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ICBB 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 460 (2020) 012006 doi:10.1088/1755-1315/460/1/012006

Formulation of alternative demulsifiers with palm oil based

surfactants for crude oil demulsification

Fajar Bagas Saputra1 , Haruhiro Fujita2 , and Erliza Hambali3

1
P.T. Great Giant Food, Indonesia
2
Niigata University of International and Information Studies, Japan
3
Surfactant and Bioenergy Research Center, IPB University, Indonesia

*Email: [email protected]

Abstract. Palm oil-based surfactants were used to formulate demulsifiers for crude oil
demulsificat ion as alternatives to petroleu m-based surfactants. A light crude o il sample
obtained from x field crude oil well contained 0.713% (w/w) asphaltene and 25.75% BS&W.
The formulat ion of demu lsifiers was carried out by the selection of a primary surfactant fro m
Sodiu m Methyl Ester Sulfonate (SMES) and Diethanolamide (DEA ), and the concentration of
co-surfactant addition. The best formu lation was SM ES as a primary surfactant with the
addition of a 10% DEA co-surfactant. The best solvent was the solution of toluene and xylene
(1:1). The temperature treat ment of 80 ℃ separated 100% water fro m crude oil emulsion and
decreased BS&W to 5.45%.
Keywords: Alternative demu lsifiers, Crude oil demu lsification, Palm oil-based surfactants

1. Introduction
Crude oil emulsion is of water-in-oil type and stabilized by various natural surface active agents such
as resins and asphaltenes. It is formed when two immiscible liquids (oil and water) are agitated
together to disperse droplets of one liquid into another. The agitation is taken place by the flow of
crude oil from the well to the surface line. The agitation of water and crude oil stabilizes the crude oil
emulsion in which water remains dispersed for a long time [1].

The crude oil emulsion is one of the major obstacles in crude oil production. Water in the crude oil
emulsion can contain gas hydrates and salts such as NaCl, MgCl2 , CaCl2 , and KCl which are
responsible for corrosion of production equipment and pipelines. They also decrease the quality of
petroleum distillates, especially by the reactions of heavy components such as boiler fuel, the raw
material for catalytic cracking and others [2]. In addition, the crude oil emulsion increases
transportation cost as it occupies extra spaces and increases the viscosity of the crude oil. Therefore,
the demulsification of crude oil emulsion is one of the most important processes in all oil fields.

The demulsification is the basic process used to separate water from the crude oil emulsion. The
demulsification can be classified into electrical, mechanical, and chemical methods. Chemical
demulsification is the most common method in the industry due to its applicability. This method
involves the use of chemical additives to enhance emulsion separation processes, of which surfactants
are commonly used. Demulsifiers being used in the petroleum industry are usually petroleum-based or

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ICBB 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 460 (2020) 012006 doi:10.1088/1755-1315/460/1/012006

polymer-based surfactants. The petroleum-based surfactant is less environmental-friendly, while the

polymer-based surfactant costs higher as raw materials are not easily available.

The development of demulsifier by palm oil-based surfactants is of necessity considering the use of
abundant biomass materials, hence zero carbon emission, as the Republic of Indonesia produced 35
million tons of CPO from a total plantation area of 12 million ha in 2017 [3]. In this study, a formula
of a demulsifier was developed to break emulsion in crude oil using palm oil-based surfactants, i.e.,
diethanolamine (DEA) and sodium methyl ester sulphonate (SMES). The objectives of this study are
to formulate a demulsifier by palm oil-based surfactants, applying a mixture of a primary surfactant
and a co-surfactant, and to determine the effects of solvent and temperature on crude oil
demulsification.

2. Materials and Methods

The materials used in this study were crude oil, formation water, anionic surfactant sodium methyl
ester sulfonate (SMES) and nonionic diethanolamide (DEA) surfactants and other chemicals for
analyses.
The physicochemical analysis of the crude oil fluid was carried out, to observe density, API gravity,
specific gravity, viscosity, Basic Sediment and Water (BS&W) using the ASTM 6560 method and
asphaltene contents.
Demulsification performance test by the fast water drop (FWD) and BS&W, to compare SMES and
DEA as the primary surfactant. Then the co-surfactant concentrations at 10%, 20%, and 30% were
tested for the performance.
The solvents, i.e., toluene, xylene, and a solution of toluene and xylene (1:1), and heating temperature
variations of 50 °C, 60 °C, 70 °C, and 80 °C were also tested for the performance.

3. Results and Discussions

3.1. Physicochemical properties

The physicochemical properties of the crude oil are shown in Table 1.

Table 1. Physicochemical properties of crude oil

Parameter Results Unit
API density 0.85334 g/cm3
Density 0.82059 g/cm3
○
API specific gravity 0.85418
○
API gravity 34.16
Asphaltene content 0.713 %
BS&W 27.73 %
The density and API density were 0.82059 and 0.85334 g/cm3 respectively. The API specific gravity
and API gravity were 0,85418o and 34,16o respectively. The oil with smaller specific gravity value
contains a shorter chain of alkanes fraction so that the molecular density gets lower. The sample crude
oil was classified as a light crude oil as the API Gravity value was higher than 31.1o [4].

The concentration of asphaltene was 0.713%. Asphaltene is a natural emulsifier in crude oil that
affects oil and water emulsions stability. Asphaltene is the heaviest molecule and the most polar
fraction of crude oil composing condensed aromatic rings with aliphatic side chains and various types
of functional groups. With these attributes, the asphaltene acts as a natural emulsifier agent [5], as in
Figure 1.

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ICBB 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 460 (2020) 012006 doi:10.1088/1755-1315/460/1/012006

Figure 1 Mechanism of emulsion stabilization: asphaltenic thin film formation

at the oil/water interface (after [5] and [6])

The basic value of sediment and water (BS&W) was 27.73%. The sediment is an impurity component
of the mud-shaped oil. The higher the value of BS&W, the quality of oil decreases. The sediment in
the oil should be decreased, hence, the oil demulsification process is conducted to decrease the value
of BS&W. The standard value of BS&W of crude oil after the demulsification process is expected to
be between 0.2-5% [7].

3.2. Formulation of Demulsifier

3.2.1 Primary surfactant selection

Surfactant is a compound that has an ability to reduce the surface tension of a media as it has a
hydrophilic group at a polar part and a lipophilic group at nonpolar parts. Surfactants are generally
used as emulsifying agents of a distinctly different mixture, as presented in Figure 2. Contrarily,
surfactants perform as demulsifiers. Roodbari et. al. [8] proved that surfactants had both emulsification
and demulsification functions in different cases and some surfactants for making oil in water
emulsions could demulsify water in oil emulsions.

Figure 2 Schematic display of demulsifier structure and its penetration into the layer around water
droplet (after Roodbari et al. [8])

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ICBB 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 460 (2020) 012006 doi:10.1088/1755-1315/460/1/012006

In recent years, many studies were carried out on ionic and nonionic demulsifiers. Studies have shown
that the presence of more hydrophilic parts in demulsifiers cause more separation of water from oil
and it had a substantial effect on the amount of HLB number of surfactant [9]. Generally the nonpolar
(lipophilic) has a long alkyl chain, while the polar (hydrophilic) contains hydroxyl groups [10]. The
surfactants used in this study were sodium methyl ester sulfonate (SMES) and diethanolamide (DEA)
from palm oil. The SMES surfactant is anionic one that is a negatively charged surfactant on its
hydrophilic group or surface-active part. The formulation of the SMES surfactant starts with the
formulation of MESA (methyl esters sulfonic acid) synthesis of methyl ester by the sulfonation
followed by the neutralization using 50% NaOH to produce the SMES. DEA is a nonionic surfactant
synthesized from methyl ester olein and diethanolamine by the amidation process. The effects of
surfactants on demulsification are shown in Table 2.

Table 2. Effects of surfactants on demulsification

Surfactant FWD (%) BS&W (%)
SMES 38,12 12,67
DEA 6,88 25,73
Control 3,75 26,31

The separation value of water at 15 minutes (FWD), the SMES surfactant showed 38.125% compared
to the DEA surfactant of 6.875%. The SMES had better water separation capability than the DEA
surfactant. BS&W values were decreased after the demulsification process. The SMES surfactant
decreased BS&W to 12.67%, while DEA surfactant to 25.31%. The smaller value of BS&W shows
the better quality of crude oil as the impurities on the oil decreases. SMES surfactant had better
performance in solving crude oil emulsion as SMES might have had sulphonate groups which are
appropriate hydrophilic parts. This group allows the surfactant more hydrogen bonds and has stronger
hydrophilic parts.

3.2.2 Co-surfactant addition

In the industry, the use of more than one type of surfactant is very common to improve the
demulsification performance. Every surfactant has different characteristics. Nonionic surfactants are
often used as co-surfactants and mixed with other surfactants as they are generally lipophilic. The
performance of nonionic surfactants is stronger when mixed with ionic surfactants and amphoteric
surfactants in their applications. SMES was selected as the primary surfactant and DEA as a co-
surfactant. The effects of co-surfactant addition on demulsification are shown in Table 3.

Table 3. Effects of co-surfactant addition on demulsification

Level of co-surfactant FWD (%) BS&W (%)
addition (%)
0 38.12 12.67
10 55.00 11.92
20 49.75 12.40
30 10.00 19.43

Co-surfactant addition has an effect in increasing the performance of the demulsifier. The 10% and
20% co-surfactant additions increased the demulsifier performance on water separation in 15 minutes
to 55% and 49.75% respectively. While the 30% addition, FWD declined to 10%. The same result was
also shown on the value of BS&W. The 10% addition of 11.92% and 20% of 12.40% respectively.
The 30% co-surfactant addition increased BS&W to 19.43%. The 10% DEA addition was selected for
the co-surfactant addition.

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ICBB 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 460 (2020) 012006 doi:10.1088/1755-1315/460/1/012006

The analysis of variance showed that the addition of co-surfactant significantly (α = 0.05) influenced
the increase of water separation and the decrease in BS&W. The Duncan test showed that each level of
co-surfactant addition was significantly different from other levels in the water separation response
and the value of BS&W. The analysis showed that the 10% co-surfactant addition showed the best
result of FWD 55% and of BS&W 11.92%. It was also demonstrated that the higher co-surfactant
addition with the reverse demulsification performance. The demulsifier performance decreased when
the addition level exceeded 20%. This may have associated, an increase in the nonionic surfactant
addition that might have precluded interfacial activity. Muhpidah [11] observed that increasing the
addition of nonionic co-surfactants to anionic surfactants would inhibit the performance of anionic
surfactants in demulsification.

3.2.3 Solvent selection

The demulsification is a process to break the emulsion by disrupting the viscoelastic film layer in the
droplet. The film layer acts in stabilizing the emulsion composed of aromatic groups and hydrogen
interactions between the resin and asphaltene [12]. Therefore, in demulsifier formulation, the solvent
is necessary to disrupt the interaction between the asphaltenes-resin.
In this study, xylene, toluene , and an equal mixture were applied. The selection of xylene and toluene
was based on previous studies that this solution was able to disrupt the emulsion stability in crude oil.
Atta (2013) [13] used xylene and toluene solutions for the solvents on polymer-based demulsifier
formulations and it was proven that both solutions could decrease the interface tension to disturb the
stability of crude oil emulsions. The effects of solvents on demulsification are shown in Table 4.

Table 4. Effects of solvents on demulsification

Solvents FWD (%) BS&W (%)
Xylene 10.30 22.00
Toluene 15.10 20.10
Xylene:Toluene (1:1) 20.00 18.80

The result showed that the toluene destabilized the emulsion 40.25%, slightly higher than the xylene’s
FWD 39.25%. The mixed solution of xylene and toluene (1:1) improved the separation at 59.83% as
well as the lowest BS&W. Hence the mixed solution of xylene and toluene (1:1) was selected as a
solvent for demulsifier formulation.
The results indicate the possible solvent disruption on crude oil emulsion stability. Toluene and xylene
solvents might have interfered asphaltene-resin aggregation by interacting with aromatic groups.
Toluene and xylene are classified as aromatic hydrocarbons. Toluene (C 6 H5-CH3) is a benzene-derived
compound with one of its hydrogen atoms binding to a methyl group (CH 3 ). Toluene is used to
separate the asphaltene from crude oil. Toluene is able to dissolve the asphaltene up to 65.09% [14].
Xylene (C8 H10 ) or dimethyl benzene is an aromatic compound in the form of 3 isomers: ortho-, meta-
and para-xylene or 1,2-, 1,3-, and 1,4-dimethyl benzene. Xylene is also capable of dissolving
asphaltene to 61.95% [14]. Asphaltene has varying degrees of solubility from certain types of solvents.
Therefore, it is sometimes necessary to mix two types of solvents to increase the solubility efficiency
of asphaltene. Lightford et al. [15] confirmed that additional solvents can be used to improve the
solubility efficiency of asphaltene.

Table 5. Effects of temperature on demulsification with demulsifier

Solvents (0.4 v/v) FWD (%) BS&W (%)
Xylene 39.25 15.83
Toluene 40.25 10.00
Xylene:Toluene (1:1) 59.83 9.85

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ICBB 2019 IOP Publishing
IOP Conf. Series: Earth and Environmental Science 460 (2020) 012006 doi:10.1088/1755-1315/460/1/012006

3.2.4 Effects of temperature

The effects of temperature on demulsification with demulsifier are shown in Table 5. Fernando [16]
reported that the temperature had a significant influence on emulsion demulsification in crude oil. The
increase of temperature leads to decrease oil density and viscosity, increased collision frequencies
between emulsion droplets, and increased solubility of compounds contained in the emulsion system.
The temperature rise played a role in weakening the resin solvent to asphaltene and weakening the
interaction of Van der Waals aggregate asphaltene resin. The effects of temperature on demulsification
with demulsifiers are shown in Table 6.

Table 6. Effects of temperature on demulsification with demulsifiers

Temperature FWD (%) BS&W (%)
50o C 59.83 9.85
60o C 80.90 6.60
70o C 95.40 5.80
80o C 100.00 5.45

The analysis of variance showed that the heating temperature had a significant effect (α = 0.05) on
increasing the water separation and decreasing BS&W value. Duncan test showed that each
temperature level was significantly different from other temperature levels in the water-splitting
response and BS&W values. The analysis showed that 80o C resulted in 100% water separation and
the smallest value of BS&W, 5.45%.

4. Conclusions
A crude oil sample was classified as light crude oil. The crude oil contained 0.713% asphaltene and
27.73% basic sediment. The best palm oil-based demulsifier formulation was SMES as a primary
surfactant with the addition of 10% DEA co-surfactant applying xylene:toluene (1:1). The formulation
separated 100% water from crude oil emulsion and decreased BS&W to 5.45% at 80°C. Increasing
the temperature of the demulsification process might have affected the emulsion stability so that the
demulsification of crude oil emulsion increased.

Acknowledgments
Authors owe a great deal to Surfactant and Bioenergy Research Center of IPB University for the
whole process of the study. This study owes Pertamina Foundation for its kind financial support.

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