Accepted Manuscript

Demulsification of heavy crude oil using new nonionic cardanol

surfactants

Ayman M. Atta, Mahmood M.S. Abdullah, Hamad A. Al-

Lohedan, Abdelrhman O. Ezzat

PII: S0167-7322(17)34836-5
DOI: https://doi.org/10.1016/j.molliq.2017.12.154
Reference: MOLLIQ 8450
To appear in: Journal of Molecular Liquids
Received date: 11 October 2017
Revised date: 28 December 2017
Accepted date: 29 December 2017

Please cite this article as: Ayman M. Atta, Mahmood M.S. Abdullah, Hamad A. Al-
Lohedan, Abdelrhman O. Ezzat , Demulsification of heavy crude oil using new nonionic
cardanol surfactants. The address for the corresponding author was captured as affiliation
for all authors. Please check if appropriate. Molliq(2017), https://doi.org/10.1016/
j.molliq.2017.12.154

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 ACCEPTED MANUSCRIPT

Demulsification of Heavy Crude Oil Using New Nonionic Cardanol

Surfactants

By

Ayman M. Atta1,* Mahmood M. S. Abdullah 1 Hamad A. Al-Lohedan1, and

Abdelrhman O. Ezzat1

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1
Surfactants research chair, Chemistry department, college of science, King
Saud University, Riyadh 11451, Saudi Arabia. (* E-mail: aatta@ksu.edu.sa)

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Abstract: Amphiphilic materials based on natural products and biomaterials

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attracted great attention to replace the petroleum based oil field chemicals as
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environmentally and ecofriendly materials. The present study modified and
characterized the chemical structure of cardanol produced from cashew nut
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oil with amines and glycols to produce new ionic surfactants. The surface
and interfacial activities of the prepared nonionic cardanol surfactants were
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investigated to study their adsorption at water and oil surfaces. The ability of
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the cardanol surfactants to act as asphaltene dispersant and water in crude oil
emulsion breaker for heavy crude oil were evaluated and showed good
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results as single surfactant to acts as dispersant and demulsifier for heavy

crude.
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Keywords: Cardanol; asphaltene; demulsifier; petroleum emulsion;

nonionic surfactants.

1. Introduction:

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One of the more serious problems affected the crude oil production, storage,
transportation and refining is asphaltenes precipitation and emulsion
formation especially in the heavy crude oil [1]. Asphaltenes form deposits
and water in crude oil emulsions during the production of the oil reservoirs
can block the crude oil production facilities and reduce the crude oil
productivity that significantly increase the processing operational costs [2-

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4]. These problems produced from the changes of the temperature, pressure

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and composition of crude oils during production [5]. Moreover, the changes

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in the balancing of the crude oil phases also formed hard solid sludge that
produced from the precipitation of heavy fractions, such as asphaltenes,

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resins, waxes, paraffin, clay, sand, salt and water. The formation of emulsion
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and sludge during the production and processing blocks the production,
transportation and storage processing facilities [6]. There are many potential
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and advanced solutions for these problems included mechanical removal of

deposits, thermal treatment, electrical desalting and treatment with oil field
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chemicals such as solvents or asphaltene dispersant agents [7]. Moreover,

the analyses of asphaltenes using the theoretical models and study of
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asphaltene interfacial and colloidal behavior in crude oils facilitated the

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selection of the suitable method and chemicals for the inhibition of the
asphaltene precipitation of heavy crude oils [8-10]. The application of
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soluble amphiphile dispersants is the most practical and economical solution

for the emulsion and deposits treatment. However, these materials have toxic
and hazardous effects due to they composed several solvents used to solve
the asphaltene deposition. There are several commercial asphaltene
dispersants and demulsifiers based on petroleum products have been widely
used to solve the asphaltene deposition and emulsion formation. These
oilfield chemicals are composed surfactants mixtures that based on

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ethoxylated nonylphenols, alkyl benzene sulfonic and polyisobutylene

succinimide derivatives [11-14]. Recently green chemicals based on natural
products and nonedible oils have been modified to apply as oilfield
chemicals [3, 15-18]. The application of natural oils as emulsifier and
asphaltene dispersant is favorable due to their lower production cost, cheaper
than the cost of the petroleum based chemicals, easy handling and nontoxic

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environmentally friendly materials.

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Cardanol is one of the natural alkyl phenols that extracted from cashew-nut
shell liquid and applied as oilfield chemicals [19-21]. Its chemical structure

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based on phenolic compounds with meta-substituted linear unsaturated alkyl
chains (fifteen carbon atoms) in aromatic rings can be polymerized to apply
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as asphaltene dispersants [19, 20]. Moreover, the compatibility between the
crude oil chemical structures and cardanol affected the crude oil quality. The
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chemical structure of cardanol is similar to amphiphiles used as asphaltene

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dispersants that have ability to interact with asphaltene. It was previously

reported that [19, 20], the modification of the cardanol chemical structure
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either by polycondensation with formaldehyde or with polymerization of

unsauturated alkyl substituent with BF3O(CH2CH3)2produced cardanol
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polymeric derivatives have strong ability to act as asphaltene precipitation

inhibitors. These polymers were not effectively used as emulsion breaker for
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heavy crude oil water emulsions that required surfactants blends. The
polycondensation of cardanol with formaldehyde produced crosslinked
polymers [22]. Moreover, the addition reactions of cardanol with a Lewis
acid, more specifically with BF3O(CH2CH3)2, produced a crosslinked
polymer [23]. The present work aims to modify the chemical structure of
cardanol to produce nonionic surfactants using oxyethylene materials which

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are more environmentally friendly. On the other hand, the prepared linear
cardanol polymers [19, 20] were tested here on the tested Arabic heavy
crude and did not achieve any demulsification results. The preparation of
new surfactants from cardanol was a target for different researches due to
their greater DNA interaction capability, low cytotoxicity, high surface
activity, and effective cost [24-32]. Cardanol surfactants replaced the

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conventional petroleum-derived nonylphenols for the preparation of

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surfactants and they are just emerging as green chemical alternatives [24].

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The amine based cardanol surfactants showed great efficiencies to act as
dispersants for different nanomaterials based on needle-like clays and silica

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[9, 24, 25]. In the present work, new cardanol ethoxylate amine based
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surfactants are synthesized which can act as asphaltene dispersants for
Arabic heavy crude oil or demulsifier for its emulsion. The relationship
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between the surface activity and the chemical structure of the prepared
surfactants is investigated. The objective of this work was to assess the
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performance of the modified cardanol surfactants as demulsifiers and as

asphaltene-stabilizing agents.
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2. Experimental
2.1. Materials
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The chemicals used in the present work are pure and purchased from Sigma-
Aldrish chemicals Co. Cardanol extracted from Cashew nut oil was obtained
by Shanghai Judong Trading Company Ltd. Ethanolamine, diethanolamine
(DEA), β,β-dicholorodiethylether (DCDE), epichlorohydrine (ECH),
tetraethylene glycol (TEG) and sodium hydroxide, were used to prepare
amphiphilic materials based on cardanol. Solvents such as toluene, heptane,

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xylene and isooctane have analytical grade and purity more than 99 % were
used in both synthesis and evaluation of the cardanol surfactants.
Heavy Arabic crude oil (19.8 API) produced from Ras Tanora wells by
Aramco, Saudi Arabia with water and asphaltene contents 0.145 wt% and 12
wt% respectively was used in this study. Sea water of Arabic Gulf was used
to prepare synthetic water in crude oil emulsions having different

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compositions ranged from 90/10 to 50/50 ( crude oil / water Vol %) as

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reported in the previous work [33]. Toluene: n-heptane solvents (1:40 vol %)

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used to isolate the asphaltene fractions from crude oil according to procedure
ASTM D2007.

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2.2. Preparation methods
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a) Preparation of DECA
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The di-etherified cardanoxy amine (DECA) surfactant was synthesized from

the etherification of cardanol with DEA in the presence of DCDE and
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sodium hydroxide as linking agent and catalyst, respectively. Cardanol (0.04

mol; 11.93 g), DEA (0.04 mol; 4.2 g), DCDE (0.04 mol; 5.7 g) were
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vigorously stirred with NaOH powder (0.08 mol; 3.2 g) to obtain clear
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solution under N2 atmosphere. The reaction was heated and refluxed at 150
o
C for 4h. The NaCl was separated from the reaction mixture by filtration
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after adding 50 mL of acetone to the cooled reaction mixture. The acetone

was isolated from the filtrate by rotary evaporator under reduced pressure.
DCDE (0.08 mol; 11.44 g), TEG (0.08 mol; 15.53 g) and NaOH powder
(0.16 mol; 6.4 g) were added to filtrate after acetone evaporation with
vigorous stirring at reaction temperature 100 oC under N2 atmosphere for 5h.
The same procedure used to isolate NaCl was repeated. The unreacted
materials were salted out using hot aqueous solution of saturated NaCl and

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extracted by isopropanol as organic solvent. The reaction yield percentage of

liquid product DECA was 90.2 %. The N content was calculated and
determined as 1.52 and 1.51 %, respectively.

b) Preparation of TECA

The tri-etherified cardanoxy amine (TECA) was synthesized using different

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technique based on etherification of cardanol with ECH, ethanolamine and

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TEG in the presence of DCDE and NaOH. In this respect, cardanol ( 0.1

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mol; 29.8 g) was reacted with excess of ECH (0.3 mol; 27.7 g) and NaOH
(0.1 mol; 4g dissolved in 5 mL of water) under stirring and N2 atmosphere.

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The reaction mixture was heated and refluxed for 9 h. The NaCl precipitate
and excess of ECH were removed from the cooled reaction mixture by
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filtration and rotary evaporation, respectively to obtain dark brown liquid.
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Ethanol amine (0.1 mol; 6.1 g) was added and heated with the reaction
mixture at 100 oC under N2 atmosphere for 3h. Toluene (50 mL), TEG (0.09
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mol; 17.5 g), DCDE (0.09 mol; 12.8 g), and NaOH powder (0.09 mol) were
added to the cooled reaction mixture.
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The stirred reaction mixture was heated at 120 oC for 6h under N2

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atmosphere. The same procedure used to isolate NaCl was repeated. The
unreacted materials were salted out using hot aqueous solution of saturated
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NaCl and extracted by isopropanol as organic solvent. The reaction yield

percentage of liquid product TECA was 93.8 %. The N content was
calculated and determined as 1.31 and 1.32 %, respectively.

2.3. Characterization of the prepared surfactants

The N content of DECA and TECA was determined using a Carlo Erba 1106
elemental analyzer.

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1
HNMR and 13CNMR spectroscopy model a 400MHz Bruker Avance DRX-
400 spectrometer used to investigate the chemical structure of DECA and
TECA using deutrated DMSO as solvent.

The relative solubility number (RSN) determined as the volume of water

(mL) used to obtain cloud solutions for surfactants solutions (2g in 60 mL of

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solution consisting of 97.4 wt.% ethylene glycol diethylether and 2.6 wt.%

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toluene). The surfactants solutions were titrated against distilled water until

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their clear solutions turned to cloudy solutions under stirring at room
temperature.

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Drop shape analyzer ( DSA-100) was used to determine both the interfacial
and surface tension measurements for different concentrations of DECA and
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TECA in aqueous solutions based on pendant drop method at room
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temperature.
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Dynamic light scattering (DLS; Zetasizer Nano ZS, Malvern Instrument

Ltd., Malvern, UK) was used to determine the hydrodynamic diameter ( Hd)
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and polydispersity index (PDI) for the DECA, TECA and asphaltene
aggregates in both aqueous and heptane solutions at 25 °C. The
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concentration of DECA or TECA was 0.01 M in aqueous solution.

Polarized optical microscope (Olympus BX-51 microscope attached with a
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100 W mercury lamp) was used to investigate the size and shape of the
crude oil/ seawater emulsions. The emulsions were diluted with toluene to
show the particle sizes of emulsions.

2.4. Asphaltene dispersing efficiency of the prepared surfactants

The asphaltene separated from the crude oil was solubilized by toluene (10
mL; 5.0 g L−1) and blended with heptane (8.8 mL) under vigorous stirring to

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record as reference sample. DECA or TECA was added to asphaltene

heptane solution with different ratios ranged from 1:1 to 1:5 Wt %. The
same quantity of heptane was mixed with asphaltene, surfactants and toluene
with continuous stirring for 5h. The resulting mixture was centrifuged at
2000 rpm for 25 min to isolate asphaltene precipitate to determine its
particle sizes by DLS measurement [34].

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2.5. Emulsion breaking of the water in crude oil emulsions

The synthetic emulsions prepared with different crude oil sea water

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compositions ranged from 50/50 to 90/10 Vol % using homogenizer at speed
10000 rpm for 30 minutes. The DECA or TECA was dissolved into xylene /
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ethanol (75/25 Vol. %) with concentrations of 70 Wt %. The DECA or
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TECA solutions was injected into the heated water in crude oil emulsions at
60 oC with different concentrations ranged from 25 to 100 mgL-1. The same
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volume of solvent (xylene/ethanol; 75/25) was injected into the water in

crude oil emulsion without DECA or TECA to obtain the blank sample. The
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demulsification efficiencies (DE %) are determined as DE %= Vs/Ve;

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where Vs and Ve are the separated volume of water at definite time and total
emulsified water, respectively [33].
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The separated water from demulsification experiment was acidified by

sulphuric acid to pH (2 to 3), and the oil was extracted twice by 2 mL of
isooctane to determine the residual oil in water. The concentration of oil in
isooctane was measured by using the UV-VIS (PerkinElmer, model Lambda
35) at λmax of 255 nm.

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3. Results and discussion

3.1. Characterization of DECA and TECA
The present work aims to prepare new nonionic surfactants containing amine
group and oxyethylene units to apply as demulsifier for petroleum crude oil
emulsions using two routes as illustrated in the schemes 1 and 2. The
preparation of DECA (scheme 1) is based on reacting of hydroxyl phenol

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groups with DEA in the presence of the DCDE and NaOH as linking agent
and catalyst, respectively. It is proposed that the DCDE reacts with amine

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reactive group and hydroxyl phenol better than reaction with hydroxyl

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groups of DEA [35]. The dihydroxy amine groups of the product were
etherified with TEG in the presence of DCDE and NaOH to produce the
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DECA surfactant that contains cardanoxy dioxyethylene amine nonionic
group as represented in the experimental section. The second route to
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prepare nonionic surfactant based on TECA (scheme 2) aims to prepare

cardanoxy trioxyethylene amine nonionic by reacting epoxy with amine
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groups [23] followed by etherification with TEG. The preparation of DECA

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and TECA is confirmed by the agreements between the theoretical and

determined N %.
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The chemical structures of DECA and TECA are confirmed by 1H and

13
CNMR analyses as represented in Figures 1 and 2 a, b. The disappearance
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of hydroxyl proton peak of cardanol at 3.2 ppm and appearance of strong

new peaks at 3.5 and 4.2 ppm that attributed to ethoxy and methoxy group of
TEG and cardanoxy groups respectively ( Figure 1 a and b) confirm the
etherification of cardanol. Moreover, the appearance of new peak at 3.9-4.1
ppm that attributed to methylene groups attached to amine elucidate the
contribution of amine in the etherified products of cardanol to form the
chemical structures of DECA and TECA ( Schemes 1 and 2). More details

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on the chemical structures of DECA and TECA are represented and assigned
on the Figure 1 a to confirm the ethoxylation of cardanol with EA, DEA and
TEG. The presence of unsaturation at the m- substituted alkyl groups of
cardanol without changes is confirmed by the appearance of peaks at 5.2-
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5.36 ppm (Figure 1 a and b). CNMR of DECA and TECA ( Figure 2 a
and b) was also used to elucidate their chemical structure from the

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appearance of peaks at 155, 72, 40 ppm which attributed to carbons attached

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to phenoxy, ethoxy, amine groups, respectively of DECA and TECA. More

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details on the peaks of DECA and TECA which confirm their chemical
structures are assigned in Figures 2 a and b that indicate the etherification

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of cardanol with saturation or distortion of the unsaturated alkyl groups at
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m- position of cardanol.
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3.2. Surface activity of DECA and TECA at interfaces

The cardanol has hydrophobic skeleton which contains unsaturated alkyl
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groups at m- position of phenol ring that was subject for different chemical
modification to obtain different types of nonionic and anionic surfactants
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and polymeric surfactants [24-32]. The present work aims to prepare

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cardanol nonionic surfactants with different hydrophile-lipophile balances

(HLB) to investigate their behaviors in water and oil/ water interface to
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apply as demulsifier for crude oil / water emulsions. It was previously

reported that [36, 37], the suitable HLB of the surfactants blends used as
demulsifier were ranged from 11 to 15 based on the emulsion types. The
HLB values of the prepared DECA and TECA were calculated from
Griffin’s equation HLB = MH x 20 / MA; where MA and MT are the
average and hydrophilic molecular weights of the nonionic surfactants,
respectively. The relative solubility number, RSN, is a practical alternative

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value used to replace HLB that calculated theoretically and to confirm the
solubility of the surfactant either in water or toluene [38]. The HLB and
RSN values for DECA and TECA are determined and listed in Table 1. The
data of HLB and RSN are above 10 and below 13 which confirm more water
and less water solubility, respectively [38]. However, the solubility of
DECA and TECA surfactants in the water is decreased with increment their

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molar concentrations above 0.05 mol /L. Consequently, the solubility of the

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DECA and TECA is more reliable to RSN than HLB values. The relation

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between HLB and RSN can be expressed as; HLB=0.6029 RSN + 6.7624
which similar and agrees with the data reported on Tween surfactants [38].

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The solubility, aggregation and adsorption of DECA and TECA in the water
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and water/air interfaces can be investigated from the relationship between
their concentrations (ln c; mol/L) and their surface tension in the aqueous
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solutions as represented in Figure 3. The critical micelle concentration

(cmc; mol.L-1), surface tension at cmc (γcac; mN.m-1) are determined for
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DECA and TECA from Figure 3 and summarized in Table 1. The

appearance of one-adsorption isotherm for DECA and TECA confirms the
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purity of these surfactants as elucidated from the nitrogen content as

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reported in the experimental section. The lower cmc value of DECA than
TECA agrees with its RSN that elucidates its low solubility in water.
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Moreover, the greater ability of TECA to reduce the surface tension of water
more than DECA proves the strong hydrogen bond between water and high
hydroxyl groups content of TECA more than DECA, which reduces both the
water-water and surfactant-surfactant interactions. These data also elucidate
that the oxyethylene groups of TECA expand and interact with water more
than DECA to affect their hydrodynamic diameters (H d; nm) at aggregation
above their cmc. The Hd of DECA and TECA are determined from their

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DLS measurement as represented in Figure 4 a and b. The low

polydispersity index ( PDI) and high Hd of DECA elucidate the strong
ability of DECA to form aggregates above its cmc with strong hydrophobic
interaction of alkyl phenoxy of cardanol at the core of its micelles and
packing of oxyethylene groups at the micelle shell more than TECA [39].
The adsorption of DECA and TECA at water/air interface is investigated

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from the surface excess concentration, Г max, and the minimum area of

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molecules, Amin, at the aqueous–air interface. The Г max is determined from

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the following relation: Г max = (-∂ γ / ∂ ln c)T /RT, where (−∂γ / ∂ ln c) T is
the slope of the plot of γ versus ln c at constant temperature (T) and R is the

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gas constant (in J mol−1 K−1) [40]. The Amin is calculated from the equation:
Amin = 1016/ N Гmax, where N is Avogadro’s number. The data of Гmax, Amin,
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and (-∂ γ / ∂ ln c) for DECA and TECA, are summarized in Table 1. The
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increment of Г max value of DECA more than TECA elucidates that the
branching of the hydrophilic groups of TECA increases its A min to reduce its
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order at air/water interface. Consequently, the great order of both

hydrophobic group at air and hydrophilic group in water for DECA increase
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their concentration at air / water interface.

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The relation between the interfacial tension (IFT; mN.m-1) and

concentrations of DECA and TECA in water with heavy crude oil is plotted
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in Figure 5. The IFT measurement is used to determine the ability of the

surfactant to adsorb at water/crude oil interface more than asphaltenes [41].
The IFT data elucidate the greater ability of DECA to reduce IFT more than
TECA with increment their concentrations. The greater affinity of TECA to
strongly interact with water in bulk solution reduces its ability to adsorb at
interfaces. Consequently, the DECA has strong tendency to irreversibly
adsorb at the water-oil interface [42]. Hence, the interfacial activity of

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DECA will increase more than TECA when their molecules are dispersed in
the water.

3.3. Interaction of DECA and TECA with asphaltene

Asphaltenes as natural surfactants in the heavy crude oil are responsible to
form stable water in crude oil emulsions due to the repulsive forces at the

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oil- water interfaces. These repulsive forces are attributed to the surface

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charges layer between oil droplets and the asphaltenes protective film [43].

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The good interaction forces between demulsifier molecules and asphaltene
moieties are the demulsification keys used to reduce the repulsive forces and

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and/or destroying the viscoelastic film at the oil/water interface [3, 44, 45].
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In this respect, it is expected that there are strong interaction forces could
produce between the prepared amphiphiles and asphaltenes beside cardanol
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hydrophobic interactions with asphaltenes [19]. The asphaltene stabilization

experiments in the heptane/toluene solvent in the presence different
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concentrations of DECA and TECA are investigated using DLS as reported

in the experimental section. The asphaltene dispersion efficiencies were
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determined and listed in Table 2. The effect of DECA and TECA on the
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asphaltene aggregations and its Hd in toluene/heptane is illustrated in Figure

6a-c. The data confirm that the asphaltene dispersion efficiencies are
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increased with increasing the concentration and presence of DECA more

than TECA. Moreover, the size of asphaltene aggregates and PDI are
reduced (Figure 6 a-c and Table 2) in the presence of DECA more than
TECA. These data can be illustrated in a very simplistic model to account
for the dispersing effect of DCEA and TECA amphiphilic molecules on the
asphaltenes as represented in Scheme 3 a and b. It is proposed that the
phenoxy ring and unsaturated alkyl groups of cardanoxy group interacted

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with asphaltenes using π-π interaction, hydrogen bond interaction and van
der Waals forces enhanced among the alkyl groups [3, 19]. The lower
adsorption of TECA amphiphile that is sterically hindered with hydrophilic
oxyethylene groups (scheme 3) turns the asphaltene surfaces to be more
polar and, hence, decreasing its capacity to interact with heptane aliphatic
solvents. Moreover, the phenol groups of TECA could interact with more

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than one asphaltene particle leaving its various polar hydroxyl groups

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exposed to heptane causing the flocculation and subsequent aggregation of

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the asphaltene dispersion (scheme 3 b). Accordingly, the less sterically
hindered alkylphenoxy groups of DECA (Scheme 3a) are relatively free to

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interact with the sites on the asphaltene molecules. These explanations were
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correlated to the interactions of polystyrene-block poly (ethylene oxide)
polymers, PS-POE, with toluene/heptane mixed solvents [46]. The
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interaction between oxygen pair of electron of oxyethylene (n) and π-

electron of toluene through n-π increases the dispersion of PS-POE
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copolymer more than homopolymers in the toluene/heptane mixed solvents.

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3.4. Demulsification of Water in crude oil emulsion

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Synthetic water in crude oil emulsions having different oil/water

compositions (90/10, 70/30 and 50/50 Vol %) were used to obtain water/oil
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emulsions (W/O) as reported in the experimental section. The type of

emulsion is tested by dropping method and all emulsions are dispersed in
toluene to elucidate the formation of stable W/O emulsion. The stability of
all emulsions is tested by heating at 60 oC for several weeks in the absence
of any additives. The microscopic photos of emulsions show the formation
of uniform emulsion droplets with small sizes to confirm the stability of all
emulsions as represented in Figure 7a. The demulsification experiments for

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crude water emulsions in the presence of different DECA and TECA

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concentrations were carried out at heating temperature 60 C. The
concentrations of the injected DECA and TECA solutions (30 Wt %) in
toluene / ethanol (75/25 Vol %) were ranged from 25 to 250 mg.L-1 to study
the effect of demulsifier concentrations on the demulsification efficiencies
(DE %). The demulsification times were recorded up to 10 h to study the

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relation between DE % and demulsification times of the water in crude oil

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emulsions. The demulsification data (demulsification times and DE %) for

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different water in crude oil emulsions were summarized in Table 3. The
relation between demulsification times and DE % of DECA and TECA

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solutions for water in crude oil emulsion (90/10 Vol %) was selected and
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represented in Figure 8. Moreover, the effect of demulsification time on the
water separation was illustrated from microscopic photos as summarized in
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Figure 7 a-c. The demulsification data show two different behaviors for
DECA and TECA solutions. The DECA achieved high demulsification data
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at low concentration and short time ( Table 3 and Figure 8) at water in

crude oil emulsion (90/10 Vol %). The TECA achieved high demulsification
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data to cause 100 % water separation ( 50 mL) at high concentration (Table

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3) at water in crude oil emulsion (50/50 Vol %). These data seem to be
unexpected for one surfactant because the commercial demulsifiers are
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based on the mixtures of surfactant formulations [47]. These data confirm

the high demulsification efficiencies for DECA and TECA solutions at high
crude oil and high water contents in emulsions, respectively. This can be
referred to the hydrophobicity of DECA increases its ability to disperse in
the continuous phase of emulsion that contains more oil (90/10 Vol %) [48].
The hydrophilicity of TECA molecules increases its ability to surround the
water droplets that contains low crude oil as continuous phase (50/50 Vol

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%). The microscopic photos (Figure 7 a-c) elucidate the demulsification

mechanisms based on dispersion of demulsifier in the continuous phase
followed by asphaltene layer removal at water droplet surfaces and water
coalescence with complete gravity water separation [49]. The higher ability
of DECA to disperse asphaltene ( Figure 6 and Table 2) and to reduce IFT (
Figure 5) more than TECA increase the water separation at short time for

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the water in crude oil emulsion (90/10 Vol %).

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It is necessary to determine both the residual oil in separated water (i.e.

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produced water) which becomes wastewater and residual water in crude oil
after demulsification to meet the specification for transporting of crude oil or

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entering the refinery plant. The photos for separation of the water in crude
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oil emulsion (90/10 Vol %) using different concentrations of DECA are
summarized in Figure 9 a-d. The oil residues in the separated crude oil are
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1972.04 mg L-1 and 1025.90 mg L-1, for DECA concentrations 50 and 100
mg L-1, respectively which are in the range of industrial acceptable limit. It
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represents the clarity of the separated water with increment of DECA

concentrations.
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4. Conclusions

New nonionic surfactants based on cardanol containing amine group and

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oxyethylene DECA and TECA having different solubility degrees in water

were prepared. The DLS data elucidate that the oxyethylene groups of
TECA expand and interact with water more than DECA to affect their
hydrodynamic diameters (Hd) at aggregation above their cmc. The strong
hydrophobic interaction of alkyl phenoxy of cardanol at the core of its
micelles and packing of oxyethylene groups at the micelle shell more for

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DECA are more than TECA. The IFT data elucidate the greater ability of
DECA to reduce IFT more than TECA due to the affinity of TECA to
strongly interact with water in bulk solution which reduces its ability to
adsorb at interfaces. Consequently, the DECA has strong tendency to
irreversibly adsorb at the water-oil interface. The lower adsorption of TECA

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amphiphile on the asphaltene surfaces turns the asphaltene surfaces to be

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more polar and, hence, decreasing its capacity to interact with heptane

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aliphatic solvents. The good ability of DECA to act as asphaltene dispersants
facilitated the demulsification of highly stable water in crude oil emulsions

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with low water contents.

Acknowledgment:
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The authors extend their appreciation to the Deanship of Scientific Research
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at King Saud University for funding this work through research group No.
(RGP-235).
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Table 1. Solubility and surface activity data of DECA and TECA

in water at 25 oC.
RSN Гmax
mL cac γcac Δγ × 10 10 Amin
compounds HLB (−∂γ/∂lnc)T
of mmol/L mN/m mN/m µmol/ nm2
water m2
DECA 11.17 13.5 0.340 33.35 38.85 8.76 3.54 0.047
TECA 12.60 14.36 0.587 31.22 40.98 5.34 2.19 0.076

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Table 2: DLS data and dispersion efficiencies of asphaltenes fraction of

heavy crude oil in heptane in the absence and presence of DECA
and TECA.

Samples Conc. Asphaltenes PDI Asphaltene

g/L Particle sizes dispersion

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(nm) efficiencies
(%)

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Asphaltenes 0 2827.0 0.781 0
DECA 2.5 884.6 0.477 35.6

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5 385.8 0.246 45.6
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10 186.3 0.134 65.7
TECA 2.5 2345.6 0.596 18.6
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5 1890.4 0.518 24.2

10 1404.4 0.450 40.8
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Table 3: Demulsification data of DECA and TECA for the crude oil
emulsions at 60 oC.

90/10 70/30 50/50

Concentrations
compounds DE Time %DE Time %DE Time
(mgL-1)
(%) (minute) (%) (minute) (%) (minute)
25 84 600 68 600 0 -
DECA 50 100 120 68 420 0 -

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100 100 40 68 360 25 600

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50 20 600 46 600 12 600
TECA 100 24 600 60 600 60 600

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250 40 360 20 300 100 420

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Scheme 1. Synthetic route of DECA.

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Scheme 2. Synthetic route of TECA.

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Scheme 3. Adsorption of a) DECA and b) TECA on the asphaltene
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surface into toluene/heptane solutions.

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Figure 1. 1HNMR spectra of a) DECA and b) TECA.

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Figure 2. 13CNMR spectra of a) DECA and b) TECA.

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Figure 3. Relation between water surface tension and different

concentrations of TECA and DECA in water at 25 oC.
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Figure 4. DLS measurements of a)TECA and b) DECA at their cmc in

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Figure 5: IFT data of heavy Arabic crude oil with different concentrations
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of DECA and TECA at 25 oC.

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Figure 6. DLS data for a) asphaltene , b) 10 gL-1 of DECA and c) 10 gL-1 of

DECA in asphaltene n-heptane solutions at 25 oC.

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Figure 7. Optical microscope photos of crude oil water (90/10 Vol %)

emulsion at different times a) 0, b) 10 minute and c) 30 minute
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Figure 8. Relation between DE % and demulsification time of crude oil

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Figure 9. Demulsification photos of crude oil water (90/10 Vol %) emulsion
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Highlights
Demulsification of Heavy Crude Oil Using New Nonionic Cardanol
Surfactants

 New Amphiphilic surfactant was derived from cardanol Cashew nut

oil.

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 Surfactants dispersed asphaltene were used as demulsifier.

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 Surfactants flocculated asphaltenes achieved low demulsification

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rate.

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