Journal of Industrial and Engineering Chemistry 33 (2016) 122130

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Application of new amphiphilic ionic liquid based on ethoxylated

octadecylammonium tosylate as demulsier and petroleum crude oil
spill dispersant
Ayman M. Atta a,b,*, Hamad A. Al-Lohedan a, Mahmood M.S. Abdullah a, Shymaa M. ElSaeed b
a
b

Surfactants Research chair, Department of Chemistry, College of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia
Petroleum Application Department, Egyptian Petroleum Research Institute, Cairo 11727, Egypt

A R T I C L E I N F O

Article history:
Received 21 August 2015
Received in revised form 8 September 2015
Accepted 12 September 2015
Available online 1 October 2015
Keywords:
Amphiphiles
Ionic liquid
Aggregation
Adsorption
Demulsiers

A B S T R A C T

This work reports the synthesis and application of amphiphilic ionic liquid (IL) in the petroleum eld. The
ionic liquid was synthesized by etherication of octadecylamine with tetraethylene glycol followed by
quaternization with p-toluene sulfonic acid. The chemical structure was conrmed by NMR
spectroscopy. The surface activity, aggregation, adsorption, and the solubility of the ethoxylated
octadecylammonium tosylate were investigated. The interfacial parameters between IL aqueous
solution and crude oil emulsions were determined from interfacial tension measurement. The results
showed the dependence of interfacial tension on the concentration, crude oil emulsion composition and
chemical structure of the prepared amphiphiles. The mechanism of aggregation and adsorption
ethoxylated octadecylammonium tosylate was proposed and conrmed at different interfaces. The
demulsication and oil spill dispersion efciencies were investigated at different amphiphile
concentrations. The performance of amphiphilic ILs revealed that their demulsication efciency
reached 100% and the settling time required for efcient separation decreased with increment of water
contents of crude oil emulsions. Moreover, the prepared amphiphilic ILs achieved oil spill dispersion
efciency more than 80% at surfactant oil ratio (1:25).
2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
Recently, the sustainable technologies became the rst priority
in the petroleum and chemicals industry [1]. Ionic liquids (IL)
attracted great attentions as sustainable materials due to their low
volatility(low vapor pressure), thermal stability, low toxicity, high
surface activity due to the presence of cations and anions species in
the same molecules, and high performance as catalysts, and
desulfurization solvents in the petroleum elds [25]. ILs are ionic
molecules that contain both organic cations and inorganic or
organic anions. The difference between inorganic salts and ionic
liquids is based on the size of cations and anions when compared
with sodium or halides. Commonly, the derivatives organic cations
were imidazolium, pyridinium, pyrrolidinium, ammonium,

* Corresponding author at: King Saud University, Department of Chemistry,

College of Science, PO Box 2455, Riyadh 11451, Saudi Arabia.
Tel.:+00966 561557975; fax: +00966 0114675998.
E-mail address: aatta@ksu.edu.sa (A.M. Atta).

phosphonium and sulfonium. The organic anions were alkylsulfate, alkylsulfonate, p-toluenesulfonate (tosylate) and triuoroacetate. The inorganic anions were halides, tetrachloroaluminate,
hexauorophosphate, tetrauoroborate and bis(triuoromethylsulfonyl) imide as examples. The properties of ILs depend on
choosing the correct cations and anion for a specic synthesis.
There are several petroleum processes used different oil-eld
chemicals such as emulsiers, demulsiers, inhibitors, dispersants
and scavengers to modify the crude oils and their products
specications [69]. These chemicals are based on amphiphiles or
polymeric surfactants mixtures having different hydrophile
lipophile balances [10]. They have several advantages over organic
surfactants used in petroleum oileld chemicals due to their
excellent rheology, better solubility in oils and solvents, anticorrosion and recyclability [11,12]. The demulsiers were selected in
the petroleum eld after some preliminary screening based on
bottle test. There are some proposed mechanisms such as masstransfer velocity and the coalescence mechanisms used to
correlate the surfactants efciencies as demulsiers and as oil
spill dispersants with their hydrophiliclipophilic balance (HLB)

http://dx.doi.org/10.1016/j.jiec.2015.09.028
1226-086X/ 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

value and the size of hydrophilic groups of polymeric surfactants

[1316]. Moreover, it was reported that the solubility and high
ability of demulsiers to reach the interfaces affected their
demulsication performances. ILs have greater tendency to reduce
the interfacial tension between polar and nonpolar solvents and to
reduce the water surface tension even at high salt contents or
higher temperature [17]. In this respect, ILs achieved good results
as demulsier for petroleum crude oil emulsions, as asphaltene
dispersants, parafn deposition inhibitors, and as enhanced oil
recovery [18,19].
It is very important to select the best method to synthesis ILs by
choice the suitable hydrophobic cations and anions to use as oileld chemicals. It was previously reported that, ILs as monomers,
polymerizable monomers, oligomers and polymers were prepared
using amines, phosphanes or sulfonates [2022]. Usually, the
tertairyalkyl amines were quaternized with alkylhalides, alkyl or
aryl sulfonates followed by anion exchange reactions. It is better to
complete this reaction without solvent; however, microwave was
used as source of energy to complete these reactions [2325].
Moreover, the ability of ILs to adsorb at interfaces without
aggregations to reduce the interfacial tension between interfaces
and their ability to emulsify, dehydrate the crude oil emulsion or
disperse crude oils are the main principles to design ILs. To achieve
these goals, tertiary amine based on etheried octadecyl amine
was quaternized with p-toluene sulfonic acid to produce
ethoxylated octadecylammonium tosylate as hydrophobic IL.
The reaction was carried out without solvent. The surface and
interfacial activities of the prepared IL were measured to conrm
the dispersion and demulsication mechanisms of IL as dehydrating agents and oil spill dispersant for crude oil emulsions and spills.
Experimental
Materials
All chemicals were analytical grade and produced from Sigma
Aldrich Chemicals Co. Octadecylamine (ODA), p-toluene sulfonic
acid monohydrate (PTSA; 99.5%), were used without further
purication. Tetraethylene glycol (TEG), 2, 2-dichlorodiethyl
ether(DCDE), and sodium hydroxide were used for etherication
of ODA. Toluene, xylene, dioxan, ethylene glycol dimethylether and
ethanol were used as solvents. Double distilled water (DDW) is
used for different measurements. Sea water of Arabic Gulf was
used to prepare synthetic crude oil emulsions and oil spill. Its
salinity, current resistivity and conductivity are 39.99 g/L, 0.019 V
and 2.2 mS/M, respectively. ARBREAKTM 8141 as commercial
demulsier produced by Baker Petrolite based on a high-molecular
weight oxyalkylated phenolic resin was used to compare its results
with the present work. It was generally used in dilute form in
aromatic solvent or blended with chemicals of different generic
structure to give synergistic formulas which may have greater
efciency.
Arabian heavy crude oil produced by Aramco, Saudi Arabia was
used and its specications are reported in previous work [26]. The
asphaltene and water contents are 8.3 and 0.145 wt.%, respectively. The crude oil emulsions having different crude oil compositions
were prepared according to previous reported method [26]. The
crude oil/water ratios were 90/10, 70/30 and 50/50 used to prepare
different crude oil emulsions. The crude oil and sea water mixtures
were stirred using mechanical homogenizer at 9000 rpm for
30 min.

123

(14.3 g) of DCDE as linking agent and 0.2 mol (8 g) of NaOH. The

mixture was heated under nitrogen atmosphere and reuxed for
5 h. The remained solid NaCl precipitate was ltered after
removing of 50 mL of xylene solvent by evaporation under vacuum
using rotary evaporator. The remained product was mixed with hot
super saturated NaCl aqueous solution and extracted by mixing
with isopropanol. The organic layer was removed and the
etheried product of N,N-bis-hexaoxyethlene octadecylamine
was separated as wax solid product and abbreviated as HEOD.
The melting temperature and yield % of HEOD are 56 8C and 85%,
respectively.
Equal mol amounts of HEOD and PTSA were mixed and stirred
after heating at 185 8C for 24 h under nitrogen atmosphere. The
reaction mixture was heated under reduced pressure of 10 mm.Hg
for 24 h using rotary evaporator. The solid product of N,N-bishexaoxyethlene octadecylammonium tosylate (HEOD-TS) was
obtained after cooling to room temperature. The melting
temperature, and yield % of HEOD-TS were 8385 8C and 99.3%,
respectively.
Characterization
The chemical structure of HEOD and HEOD-TS were elucidated
using 1H and 13C NMR spectroscopy model a 400 MHz Bruker
Avance DRX-400 spectrometer.
The surface and interfacial tension of HEOD and HEOD-TS
solution were determined using drop shape analyzer model DSA100(Kruss GmbH, Hamburg, Germany).
Krafft temperature (TK) was determined from measuring the
conductivity of HEOD and HEOD-TS aqueous solution at different
temperatures using Fisher scientic AB30 conductivity meter.
Fluorescence optical microscopy (Olympus BX-41 tted with
DP70 digital camera) was used at an excitation wavelength of
280 nm to investigate the dispersion of crude oil droplets.
Images of dispersed oil droplet were recorded using Olympus
BX51 polarized-light microscope equipped with a Linkam THMS
600 hot stage.
The relative solubility number (RSN) of HEOD and HEOD-TS was
determined by titration their solutions (1 g in mL of dioxane 96 mL
and toluene 4 mL) against water. The volume of water (mL) was
determined as RSN.
Application of HEOD and HEOD-TS as oil spill dispersants [27]
Solutions of 50 g of either HEOD or HEOD-TS in 100 mL of
ethanol were used to disperse oil spill. The evaluation process was
carried out according reported method in previous work [27]. In
brief, Arabian heavy crude oil (5 g) was added on the surface of
250 mL of sea water in 500 mL beaker. The oil spill was stirred with
magnetic stirrer at 700 rpm to obtain vortex with depth of 1 cm.
Different surfactants to oil ratios (SOR) ranged from 1:1 to 1:100
were added to crude oil mixture during 1 min. The stirring was
stopped and 50 mL of the dispersed solution of crude oil in sea
water was removed after 2 min. The dispersed crude oil in water
(50 mL) was extracted with 50 mL of chloroform two times. The
chloroform was evaporated using rotary evaporator to determine
the weight of extracted crude oil. The oil spill dispersant efciency
(OSE) was calculated as [27]:
OSE

Wt: of extracted crude oil  500

Wt: of crude oil

(1)

Synthesis procedure

Application of HEOD and HEOD-TS as demulsier [26]

ODA (0.05 mol; 13.47 g) was dissolved into 100 mL of xylene

and mixed with 0.1 mol of TEG (18.6 g) in the presence of 0.1 mol

The demulsication of crude oil emulsions using different

concentrations of HEOD and HEOD-TS was carried out according

A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

124

CH 3(CH 2)17 NH 2 + ClCH 2CH 2OCH 2CH 2Cl + HO [CH 2CH 2O ] H

DCDE

CH 3(CH 2)17 N

ODA

[CH 2CH 2 O]-H

NaOH

TEG

[CH 2CH 2 O]-H

8

SO 3H

CH 3
PTSA

[CH 2CH 2 O]-H

8

CH 3(CH 2)17 HN O 3S

CH 3

[CH 2CH 2 O]-H

8

Scheme 1. Synthesis of HEOD-TS.

reported bottle test method at 65 8C [26]. The prepared HEOD and

HEOD-TS were diluted with xylene/ethanol (75/25 vol.%) solvent
at concentration of 30 wt.%. The crude oil emulsions (100 mL) were
placed in closed measuring cylinder and heated in water bath at
65 8C. Different concentrations of HEOD and HEOD-TS xylene/
ethanol solutions ranged from 100 to 500 ppm were injected into
crude oil emulsion and shaken vigorously 100 times. The
separation or zero time is determined after injection of the
demulsiers. The demulsication efciency (DE) was determined
from ratios between separated water and emulsied water [26].
Results and discussion
Chemical structure of HEOD-TS
The ODA was etheried with TEG in the presence of DCDE as
linking agent and NaOH as illustrated in the experimental work.
The etherication of amines, phenols, and alcohols were carried
out as reported in our previous procedure [2830]. The etherication reaction of ODA indicated by removing the NaCl precipitate
that produced from reaction of ODA, DCDE, TEG and NaOH as

represented in the Scheme 1. The tertiary amine of HEOD is

quaternized using PTSA to produce HEOD-TS as new IL. The
unreacted TEG and DCDE were desalted out using supersaturated
solution of NaCl to extract from organic layer of xylene/
isopropanol solvent. The remained unreacted NaOH was removed
after washing the products with water until pH of solution reached
pH 6.8. The purity of HEOD and HEOD-TS was conrmed from NMR
analyses and surface tension measurements as it will discuss in the
forthcoming section.
The chemical structures of HEOD and HEOD-TS elucidate from
1
H NMR and 13C NMR as represented in Figs. 1 and 2, respectively.
The etherication of ODA conrms from the presence of peaks that
appeared at 3.58 ppm and 2.27 ppm which attributed to OCH2
CH2O and OH, respectively (Fig. 1). The peaks appeared at
chemical shifts (d, ppm) 0.722 ppm (triplet, 3H, J = 6.6 Hz),
0.923 ppm (singlet, 3H), 1.18 ppm and (multiplet, 32H,
J = 6.6 Hz) can be attributed to CH3 of ODA, CH3 attached to
tosylate and (CH2)16, respectively conrm the presence of alkyl
chains of ODA in chemical structures of HEOD-TS. The peaks at
7.69 ppm (doublet of doublet, 2H, J = 8.1 Hz), and 7.09 ppm
(doublet of doublet, 2H, J = 8.4 Hz) indicate phenyl protons of

Fig. 1. 1H NMR spectrum of HEOD-TS.

A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

125

Fig. 3. Relation between conductivity of aqueous solution of HEOD and HEOD-TS

and solubilization temperature.

Fig. 2.

13

C NMR spectrum of HEOD-TS.

tosylate and conrm the incorporation of PTSA of HEOD-TS (Fig. 1).

The peaks at 3.892 (triplet, 4H, J = 6.9 Hz) and broad peak at
7.25 ppm (singlet, H) represent the CH2N and +NH, respectively
(Fig. 1). These peaks elucidate the quaternization of tertiary amine
group of HEOD. The disappearance of amine group NH2 or NH
groups, that appeared at broad peaks at 2.3 ppm conrms that the
conversion of ODA to tertiary amine without side products [28].
13
C NMR spectrum of HEOD-TS (Fig. 2) showed peaks at
d = 142.63, 139.86, 128.99 and 125.09 ppm which conrm phenyl
carbons of tosylate group. The peaks at 77.72, 61.23, 30.77, 29.69,
29.39, 28.72, 27.60, 29.16, 22.49 and 13.61 ppm in spectra of HEOD
and HEOD-TS conrm the presence of OCH2, NCH2, CH2 and CH3
carbons of TEG and ODA (Fig. 2).
Surface activity of HEOD-TS
Recently amphiphilic ILs attracted great attention due to their
superior behaviors in water which corresponded to their
amphiphilic and electrolytes behaviors in solution [31,32]. The
etherication of ODA with TEG is used to enhance its interactions
with water and organic solvents. These interactions were
controlled by balance between hydrophilic groups and hydrophobic groups that are used to design the surfactant molecules. This
balance can be calculated theoretically for nonionic surfactants
from hydrophile lipophile balance (HLP) which calculated from
Grifn formula [33]:
HLB

M:Wt: of hydrophilic moieties  20

M:Wt: of molecules

(2)

The calculated HLB value of HEOD was 11.58 which conrmed

that the HEOD can be solubilized in both polar and nonpolar
organic solvents. Moreover, the quaternization of HEOD with PTSA
alters its solubility in organic solvents. In this respect, the solubility
of both HEOD and HEOD-TS was evaluated from RSN, as described
in the Experimental section, and listed in Table 1. The RSN values

indicate that the solubility of HEOD in water is greater than HEODTS. It means that the hydrophobic tolyl groups of PTSA controls the
solubility of HEOD-TS in organic solvent. Moreover, the Krafft
temperature (TK) values determined from conductivity temperature relationship as represented in Fig. 3 also used to investigate
the interaction of the prepared IL (HEOD-TS) with water. TK values
of HEOD and HEOD-TS are 44.1 and 46.9 8C, respectively. These
data conrm that the solubility of HEOD in water is greater than
HEOD-TS. This means that the tosylate anion reduces the water
solubility of HEOD-TS in water due to hydrophobic effect of their
methyl and phenyl groups.
It was previously reported that the ILs form aggregates in the
aqueous solutions [34]. The aggregations of ILs in the solution
control their applications as dispersants, wetting agents, emulsiers and demulsiers. It was previously reported that, the ILs
formed several types of aggregates such as vesicles, [35] liquid
crystal [36] and micro-emulsions [3739]. The chemical structure
of HEOD-TS possesses three different types of interaction derived
from hydrophobicity of OD hydrophobe, interactions of hydrophilic groups of TEG and ionic nature of tosylate ions. The
aggregations of HEOD and HEOD-TS in aqueous solution were
estimated from relation between the surface tension of water and
different concentrations of HEOD and HEOD-TS (ln c; mol/L) as
illustrated in Fig. 4. The ability of surfactants and ILs to form
micelle or aggregates can be determined from critical micelle or
aggregation concentrations (cmc or cac; mol/L) as illustrated in
Fig. 4. The appearance of uniform curves from the relation between
HEOD or HEOD-TS concentrations and their surface tension
conrms the purity of the prepared IL. The cac value of HEOD
and HEOD-TS were determined and listed in Table 1. The data
indicate that cac of HEOD-TS equals 0.64 mM which is lower than
that of HEOD (1.57 mM) surfactant and other amphiphile IL [39].
The cac values of HEOD-TS and HEOD indicate the lower solubility
of HEOD-TS in water than HEOD as indicated also from RSN value.
This means that HEOD-TS aggregates at lower concentration more
than HEOD. This was referred to the hydrophobic nature of tosylate
ions of HEOD-TS. Moreover, pp interaction between phenyl
groups of tosylate affects the packing of HEOD-TS at interfaces and
in bulk solution to form compact at aggregates [40]. The balance
between the hydrophilicity and hydrophobicity affects the

Table 1
Surface activity parameters of HEOD and HEOD-TS concentrations in water at 25 8C.
Compounds

Cac (mM)

gcac (mN/m)

pcac (mN/m)

@g/@ ln c

max  1010 (mol/cm2)

Amin (nm2/molecule)

RSN (mL)

TK (8C)

HEOD
HEOD-TS

1.57
0.64

37.10
33.78

35.0
38.0

7.82
7.62

3.16
3.07

0.52
0.54

13.70
11.40

44.10
46.90

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A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

Fig. 4. Adsorption isotherm of HEOD and HEOD-TS aqueous solution at 25 8C.

formation of aggregates. This means the hydrophobic interactions

between hydrophobic groups are the main reason for aggregation
of HEOD-TS in water.
The good interaction between water and ILs reduces the surface
tension of water. The nature of both cations and anions of ILs
control the interaction between IL and water molecules. It was
reported that [41] the cations of ILs control their hydrophobicity.
Moreover, the polarity of ILs was controlled their ability to reduce
water surface tension [42]. The relation between surface tension
and ln c of HEOD and HEOD-TS (Fig. 4) indicates that HEOD-TS
reduced the water surface tension more than HEOD. The relation
between surface tension values of HEOD and HEOD-TS and ageing
time was represented in Fig. 5. The data indicate that HEOD-TS
adsorbed at interface in short time more than HEOD which
increased with increasing their concentrations. The effectiveness
of HEOD and HEOD-TS to reduce the surface tension (pcmc) was
calculated from the equation [43]:

pcac g 0  g cac

(3)

where g0 and gcac are water surface tension (72.1 mN/m) and
surface tension at cac, respectively. The greater p cac value of
HEOD-TS more than HEOD indicates that the sulfonate anions of
HEOD-TS interact with water via dipole -dipole interaction
mechanism.
The adsorption at air water interfaces is an alternative
mechanism for aggregation or micellization of HEOD and HEODTS in bulk solution. The concentrations of HEOD and HEOD-TS at air
water interface were investigated from surface excess (max)

Fig. 5. Relation between surface tension and ageing temperature of (a) HEOD-TS
and (b) HEOD at 25 8C.

equation [43]:


1
@ g

G max
RT
@ ln c T

(4)

where (@g/@ ln c)T is the slope of the straight lines of g versus ln c

at T (constant temperature) and R gas constant (in J/(mol K)).
Moreover the max was used to calculate the minimum area Amin of
HEOD and HEOD-TS at the air/water interface from equation [43]:
Amin

1016
N G max

(5)

where N is Avogadros number. The value of max and Amin were

calculated and listed in Table 1. The data conrm that the

Scheme 2. Behavior of HEOD-TS in aqueous solution (a) aggregation and (b) adsorption.

A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

127

concentration of HEOD at interface, max, is higher than HEOD-TS

that attributed to increment of its Amin value more than HEOD.
Although Fig. 5 indicates that HEOD-TS molecules are greatly
adsorbed at interface and attained equilibrium in shorter time
more than HEOD. This behavior was referred to packing of
molecules at air/water interface [44]. In this respect, there are two
types of hydrophilic interactions and one hydrophobic interaction
controlled the adsorption and aggregation of HEOD-TS. The
electrostatic interactions between ammonium cation and tosylate
anion via hydrogen bonds between ethoxy groups or hydroxyl
group with water are the deriving for hydrophilic interactions.
While the hydrogen bonds between ether groups and water and
hydrophobic with van der Waals interactions between alkyl
groups of HEOD control its surface activity. The electrostatic
interactions between cations and anions of HEOD-TS are preferred
to create networks rather than hydrogen bond as illustrated in
Scheme 2 which increases the area per molecule of HEOD-TS more
than HEOD and consequently reduces its concentration at air/
water interface.
Application as oil spill dispersants
Oil spills, produced from ship accidents during crude oil
transportation or during production of crude oil from off-shore
wells, have serious hazardous and economic problems [45]. There
are several methods were used to control the oil spill pollution
such as mechanical, chemicals and bioremediation techniques
[45]. The chemical methods attracted great attention due to their
high efciencies and effectiveness, fast treatment of oil spill such
as dispersants, washing agents, demulsiers, adsorbents with
applying advanced magnetic separation method [27,4648].
Among several chemical treatments, dispersants still play an
important technique for oil spill removal due to availability of
chemicals based on mixtures of nonionic surfactants mixed with
10% of ionic surfactants [45]. It was reported that the nonionic
surfactants based on poly (ethylene oxide-b-propylene oxide),
polyoxyethylene sorbitol oleates have been used as oil spill
disperants due to nontoxic behaviors [49,50]. In the present work,
IL based on HEOD-TS will be evaluate as oil spill dispersant as well
as HEOD due to presence of oxyethylene unit, ODA and tosylate
groups that combined between nonionic and anionic surfactants.
Different surfactant to oil ratios (SOR) ranged from 1:1 to 1:100
(vol:vol%) were used to determine the efciencies of dispersion as
illustrated in the experimental work. The OSE data were
determined and listed in Table 2. The uorescence optical
microscopy photos of dispersed oil droplets in the presence of
HEOD-TS were illustrated in Fig. 6. The polarized optical
microscope photos of the crude oil droplets in the presence of
different concentrations of HEOD-TS were represented in Fig. 7.
The data listed in Table 2 and photos in Fig. 6 indicate that the OSE
values of dispersion increased with increment of HEOD-TS
concentrations (SOR) as indicated from the smaller of particle
size distribution of dispersed oil droplet (Fig. 6). Moreover, the
optical polarized microscope images (Fig. 7a and b) indicate the
formation of thin lms at oil droplet periphery with increasing
Table 2
Results of oil spill dispersion efciency using different SOR of HEOD and HEOD-TS
and their mixture as oil spill dispersant at 25 8C.
Compounds

HEOD
HEOD-TS
HEOD: HEOD-TS (80:20)

Oil spill dispersion efciency OSE (%) at

different SOR
(1:100)

(1:25)

(1:10)

(1:1)

32.62
43.06
40.34

64.64
81.46
80.32

72.62
86.04
83.06

83.82
93.74
91.26

Fig. 6. Optical microscope image of dispersed oil droplet using HEOD-TS at different
SOR (a) 1:1, (b) 1:25 and (c) 1:100.

HEOD-TS concentrations. An interesting behavior was observed at

SOR 1:25 (Fig. 7c) in which the HEOD-TS agglomerates at the
center of crude oil droplet to form emulsions as water in oil (W/O).
The decrement of SOR to 1:100 (Fig. 6d) decreases the crude oil
dispersion. These data indicate that HEOD-TS assemble at water
crude oil interface (liquid liquid interface) with interfacial selfassembled particle structure as illustrated in Fig. 6. The partitioning of HEOD-TS at preference of dispersed oil droplet and water
continuous phases determines the oil spill dispersion efciencies.
Moreover, the oil drop sizes reduced to prevent agglomeration of
crude oil at water surface. The photos of Fig. 6 conrm the closepacked assemble and fully covered layer of IL at ionic liquidwater
interfaces as partially covered droplets. From these data, it can be
concluded that HEOD-TS shows high oil spill extraction efciency,
whereas the HEOD remains in the water phase and cannot form
layer at oil droplets.
From previous discussed data, it can be estimated that the
tosylate ions and tertiary ammonium cations play important factor
for electrostatic adsorption mechanism at the oil droplet. It is well

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A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

Fig. 7. Polarized optical microscope of dispersed oil droplet using HEOD-TS at different SOR (a) 1:1, (b) 1:10, (c) 1:25 and (d) 1:100.

known that, the presence heteroatoms such as N, O, S etc. and

presence of polycondensed cycles and aliphatic chains in the
chemical structure of asphaltene (determined for Arabian heavy
crude oil as 8 wt%) affect their behavior to be natural amphiphile
surfactants [51,52]. In this respect, the HEOD-TS can interacts with
asphaltene at oil droplet to replace it with the formation of selfassembled layer on oil droplet which increases the dispersion of
crude oil droplet due to repulsion between charged oil droplet. This
mechanism will be elucidate in the forthcoming section from
interfacial tension measurements.
Demulsication of crude oil emulsions
Demulsiers are the best oil-eld chemicals that can be used to
solve the petroleum crude oil emulsions, petroleum sludge and gas
hydrates problems [53,54]. The demulsiers usually are mixtures
of surfactants having HLP ranged from 10 to 13 based on types of
crude oil emulsions [53]. The ability of surfactants to adsorb at
water/oil interfaces, replace the asphaltene rigid lms at interfaces
with the formation of soft lm and reduction the interfacial tension
are very important parameters to select the demulsiers [55]. It
was also reported that the xylene/ethanol 75/25 (vol%) solvent,
used to solubilize demulsiers, achieved good results to reduce the
interfacial tension in the presence of demulsier surfactants
[26,55]. In this respect, the interfacial tension (IFT; mN/m)
between crude oil and water solutions of HEOD and HEOD-TS
were determined and listed in Table 3. The petroleum emulsions
were produced during oil production has several disadvantages on
the petroleum industry [53]. The synthetic crude oil/water

emulsions, ranged from 90/10 to 50/50, prepared in this study

are W/O emulsions as indicated from drop test method that
conrms that the outer phase is oil because it was completely
dispersed in toluene.
The data of IFT represented in Table 3 show that the interfacial
tension between crude oil emulsions and water were reduced with
increase the water contents in emulsions. Moreover, the reduction
of IFT increases with increasing the concentrations of HEOD and
HEOD-TS. The HEOD-TS shows greater reduction in IFT at higher
concentrations of HEOD-TS and increment of water contents of
emulsion. This behavior can be attributed to salt interactions
between inorganic salts of brine sea water and organic salts of
HEOD-TS [56]. In the present system the head groups of HEOD-TS

Table 3
IFT data between crude oil emulsions and aqueous solutions of HEOD and HEOD-TS
at 25 8C.
Concentrations (ppm)

Designation

IFT (mN/m)
90/10

70/30

50/50

28

25

22

100

HEOD
HEOD-TS

18
10

17
8

10
3

250

HEOD
HEOD-TS

15
5

13
2

500

HEOD
HEOD-TS

10
1.3

8
0.3

8
1.8
5
0.1

A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

is cationic due to positive charges of quaternary ammonium salts.

The HEOD-TS cannot arrange freely at water oil interface due to
low water and salt contents of emulsion 90/10. The increment of
water contents of emulsion (50/50) increases the attractive forces
between positive charge of ammonium salt and Cl of inorganic
salt of water via increment interaction between Na+ and tosylate
anion. These interactions decrease the repulsion between HEODTS cations and anions that reect on the easier accumulation of IL
at oil water interfaces. The easier accumulation of HEOD-TS at
interfaces decreases the IFT more than HEOD. This behavior
contradicts with IFT value of traditional surfactants that affected
by salt and cannot reduce IFT value [15]. This means that HEOD-TS
is suitable for demulsication of crude oils having high salt
contents.
Different concentrations of HEOD-TS and HEOD ranged from
100 to 500 ppm were used to demulsify the different crude oil
emulsions using conventional heating method as described in the
Experimental section. The same concentrations of ARBREAKTM
8141 (commercial demulsiers) were injected to compare the DE
data. The DE (%) and the separation settling times of HEOD-TS and
HEOD were determined and listed in Table 4. The relations
between DE (%) and separation time of crude oil emulsions using
different concentrations of HEOD-TS were represented in Fig. 8.
The photos of water separations of crude oil emulsions using
HEOD-TS and HEOD were claried in Fig. 9. Careful inspection of
data listed in Table 4 indicates the DE (%) increased when HEOD-TS
was used at different concentrations. Moreover, the DE (%)
increases with increasing water contents of crude oil emulsions.
It can be argued that the HEOD-TS solutions in xylene/ethanol (75/
25) have greater efciency to migrate at oilwater interfaces to
replace the asphaltene layer. However, the presence of octadecyl
alkyl chain in the chemical structure of HEOD-TS assists the
molecules to diffuse in oil as continuous phase to replace
asphaltene layer at water/oil interface [57]. The data of IFT
indicate the increment of HEOD-TS concentrations reduce the IFT
of crude oil emulsions which conrm the formation of less rigid
lm at interface from HEOD-TS. Accordingly, the ability of HEODTS to replace asphaltene layers at emulsion droplets controls the
DE (%) data. Moreover, the presence of xylene/ethanol (75/25)
provides better mixing of the HEOD-TS into the Arabian heavy
crude oil that facilitates the diffusion of HEOD-TS into the emulsion
interface [58].
The data of Fig. 8 indicate that the time of water separation of
crude oil emulsions depends on the crude oil compositions and
HEOD-TS concentrations. It was noticed that the increment
of emulsion water contents reduce the water separation time of
crude oil emulsions. The kinetics dehydration curves (Fig. 8) of
crude oil emulsions showed s-curves which indicated the

129

Fig. 8. Demulsication kinetics of HEOD-TS at different compositions of crude oil

water emulsions at (a) 90/10, (b) 70/30 and (c) 50/50.

demulsication mechanism of HEOD-TS of crude oil emulsions

[59]. The rst stage depends on HEOD-TS diffusion, second stage
conrms the replacement of asphaltene lms, third stage
represents dehydration and last forth stage claries dehydration

Table 4
Demulsication efciencies and their times at different concentrations of HEOD and HEOD-TS for different crude oil emulsions at 65 8C.
Surfactant

Conc. (ppm)

Demulsication data
70/30

90/10
DE (%)

Time (min)

DEE (%)

50/50
Time (min)

DE (%)

Time (min)

HEOD

100
250
500

0
0
20

0
0
400

66.67
73.33
80

440
360
360

100
100
100

380
340
320

HEOD-TS

100
250
500

30
40
60

400
360
340

75
80
86

360
300
280

100
100
100

320
280
240

ARBREAKTM 8141

100
250
500

25
30
40

500
450
400

100
100
100

400
350
300

100
100
100

350
220
120

130

A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 122130

References

Fig. 9. Water separation photos of crude oil emulsions using (a) HEOD-TS and HEOD
as demulsier.

equilibrium step. The rst step depends on the diffusion of HEODTS or HEOD in the crude oil emulsions controls the rate of
dehydration mechanism of demulsication process [15].
The photos of demulsication of crude oil emulsions (Fig. 9)
show that the clearances of water that separated using HEOD-TS
more than HEOD. This means that the water was not
contaminated with oil at dehydration process. This behavior
indicates the water separation using HEOD-TS proceeds through
diffusion and adsorption mechanism which permits faster
transportation of demulsier molecules to the water-droplet
interface [58].
Conclusions
New amphiphilic ionic liquid based on quaternization of
ethoxylated octadecylamine with tosylate groups show lower
cac value that referred to the nature of tosylate ions that increased
the hydrophobicity of the produced IL. Moreover, the phenyl group
of tosylate produced pp interactions increased the compact
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crude oil droplet due to repulsion between charged oil droplets.
This mechanism conrmed from interfacial tension measurements
and demulsication of crude oil emulsions.
Acknowledgement
This project was nancially supported by King Saud University
vice deanship of research chairs.

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