Petroleum Science and Technology

This article was downloaded by: [McGill University Library]
On: 18 August 2012, At: 02:07

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Petroleum Science and Technology

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lpet20
BREAKING WATER-IN-CRUDE OIL EMULSIONS BY NOVEL

DEMULSIFIERS BASED ON MALEIC ANHYDRIDE–OLEIC
ACID ADDUCT
a a a
A. M. Al-Sabagh , A. M. Badawi & M. R. Noor El-Den
a
Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
Version of record first published: 14 Feb 2007
To cite this article: A. M. Al-Sabagh, A. M. Badawi & M. R. Noor El-Den (2002): BREAKING WATER-IN-CRUDE OIL EMULSIONS BY
NOVEL DEMULSIFIERS BASED ON MALEIC ANHYDRIDE–OLEIC ACID ADDUCT, Petroleum Science and Technology, 20:9-10, 887-914
To link to this article: http://dx.doi.org/10.1081/LFT-120003685
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to
anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should
be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims,
proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in
connection with or arising out of the use of this material.
MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
PETROLEUM SCIENCE AND TECHNOLOGY

Vol. 20, Nos. 9 & 10, pp. 887–914, 2002
BREAKING WATER-IN-CRUDE OIL

EMULSIONS BY NOVEL DEMULSIFIERS
Downloaded by [McGill University Library] at 02:07 18 August 2012
BASED ON MALEIC ANHYDRIDE–OLEIC

ACID ADDUCT
A. M. Al-Sabagh,* A. M. Badawi, and

M. R. Noor El-Den
Egyptian Petroleum Research Institute,

Nasr City, Cairo, Egypt
ABSTRACT
This paper mainly concentrates on synthesis of ten novel

demulsifiers and investigate their demulsification efficiency.
The demulsifiers were derived from oleic acid–maleic
anhydride adduct (OM), which prepared by reaction of oleic
acid with maleic anhydride. The reaction was carried out
between the OM adduct and the following compounds to form
the correspondence demulsifiers; triethanolamine (OMTEA),
triglycerol (OMTG), cetylamine (OMCA), triethanolamine
with lauryl alcohol (OMTEA–LA), triethanolamine with cety-
lamine (OMTEA–CA), polyethylene glycol 600 (one mole
(OM e.o. 13.6)), polyethylene glycol 600 (two moles (OM
e.o. (13.6) 2)), polyethylene glycol 1000 (OM e.o. 22.7),
triethanolamine with polyethylene glycol 1000 (OMTEA e.o.
22.7) and triethanolamine with polyethylene glycol 6000
*Corresponding author.
887
DOI: 10.1081/LFT-120003685 1091-6466 (Print); 1532-2459 (Online)
Copyright & 2002 by Marcel Dekker, Inc. www.dekker.com
888 AL-SABAGH, BADAWI, AND NOOR EL-DEN
(OMTEA e.o. 136.4). The chemical structures of the OM

adduct and some selected demulsifiers were confirmed by
1
H NMR and FTIR. A wide range of demulsifier properties
can be obtained by changing the degree of functionalization
of the base molecules. The demulsification efficiency of these
demulsifiers was tested on w/o emulsions with 10, 30 and 50%
water content. From the obtained data, it has found that,
the investigated demulsifiers are having a great potential to
break the w/o emulsions completely in different times. The
(OMTEA e.o. 136.4) was exhibited the minimum time taken

to complete separation. The data were discussed on the light
of the chemical structure of the demulsifiers and the factors,
which effect on the demulsification process.
Key Words: Demulsifier; Monomeric surfactants; Emulsion

breakers; Emulsion resolution; Water-in-oil emulsion; Demul-
sification process; Breaking of w/o emulsions
INTRODUCTION
There is an increasing number of crude oil fields that are now produc-
ing both crude oil and water; such fields are both onshore and offshore
(Graham, 1988). The water co-produce with the crude oil can coexist in
reservoir with the crude oil in the so-called aquifer layer, which lies beneath
the crude oil zone as a second stage recovery to maintain the reservoir
operating pressure and fluid flow profile. The water produced with the
crude oil may be as a discrete phase as it flows up the well riser, but it is
mixed into the crude oil at the wellhead chokes and valves where there is
significant mixing and turbulence and pressure drops. The water-in-crude oil
emulsion so produced then will be stabilized by the variety of natural sur-
factant in the crude oil (Ivanov, 1974; Graham, 1979 and Bride, 1980). In
many processes, the formation of emulsions is undesirable and although
they are not thermodynamically stable, their rate of coalescence may be
too slow in practical situations. Emulsions, being thermodynamically
unstable, often require only a slight disturbance to speed up their resolution.
Heating, freezing, shearing, and the application of an electrical field have all
been used successfully to break emulsions. Where feasible, addition of small
concentration of chemical demulsifiers can be very simple and cost-effective.
An excellent example comes also from the area of petroleum production.
Conventional light crude oils are produced with considerable quantities of
water, which become emulsified (w/o) in the oil as it passes through the
NOVEL DEMULSIFIERS DERIVED FROM OM 889
region of very high shear at the wellhead choke. The water is removed,
preferable before transmission along pipelines, by sedimentation, which is
greatly speeded up by adding very low concentration of chemical demulsi-
fiers that promote coalescence of the water to form large droplets. A huge
number of surface-active materials have been patented as demulsifiers for
this application, ranging from simple surfactants to high molecular weight
polymers. The mechanism of their action involves flocculation of the indi-
vidual water droplets followed by coalescence. As a consequence, better
results are usually obtained with mixed demulsifiers. The most effective
demulsifiers act by displacing pre-formed rigid interfacial films composed

of indigenous surfactants in the crude oil, such as asphaltenes (Jones, 1978).
The chemical demulsification is a process in which the film-thinning rate is
enhanced and stability of the film is reduced by the chemical demulsifier. It
has been established that the role of the demulsifier is to change the inter-
facial rheological properties and to destabilize the surfactant, emulsion films
(Eley, 1987 and Mohammed, 1993). Most commercial chemical demulsifiers,
which are used to breakup water-in-oil (w/o) emulsions are oil soluble. The
interfacial activity of these oil-soluble demulsifier molecules is controlled by
the rate of the bulk diffusion process from the bulk phase to the interface
and the adsorption barrier at w/o interface. Usually the commercial chemi-
cal demulsifier is a blended mixture of several components, which have
various chemical structures and polymeric materials, as well as a wide mole-
cular weight distribution. In this case, each component of the demulsifier
formulation possesses a different partitioning ability and a different inter-
facial activity due to various chemical structures or types (Mohammed,
1994). The w/o emulsions have their stability from the presence of asphal-
tenes, which are condensed aromatic rings containing saturated carbon
chain and naphthenic rings as substituents, along with a distribution of
heteroatoms and metals (Little, 1974). Asphaltene are capable of cross link-
ing at the water drop–oil interface and preventing them from coalescence
(McMahon, 1992 and Zaki, 1997). The present work deals with the prepara-
tion of novel demulsifiers based on oleic acid–maleic anhydride adduct.
The attention was extended to evaluate them as emulsion breakers for
w/o emulsions.
EXPERIMENTAL
Crude Oil Type
Asphaltenic crude oil was submitted from Suez Oil Company

(SUOCO). The general physicochemical properties are shown in Table 1.
Table 1. Physicochemical Properties of Used Crude Oil
Specification Method Asphaltenic Crude Oil
Specific gravity (60/60 F) IP160 0.874

API gravity at 60 F IP160 40.955
Kinematic viscosity at 60 F (cSt) IP71 222.87
Asphaltene content (wt%) IP143 7.18%
Paraffin wax (wt%) UOP46 3.1%
Water content ASTM, D-4006 0.5%
Preparation of Oleic Acid–Maleic Anhydride Adduct (OM)
In a 1 l three-necked round bottom flask, fitted with a condenser, a

mechanical-stirrer and a thermometer. one mole of maleic anhydride was
heated with 1 mole of oleic acid for 2–3 h with stirring at 180–190 C
(Chales, 1947).
Preparation of the Demulsifiers
Preparation of Mono- and Di-derivatives of OM Adduct
In a 250 ml one-necked flat bottom flask fitted with Dean-Stark

and condenser, 0.1 mole of OM adduct was esterified or amidated with
0.1 mole of alcohol or cetylamine as shown in Table 2, to produce the
mono derivatives or as shown in Table 3 to produce the di-derivatives.
The reaction gradients were heated at 140 C in the presence of 20 ml
xylene as a solvent and 0.1 g% p-toluene sulfonic acid as a catalyst with
continuous stirring, until the theoretical amount of water was collected.
Then the solvent distilled off and the product was washed with hot water
several times and dried.
Preparation of Water-in-Crude-Oil Emulsions
In a 250 ml beaker, the crude oil was stirred at 25 C (200 rpm), while
seawater was added gradually to the crude oil with continuous stirring, until
the two phases become completely homogenized. The emulsion was pro-
nounced with different ratios of crude oil to water (90 : 10), (70 : 30) and
(50 : 50) respectively.
Table 2. Alcohols and Amines Reacted with the Adduct and the End Product
Alcohol and Amine Chemical Structure of Mono-derivatives Mono-derivative

(Reacted Compound) Adduct (End Product) Adduct (Abb.)
Triethanolamine OMTEA
Triglycerol OMTG
NOVEL DEMULSIFIERS DERIVED FROM OM
Polyethylene (OM e.o. 13.6)

glycol (e.o. 13.6)
Cetylamine OMCA
e.o.: ethylene oxide; p.o.: propylene oxide.

891
892
Table 3. Alcohols and Amines Reacted with the End Products in Table 2 and the End Products of Them
Mono-derivative Chemical Structure of Di-derivatives Adduct

Adduct (Abb.) Alcohol and Amine Di-derivatives Adduct (End Product) (Abb.)
OMTEA Polyethyleneglycol (OMTEA e.o. 22.7)

(e.o. 22.7)
OMTEA Polyethyleneglycol (OMTEA e.o. 136.4)

(e.o. 136.4)
OMTEA Lauryl alcohol OMTEA–LA
Polyethylene Polyethyleneglycol ((OM e.o. 13.6) 2)

glycol (e.o. 13.6) (e.o. 13.6)
OMCA Triethanolamine OMCA–TEA

AL-SABAGH, BADAWI, AND NOOR EL-DEN

Bottle Test
The bottle test is used to estimate the efficiency of demulsifiers to

resolve the water-in-oil emulsions. The demulsifier in xylene was added to
100 ml water-in-crude oil emulsion at different ppms. The mixture was stir-
red and placed in a 100 ml graduated bottle tightly stoppered with Teflon
lids. The bottle then placed in a thermostatic water bath. Water separation
(in ml) was observed every 10 min. A blank is used in each set of experiment
(Young, 1996).
RESULTS AND DISCUSSION
Chemical Structure
Spectral Analysis of Oleic Acid–Maleic

Anhydride (OM) Adduct
The 1H NMR spectrum of (OM) as shown in Figure 1 shows that,

the chemical shift at (2.3–2.5) for H proton (a) and (5.16–5.2) for H
proton (b). While the absence of the double bond C¼CH stretching vibra-
tion at 1650 cm1, out of plan bending vibration at 780–830 cm1 and in
plane bending vibration at 1415 cm1 in FT-IR spectrum, as shown in
Figure 2, with 1H NMR together confirm the predicted structure of OM
adduct.
Spectral Analysis of (OM e.o. 22.7) and OMCA as

Representative Demulsifier Samples
The 1H NMR spectra as shown in Figure 3 shows that the main char-
acteristic peak (–CH2–COO–CH2–) for demulsifier (OM e.o. 22.7) was found
at chemical shift (3.4–3.6). The chemical shifts (5–5.7) for (–CH2–O–)
and the absence of chemical shift for H proton of COOH group at (12).
While the FT-IR spectra, as shown in Figure 4 for the same demulsifier
shows that, the stretching vibration for the main characteristic band of the
ester group (–COO–) at 1733 cm1. The two confirms 1H NMR and FT-IR
predicted the chemical structure of (OM e.o. 22.7). The 1H NMR spectrum, as
shown in Figure 5, for the demulsifier OMCA shows the main characteristic
bands (–CONH–CH ¼ CH2) at (3–3.35). On the other hand, the FT-IR for
OMCA as shown in Figure 6, shows that, the main characteristic peaks

1
Figure 1. H NMR spectrum for OM.
Figure 2. FT-IR spectrum for OM.


1
Figure 3. H NMR spectrum for (OM e.o. 22.7).
Figure 4. FT-IR spectrum for (OM e.o. 22.7).


1
Figure 5. H NMR spectrum for OMCA.
Figure 6. FT-IR spectrum for OMCA.

(CONH) at 3318 cm1 and out of plane vibrational binding band at

1635 cm1.
Factors Effecting Demulsification
The Chemical Structure of the Demulsifiers
A series of experiments were performed for seek to the comparison

between demulsifier chemical structure as a factor affecting demulsification

efficiency (Ivanov, 1974). The demulsification efficiency for the OM adduct
before further modification of its chemical structure was carried out.
Figure 7, shows that, the time taken for complete water separation in
hour : minutes (5 : 05, 4 : 05 and 3 : 15), (4 : 20, 3 : 00 and 2 : 17) and (3 : 25,
2 : 40 and 1 : 55) against 10, 30 and 50% water content at 50, 100 and
200 ppm of OM concentrations respectively. The different types of demul-
sifier based on oleic acid–maleic anhydride (OM) adduct were investigated;
OMTEA, OMTG, OMCA, OMTEA–LA, OMTEA–CA, (OM e.o. 13.6),
(OM e.o. (13.6) 2), (OM e.o. 22.7), (OMTEA e.o. 22.7) and (OMTEA e.o.
136.36). The comparison between these demulsifiers were held at 100 ppm
concentrations, 30% water content, 70% crude oil (w/o emulsion) at 60 C.
From Figures 8–17, it was found that the maximum demulsification effi-
ciency (water coalescence %) for OMTEA was obtained after 3 : 56 h. But
the demulsifiers OMCA, OMCA–TEA pronounced the maximum
demulsification efficiency (100 % water separation) after 1 : 45 and
2 : 12 h, respectively. The demulsifies of (OM e.o. 13.6), (OM (e.o. 13.6)
2), (OM e.o. 22.7), (OMTEA e.o. 22.7) and (OMTEA e.o. 136.4) were
exhibited the 100% water coalescence after 1 : 18, 1 : 42, 1 : 24, 1 : 37 and
1 : 20, respectively. This observation may be due to the difference in their
partition coefficients as the result of the change of the chemical structure.
In the case of partitional system the presence of demulsifier in the oil and
water drop phases, leads to its adsorption from both phases, the rate
of demulsifier adsorbed on w/o interface is improved and a high effi-
ciency of demulsification was obtained. The partition coefficient for
asphaltenes/resins, which are stabilizing surfactants of w/o emulsions
and virtually insoluble in deionized water are zero. The partition coeffi-
cients, which greater than unity are indicative of preferentially water-
soluble compounds. While the oil soluble compounds are characterized
by partition coefficients less than unity. Wherein the partition coefficient is
defined as a ratio of demulsifier concentration in water phase into oil phase
(Averyard, 1992). It has been found that, the demulsification efficiency
enhances if the demulsifier molecule has the amphiphilic character.

Figure 7. Coalescence percentage vs. time for OM at different ppm concentrations

and 60 C.

Figure 8. Coalescence percentage vs. time for OMTEA at different ppm concen-
trations and 60 C.

Figure 9. Coalescence percentage vs. time for OMTG at different ppm concentra-
tion and 60 C.

Figure 10. Coalescence percentage vs. time for OMCA at different ppm concentra-
tions and 60 C.

Figure 11. Coalescence percentage vs. time for (OM e.o. 13.6) at different ppm
concentrations and 60 C.

Figure 12. Coalescence percentage vs. time for (OM e.o. 22.7) at different ppm

Figure 13. Coalescence percentage vs. time for OMTEA–LA at different ppm con-
centrations and 60 C.

Figure 14. Coalescence percentage vs. time for OMTEA–CA at different ppm con-
centrations and 60 C.

Figure 15. Coalescence percentage vs. time for ((OM e.o. 13.6) 2) at different ppm

Figure 16. Coalescence percentage vs. time for (OMTEA e.o. 22.7) at different ppm

Figure 17. Coalescence percentage vs. time for (OMTEA 136.36) at different ppm
Since an amphiphile is a molecule that possesses a hydrophobic part and

a hydrophilic part, it is slightly soluble both in the oil and water phases. In
fact the demulsifier is initially added to the continuous oil phase. The
demulsifier, which soluble only in water is not effective. The demulsifiers,
which possess a partition coefficient of unity, have the optimum perfor-
mance (Berger, 1987).
Effect of Demulsifier Concentration

Several sets of experiments were carried out to show the effectiveness

of the demulsifier concentration on the demulsification process. The results
were taken against 50, 100 and 200 ppm at different water content (10, 30
and 50%) at 60 C. The data plotted in Figures 8–17 reveal that,
the increasing of demulsifier concentration leads to minimize the
time taken to complete demulsification (water resolution). The increasing
of demulsifier concentration may be leads to increase the rate of
partition coefficient and to increase the adsorption of the demulsifier
molecules on the water/oil interface. This remarkable may be strongly
affects the w/o dynamic interfacial properties such as interfacial
gradient or Marangoni-Gibbs stabilizing effect. At the three different
concentrations, the all investigated demulsifier exhibited the maximum
demulsification (100% water separation) but the time taken for the
separation differs from demulsifier to the other. This may be due to the
difference of demulsifiers chemical structure which enhance the adsorp-
tion on the interface between water and oil in w/o emulsion (Young,
1996).
Effect of W/O Emulsion Ingredients
The water content in w/o emulsion may be playing an effective

role on efficiency of the demulsifiers. To investigate this parameter the
ratios of (10, 30 and 50% water content) were introduced to the oil
phase to pronounce a different w/o emulsion. By inspection the data
illustrated in Figures 8–17, it was found that, the maximum efficiency of
the water coalescence was obtained when the water content increases.
Generally in asphaltenic crude oil, the w/o emulsion was stabilized by
the highly mechanical stability of asphaltene (Zaki, 1997). In the low
water content, in w/o emulsion, the drainage of water is so difficult
because the internal water pressure of water droplets is less than
the external pressure of the continuous phase, this may leads to decrease
the chance of water droplets to collect, to growth up and thinning

the film interface (Young, 1996). On the other hand from the same
Figures 8–17 it can be shown that, the increasing of water content up to
30 and 50% leads to minimize the time taken to complete the demulsifica-
tion process. This behavior may be due to the increasing of the water
content, increases of the film thinning at the interface and enhances the
drainage velocity.
Effect of Temperature on the Demulsification Process
The demulsifier (OM e.o. 22.7) (HLB ¼ 15.3) was chosen to inves-
tigate the effect of temperature gradient on the water coalescence at (30,
45 and 60 C) with demulsifier concentration 100 ppm with crude oil
(Asph.% ¼ 7.14). The plotted data in Figure 18 reveal that, the time
taken to complete coalescence was obtained at (4 : 43, 3 : 38 and
2 : 46 h), (3 : 49, 2 : 53 and 1 : 54 h) and (1 : 55, 1 : 24 and 1 : 02 h) against
the temperature respectively. This remarkable may be due to, the increas-
ing of temperature from 30 to 60 C results in a substantial decreasing of
viscosity which leads to ease the adsorption of the demulsifier on the
interface (Venugopal, 1985). The partition coefficient may be increases
with increasing the temperature, so the distribution of the demulsifier
molecules may be equalized in the two phases (water and oil), at this
point the maximum coalescence of the water droplets will be obtained
(Graham, 1983).
The Relevance HLB of Demulsifiers on Demulsification Process
The demulsifiers have different HLB values were investigated to

know the relevance of HLB to the demulsification process (expressed in
time taken). Table 4 reveals that, the HLB values of the nine demulsifiers.
The data obtained of the demulsification show that, there is no clear
relation between the HLB values of the demulsifiers and their demulsifica-
tion efficiency. Some investigators (Singh, 1991; Schramm, 1992 and
Sharma, 1982) reported that, there was a relationship between HLB and
maximum demulsification efficiency for a series of polyalkylphenol
and their demulsification efficiency at HLB range 12–13.5. This may be
due to the change of the chemical structure depends on the alkyl
group length (Zaki, 1997). The undertaken demulsifiers have no clear
relationship between the demulsification efficiency and the HLB. This

Figure 18. Coalescence percentage vs. time for (MO e.o. 22.7) at 100 ppm and (a)
30 C, (b) 45 C, respectively.
Table 4. The General Characterisation of Mono- and Di-derivatives of OM
Mono-, Di-Derivatives Molecular Phase and Color

Adduct (Abb.) Weight HLB Solubility at 25 C
(OMTEA e.o. 136.36) 6511 18.7 Soluble Viscous, black

((OM e.o. 13.6) 2) 1562 15.32 Soluble Viscous, brown
(MOTEA e.o. 22.7) 1511 14.38 Insoluble Viscous, brown
(MO e.o. 22.7) 1362 15.31 Soluble Viscous, brown
(MO e.o. 13.6) 962 13.35 Soluble Viscous, brown
MOTEA–LA 697 5.05 Insoluble Viscous, brown

MOTG 602 8.73 Soluble Viscous, brown
MOTEA 511 6.88 Insoluble Viscous, brown
MOCA–TEA 752 5.97 Insoluble Viscous, brownish
black
MO CA 603 2.3 Soluble Viscous, brownish
black
behavior may be due to changing of the hydrophilic groups of these

demulsifiers.
CONCLUSION
The conclusion can be drawn in the following points:

1. The chemical structure of the demulsifiers, which contain poly-
ethylene glycol (e.o. 13.6, 22.7 and 13.64) may be play a central
role to facilitate the partition coefficient, which maximize the
demulsification efficiency.
2. The increasing of the demulsifier concentrations (50, 100 and
200 ppm) decrease the time taken to complete the water separa-
tion. This may be due to the increasing of demulsifier concentra-
tion makes to increase the adsorption of molecules on the
interface.
3. Increasing of the water content in the w/o emulsion leads to
increase the water coalescence rate, this attributed to the increas-
ing of the film thinning at the interface.
4. Increasing the temperature from 30 to 60 C results decreasing of
the viscosity which leads to ease the adsorption of the demulsifier
molecules on the interface, then the rate of water separation
increases.
5. There is not direct relation between the HLB values and the
demulsification efficiency.
REFERENCES
Averyard, R.; Binks, B.P.; Fletcher, P.D. The Resolution of Emulsions,

Including Crude Oil Emulsions. In Relation to HLB Behavior;
Sjoblom, J., Ed.; Kluwer Academic Publishers: Amsterdam, The

Netherlands, 1992.
Berger, P.D.; Hsu, C.; Arendell, J. Soc. Pet. Eng. 1987, 162, 457.
Bride, A.L.; Wanders, Th.H.; Zegveid, W.; Vander, H.B. Heijde. Marine
Pollut. Bull. 1980, 11(12), 343.
Chales, M. U.S. Patent 1947, 2,422,177: Jr., Webster.
Eley, D.; Hey, M.; Lee, M. Rheological Studies of Asphaltene Films Adsor-
bed at the Oil/Water Interface. J. Colloid Surface 1987, 24, 173–182.
Graham, D.E.; Neustadter, E.L.; Stockwell, A.; Whittingham, K.P.; Cairns,
R. Surface Active Agents. SCI Publication, 1979; 127.
Graham, D.E. Royal Society of Chemistry 1988, 67, 55.
Graham, D.E.; Stochwell, A.; Thompson, D.G. Royal Society of Chemistry
1993, 45.
Ivanov, I.B.; Jain, R.K.; Somasundaran, P.; Traykov, T. J. Colloid Interface
Sci. 1974, 51, 1819.
Jones, T.J.; Neustadter, E.L.; Whittttingham, K.P. Water-in-Crude Oil
Emulsion Stability and Emulsion Destabilization by Chemical
Demulsifiers. J. Canadian Petroleum Technol. 1978, 17, 1.
Little, R. Fuel 1974, 53(4), 246.
McMahon, A.J. NATO ASI Ser., 363, (Emulsions: Fundam. Pract.
Approach) 1992, 135.
Mohammed, R.A.; Baily, A.; Luckham, P.F.; Taylor, S.E. Dewatering of
Crude Oil Emulsions. 2. Interfacial Properties of the Asphaltene
Constituents of Crude Oil. J. Colloids Surf. 1993, 80, 237–242.
Mohammed, R.A.; Baily, A.; Luckham, P.F.; Taylor, S.E. Dewatering of
Crude Oil Emulsions. 3-Emulsion Resolution by Chemical Means.
J. Colloids Surf. 1994, 83, 261.
Schramm, L.L. Emulsions Fundamentals and Applications in the Petroleum
Industry. ACS: Washington, DC, 1992.
Sharma, I.C.; Haque, I.; Srivastva, S. Indian J. Technol. 1982, 20(5), 175.
Singh, B.P. Paper No. 018 presented in Fifth National Conference on
Surfactant Emulsions and Biocolloids, M.S. University, Baroda,
October 28–30th, 1991.
Venugopal, B.M.; Wasan, D.T. Encycl. Emulsion Technol. 1985, 2, 1.

Young, H.; Kim, D.; Wasan, T. Ind. Eng. Chem. Res. 1996, 35, 1141–1149.
Zaki, N.N.; Al-Sabagh, A.M. Tenside Surf. Det. 1997, 34, 1.
Received July 6, 2001

Accepted October 29, 2001

Petroleum Science and Technology

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Petroleum Science and Technology

Uploaded by

Copyright:

Available Formats

This article was downloaded by: [McGill University Library]

On: 18 August 2012, At: 02:07

Petroleum Science and Technology

BREAKING WATER-IN-CRUDE OIL EMULSIONS BY NOVEL

Version of record first published: 14 Feb 2007

To link to this article: http://dx.doi.org/10.1081/LFT-120003685

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions

PETROLEUM SCIENCE AND TECHNOLOGY

BREAKING WATER-IN-CRUDE OIL

BASED ON MALEIC ANHYDRIDE–OLEIC

A. M. Al-Sabagh,* A. M. Badawi, and

Egyptian Petroleum Research Institute,

This paper mainly concentrates on synthesis of ten novel

888 AL-SABAGH, BADAWI, AND NOOR EL-DEN

(OMTEA e.o. 136.4). The chemical structures of the OM

(OMTEA e.o. 136.4) was exhibited the minimum time taken

Key Words: Demulsiﬁer; Monomeric surfactants; Emulsion

NOVEL DEMULSIFIERS DERIVED FROM OM 889

demulsiﬁers act by displacing pre-formed rigid interfacial ﬁlms composed

Crude Oil Type

Asphaltenic crude oil was submitted from Suez Oil Company

890 AL-SABAGH, BADAWI, AND NOOR EL-DEN

Table 1. Physicochemical Properties of Used Crude Oil

Speciﬁcation Method Asphaltenic Crude Oil

Speciﬁc gravity (60/60 F) IP160 0.874

Preparation of Oleic Acid–Maleic Anhydride Adduct (OM)

In a 1 l three-necked round bottom ﬂask, ﬁtted with a condenser, a

Preparation of the Demulsiﬁers

Preparation of Mono- and Di-derivatives of OM Adduct

In a 250 ml one-necked flat bottom flask fitted with Dean-Stark

Preparation of Water-in-Crude-Oil Emulsions

Alcohol and Amine Chemical Structure of Mono-derivatives Mono-derivative

Polyethylene (OM e.o. 13.6)

e.o.: ethylene oxide; p.o.: propylene oxide.

Mono-derivative Chemical Structure of Di-derivatives Adduct

OMTEA Polyethyleneglycol (OMTEA e.o. 22.7)

OMTEA Polyethyleneglycol (OMTEA e.o. 136.4)

OMTEA Lauryl alcohol OMTEA–LA

Polyethylene Polyethyleneglycol ((OM e.o. 13.6) 2)

OMCA Triethanolamine OMCA–TEA

AL-SABAGH, BADAWI, AND NOOR EL-DEN

NOVEL DEMULSIFIERS DERIVED FROM OM 893

The bottle test is used to estimate the eﬃciency of demulsiﬁers to

RESULTS AND DISCUSSION

Spectral Analysis of Oleic Acid–Maleic

The 1H NMR spectrum of (OM) as shown in Figure 1 shows that,

Spectral Analysis of (OM e.o. 22.7) and OMCA as

894 AL-SABAGH, BADAWI, AND NOOR EL-DEN

Figure 2. FT-IR spectrum for OM.

NOVEL DEMULSIFIERS DERIVED FROM OM 895

Figure 4. FT-IR spectrum for (OM e.o. 22.7).

896 AL-SABAGH, BADAWI, AND NOOR EL-DEN

Figure 6. FT-IR spectrum for OMCA.

NOVEL DEMULSIFIERS DERIVED FROM OM 897

(CONH) at 3318 cm1 and out of plane vibrational binding band at

Factors Eﬀecting Demulsiﬁcation

The Chemical Structure of the Demulsiﬁers

A series of experiments were performed for seek to the comparison

between demulsifier chemical structure as a factor affecting demulsification

898 AL-SABAGH, BADAWI, AND NOOR EL-DEN

Figure 7. Coalescence percentage vs. time for OM at diﬀerent ppm concentrations

NOVEL DEMULSIFIERS DERIVED FROM OM 899