly stable, while those at pH > 10
exhibit low stability or are highly unstable although at
pH = 13 the emulsion was very stable.
The pH effect on emulsion stability is usually attributed to
ionization of polar groups of surface active components which
induce sufcient electrostatic repulsive interactions to break
down the interfacial lm cohesion (McLean and Kilpatrick,
1997a).
The residual aqueous-phase pH after demulsication is
plotted as a function of the corresponding initial pH in
Fig. 3. The plot shows that it is consistently less acidic when
the initial pH is acidic and less basic when the initial pH is
basic. This suggests that the native surface active compounds
in the crude adsorbed at the oil/water interface contain
strongly basic as well as weakly to strongly acidic functional
groups. Indeed, the total acid number of this Algerian crude
oil, as given on Table 1 classes it among the less acidic crudes.
Depending on the pH, the functional groups may dissociate
into the aqueous phase upon emulsication giving rise to large
surface charge densities and subsequent internal repulsion in
the lmthat destroy the lmstructure (McLean and Kilpatrick,
1997a,b).
3.2. Effect of surfactant addition
Fig. 4 is a plot of the amounts of separated water against added
surfactant type (anionic, cationic and non-ionic) 24 h after the
sample preparation. It is noticed that the maximum stability is
observed for the emulsion containing the non-ionic surfactant,
whereas the ionic surfactants confer lesser stability to the
emulsion.
Fig. 5 shows the kinetic emulsion stability for each of the
three surfactants. After 24 h, separated water is equal to 85,
82 and 18 vol.% for added DTPB, SDS and C
10
E
3
, respec-
tively. These observations conrm that the emulsion which
contains the non-ionic surfactant remains the most stable
one. In the case of the ionic surfactants the polar head groups
probably prevent or inhibit the formation of the associated
asphaltene lm at the oil/water interface leading to important
emulsion instability.
4. Conclusion
The instability of this Algerian crude oil-in-water emulsion is
enhanced either by water pH induced ionization of the polar
groups of the surface active components or the presence of
electrically charged ionic surfactant heads imbedded in the
interfacial lm. Both circumstances induce sufcient electro-
static repulsive interactions to break down the interfacial lm
cohesion. This observation may be straightforwardly valued in
an efcient demulsication process.
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Water pH and surfactant addition effects on the stability of an Algerian crude oil emulsion 337