Fuel 143 (2015) 519–526

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Ionic liquids as viscosity modifiers for heavy and extra-heavy crude oils
Deepa Subramanian a, Kathleen Wu a, Abbas Firoozabadi a,b,⇑
a
Department of Chemical and Environmental Engineering, Yale University, 9 Hillhouse Avenue, New Haven, CT 06511, United States
b
Reservoir Engineering Research Institute, 595 Lytton Ave, Palo Alto, CA 94301, United States

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Ionic liquids are used to reduce the

viscosity of heavy oil and bitumens.
 Viscosity reduction up to 35% is
observed using 5 ppm of
dodecylpyridinium chloride.
 Ionic liquids seem to interact with
asphaltenes to decrease their
aggregate size.
 Decrease in asphaltene aggregate size
seems to lower the crude viscosity.
 Intermolecular interactions include
p–p, aliphatic, acid–base, and charge-
transfer.

a r t i c l e i n f o a b s t r a c t

Article history: Heavy oils and extra-heavy oils (bitumens) are difficult to produce and transport due to problems asso-
Received 6 August 2014 ciated with the aggregation of asphaltene molecules. Asphaltenes, a primary component of heavy oils and
Received in revised form 11 November 2014 bitumens, affect the viscosity significantly. Traditional methods of viscosity reduction for heavy petro-
Accepted 17 November 2014
leum fluids include thermal or dilution methods. In this work, we employ an alternative method for vis-
Available online 3 December 2014
cosity reduction, by using functionalized molecules that could interact with the asphaltenes and change
the properties of the crude oil at the molecular level, reducing viscosity. Ionic liquids, having favorable
Keywords:
thermophysical properties such as low vapor pressure, are the functionalized molecules tested in this
Ionic liquids
Heavy oil
work. Various properties of the ionic liquids such as alkyl tail lengths (C2, C4, C6, C8, C10, and C12), coun-
Bitumen ter-ion charge density (chloride, thiocyanate, and tetrafluoroborate), and type of head group (imidazoli-
Molecular interactions um, pyridinium, and thiazolium) are tested with a Mexican heavy oil and Canadian and Venezuelan
Asphaltenes bitumens. Small amounts of the additives (between 1 and 10 ppm), dissolved in toluene, are used. Viscos-
ity reduction up to 35% is observed for the crude oils, with dodecylpyridinium chloride showing the max-
imum reduction. Various molecular interactions between the ionic liquids and the asphaltene molecules,
such as aromatic, acid–base, and charge-transfer interactions, seem to hinder the asphaltene aggregate
formation, which consequently reduces the viscosity. These results set the stage for further research
on the viscosity reduction of heavy oil and extra-heavy oils by using functionalized molecules.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction

Petroleum is amongst the most widely used natural resource

⇑ Corresponding author at: Department of Chemical and Environmental Engi- available to man. It is a heterogeneous mixture of many organic
neering, Yale University, 9 Hillhouse Avenue, New Haven, CT 06511, United States. compounds with varying molecular weights [1]. Conventional
E-mail address: abbas.firoozabadi@yale.edu (A. Firoozabadi). petroleum (oil), consists of free flowing liquid hydrocarbons

http://dx.doi.org/10.1016/j.fuel.2014.11.051
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
520 D. Subramanian et al. / Fuel 143 (2015) 519–526

extracted from reservoirs. Oil is an indispensable part of our mod- density of cation head group, and counter-ion charge density were
ern world, used for almost all activities ranging from transporta- investigated. They observed that ionic liquids having high anion
tion to industrialization [1,2]. The economies of several countries charge density and low cation charge density were effective at
are dependent on oil [3]. In 2012, the amount of oil consumed inhibiting asphaltene precipitation. They also noted that as the
world wide totaled 90 million barrels per day, a 1% increase as concentration of the ionic liquid is increased, from about 0.5 to
compared to 2011 [4,5]. At the end of 2012, the proven world about 5 wt.%, the stability of crude oil increased. They attribute this
reserves of oil was about 1700 billion barrels, an increase of about to electrostatic interactions between the ionic liquid and the
25% over the past decade [5]. The current reserves are projected to asphaltene molecule, which lowers the asphaltene aggregate size
last for about 50 years at the present level of world oil demand, but and reduces precipitation.
the global oil requirement is steadily rising [4]. Driven by the In 2009 Boukherissa et al. investigated the use of ionic liquids as
energy consumption of emerging markets such as India and China, efficient dispersants of crude oil [13]. Imidazolium ionic liquids
the world oil demand is projected to rise by 20–25% over the next consisting of the boronic acid functionality or the propenyl group
decade [4]. functionality in the cation head group, with bromide anions, were
Heavy oils, bitumens, oil sands, and shale deposits are all alter- tested. Model oils containing around 2% asphaltenes in a 2:1 hep-
natives to conventional oil [4]. The Middle East leads the world in tane:toluene mixture were treated with the ionic liquids, whose
reserves of conventional oil, while the unconventional oil reserves concentration varied from about 2% to 8%. It was observed that
are abundant in the Americas, with Venezuela leading the reserves the ionic liquids with the boronic acid head group, and having a tail
of heavy oil, and Canada leading the reserves of extra-heavy oil [5]. of at least 8 carbon atoms, reduced the viscosity of the model oil by
Oils are classified based on the American Petroleum Institute (API) about 80% (from 16 to about 3 Pa s). They attribute this effect to
Standard. According to this standard light oil is defined as having polar interactions between the Lewis-acid moiety of the boronic
an API gravity greater than 31.1 , medium oil is defined as having acid head group and the basic regions of the asphaltene molecules,
an API gravity between 22.3 and 31.3 , heavy oil has an API gravity which limits the growth of asphaltene aggregates and reduces the
between 10 and 22.3 , and extra-heavy oil (bitumen) has an API viscosity.
gravity less than 10 (API gravity is inversely related to specific Recent experimental work by Chàvez-Miyauchi et al. show the
gravity) [4]. The higher the API index of oil, the greater is the com- effect of adding polyisobutylene succinimides, consisting of long
mercial value. branched alkyl tail lengths and a boronic acid head group, on the
Heavy oils and bitumens, two unconventional oil resources viscosity of Mexican crude oil [14]. They observed that mixing
explored in this work, are characterized by high viscosities, which about 0.2 wt.% of the additive (with a tail of 16 carbon atoms)
require prodigious methods to extract them from the subsurface and 0.3 wt.% xylene with 99.5 wt.% of a Mexican crude oil, lowered
and make them transportable across long distances [4,6,7]. These the viscosity by 11% (change is compared to 99.5 wt.% crude oil
oils are extracted via two methods: (1) thermal and (2) non- containing 0.5 wt.% xylene) [14]. They ascribe this effect to p–p
thermal [4]. Thermal methods include techniques such as insitu interactions and the formation of hydrogen bonds between the
combustion, cyclic steam stimulation, and steam assisted gravity functionalized molecule and the asphaltenes, which lowers the
drainage. Non-thermal methods include techniques such as asphaltene aggregate size and reduces the viscosity of the crude.
dilution, chemical flooding and formation of oil in water emulsion. The presence of a branched tail leads to further disorder in the sys-
Thermal methods, although very effective, require huge amounts tem and hinders aggregate formation. The same group then inves-
of energy and involve high monetary expenditures. On the other tigated the effect of adding another novel chemical additive, n-aryl
hand, the non-thermal methods are not energy intensive, but amino alcohol - a tetrameric complex with cyclopentanes, benzene
require bulk amounts of chemicals. rings, amino, and hydroxyl groups with long alkyl tails and the
In this work, we implement an alternative approach for viscos- boronic acid head group. This complex, with a tail of 16 carbon
ity reduction: our goal is to use functionalized molecules that can atoms, was mixed with a different Mexican crude oil to determine
interact with the asphaltene molecules in crude oils, and lower the viscosity reduction. They noted that adding 0.3 wt.% of the additive
viscosity of the oil. Asphaltenes, the most polar fraction of crude to 1.2 wt.% heptane and 98.5 wt.% crude, reduces the viscosity of
oils, seem to be a primary factor contributing to the high viscosity the crude by about 8 wt.% (the reference being 98.5 wt.% crude
of heavy oils and bitumens [8,9]. The interactions between the containing 1.5 wt.% heptane) [15]. They attribute these effects
functionalized molecules and the asphaltene molecules could to the interactions between the functionalized molecules and
change the properties of crude oil at a molecular level, which could the asphaltene molecules [15]. The additive seems to inhibit the
then reduce the viscosity of the crude. With this outlook, we inves- growth of asphaltene aggregates, by either associating with the
tigate the scope of using ionic liquids as the functionalized mole- asphaltenes through the formation of hydrogen bonds, or by
cules to reduce the viscosity of heavy oils and bitumens. creating a steric interference that prevents the assemblage of
Ionic liquids are salts with melting points below 100  C [10]. asphaltene molecules, thus lowering the viscosity of the crude oils.
They have low vapor pressures and are environmentally more Motivated by the successful results on the application of ionic
benign than other organic solvents, such as volatile aromatics liquids to enhance stability and lower viscosity of crude oils, this
and alkanes. Properties of ionic liquids can be customized by work is focused on investigating the commercially available ionic
choosing the appropriate combination of anion and cation for spe- liquids for the same purpose. The effect of 1-alkyl-3-methyl imi-
cific applications [11]. The most important reason for the choice of dazolium salts, with varying alkyl tail length (from C2 to C12),
ionic liquids is that they exhibit a wide variety of functionalities, and varying anion charge density (chloride, thiocyanate, and tetra-
such as aromatic and acid–base interactions. These functionalities fluoroborate) are tested in this work. The ionic liquid with the
cause the ionic liquids to interact with the asphaltenes and lower dodecyl tail and the chloride anion are tested with various head
the asphaltene aggregate size, which leads to a reduction in the groups, imidazolium, thiazolium, and pyridinium. Very small con-
viscosity of the crude oil. centrations, between 1 and 10 ppm, of the ionic liquids are used,
Various researchers have used functionalized molecules to keeping in view environmental and economic considerations.
enhance stability and lower the viscosity of crude oil. Ionic liquids Results indicate that there exists a non-monotonic relationship
were first tested by Hu et al. in 2005 to reduce the precipitation of between the tail length of the ionic liquid and the observed reduc-
asphaltenes and enhance the stability of crude oils [12]. Many fea- tion in viscosity of the crude oils. Ionic liquids with higher tail
tures of the ionic liquids, such as effect of alkyl tail length, charge lengths (C8–C12) are more effective at viscosity reduction com-
 D. Subramanian et al. / Fuel 143 (2015) 519–526 521

pared to ionic liquids with smaller tail lengths (C2–C6). Anions (TBN). TAN and TBN values of crude oils seem to be correlated with
with higher charge density, such as chloride, seem to be more the asphaltene content of the oils [16]. TAN and TBN are deter-
effective at viscosity reduction compared to anions with lower mined by using a potentiometric titrator unit (Metrohm 916
charge density. Ionic liquid with the pyridinium head group is Ti-touch) combined with a glass electrode (Metrohm Solvotrode).
the most effective in reducing the viscosity (with a maximum The TAN is determined in accordance with ASTM D664, while the
reduction of about 35%) as compared to ionic liquids with imidazo- TBN is determined in accordance with ASTM 2896. The titrating
lium or thiazolium head groups. All these results are ascribed to solvent in TAN measurements is 0.1 M KOH dissolved in ethanol,
specific non-covalent interactions between the ionic liquid and while the titrating solvent in TBN is 0.1 M perchloric acid in glacial
the asphaltenes. acetic acid. The samples are sonicated for about 45 min at 40  C
before the measurements to ensure homogeneity. Each measure-
2. Materials and methods ment is repeated 4–6 times to ensure reproducibility of results.
The resultant TAN and TBN values are given in Table 2.
2.1. Materials The critical (reverse) micelle concentration, CMC, of the ionic
liquids, in solvents toluene and heptol (1:1 by volume of toluene
Three different oils, heavy oil from Mexico and bitumens from and heptane), is determined by static light scattering (SLS) exper-
Canada and Venezuela, are investigated in this work. The 1-alkyl- iments. The light scattering intensity of samples containing varying
3-methyl imidazolium chlorides are purchased from Sigma concentrations of the ionic liquid, ranging from 1 ppm to
Aldrich, (C2-ethyl, C4-butyl, C6-hexyl, and C10-decyl) and Iolitech 1000 ppm (solubility limit), are measured at a scattering angle of
Inc. (C8-octyl and C12-dodecyl). The ionic liquids 1-butyl-3-methyl 90  and T = 25  C. The concentration at which the derivative of
imidazolium with anions chloride, thiocyanate, and tetrafluorobo- the intensity exhibits a maximum is taken as the CMC concentra-
rate are from Sigma Aldrich. Dodecylpyridiniumdinium chloride is tion. These results are summarized in Table 3. Solubility experi-
purchased from Santa Cruz Biotechnology while dodecylthiazoli- ments in heptane indicate that the solubility of the ionic liquids
um chloride is purchased from Celestial Specialty Chemicals. All in heptane is below 1 ppm. As a result, due to practical limitations
ionic liquids have a purity > 98%. Toluene, ethanol, isopropanol, of sample preparation, CMC measurements are not carried out in
anhydrous KOH, and glacial acetic acid are from Avantor Chemicals heptane.
(ACS grade reagents), heptane is from Fisher Scientific (ACS grade
reagent), and 0.1 M perchloric acid in glacial acetic acid is from 2.3. Sample preparation for rheology
Sigma Aldrich.
A small amount of the crude oils, about 5 g, is weighed out in a
2.2. Characterization methods glass vial and mixed with appropriate amounts of the ionic liquid,
which is previously dissolved in toluene. The sample is then soni-
The three oils are characterized to determine properties such as cated for 20 min at room temperature, after which it is manually
asphaltene content, density, total acid number (TAN), and total mixed for about 30 s. The sample is further sonicated for 40 min
base number (TBN). The asphaltene content of the oils is measured at about 40  C and cooled to room temperature before performing
by mixing 1 g of the oil with 40 mL of heptane. The samples are rheology measurements. Before each rheology measurement, the
then sonicated for about 15 min and left to rest for about 24 h. sample is vigorously agitated for about 30 s to ensure homogene-
Next, they are vacuum filtered with 200 nm cellulose-nitrate filters ity. Multiple rheology runs (3–4) are carried out from each sample,
(purchased from Whatman) and the residue is left to dry over and 2–4 samples, for each concentration, are tested to confirm
night. Subsequently, the residue is collected and weighed to deter- reproducibility of results.
mine the amount of asphaltenes per gram of oil. Results are based
on 8–10 measurements.
The densities of the heavy and the extra-heavy oils are deter- 2.4. Rheology experiments
mined by diluting them with various concentrations of toluene,
and extrapolating the values to 0 wt.% toluene. The density of oil- Rheology experiments are carried out in an Anton-Paar MCR302
toluene mixtures is measured by using an Anton Paar densitometer Rheometer. The MCR302 functions on an air-bearing technology,
at T = 25  C. Multiple density measurements (3–4) are carried out employing parallel-plate and cone-and-plate techniques to mea-
for each concentration and 4–5 concentrations are tested for each sure viscosity. Most of the experiments in this work use the paral-
oil. The API gravity is computed from the density, as given in Eq. lel-plate system, which requires a small volume of sample for each
(1). The results are summarized in Table 1. run, and works ideally at varying temperature gradients as com-
pared to the cone-and-plate system. To maintain temperature after
141:5 loading the sample, the sample and the tool-system are enclosed
API gravity ¼  131:5 ð1Þ
Specific gravity with a thermo-protecting hood, which is an inherent part of the
The acidity and basicity of the crude oils are measured by deter- MCR302 rheometer. The thermo-protecting hood also contains a
mining the total acid number (TAN) and the total base number ’’solvent trap’’ provision, which leads to a controlled environment
around the sample and prevents drying or evaporation of the sol-
Table 1 vent and the sample. In this work, n-decane is used as the ’’solvent
Properties of the crude oils. trap’’ fluid.
Name Asphaltene Density API gravity ( )
content (wt.%) (g/cc)
3. Results
Mexican heavy Oil 34 0.978 13.2
(±1) (±0.0002)
Fig. 1 depicts the viscosity of heavy oil and the bitumens as a
Canadian bitumen 14 1.000 10.0
function of shear rate. This figure shows that these oils exhibit
(±2) (±0.0002)
Newtonian behavior at low shear rates, and seem to be shear-
Venezuelan bitumen 14 1.001 9.9
thinning at higher shear rates. In order to investigate the effect
(±1) (±0.0006)
of functionalized molecules on the viscosity of these oils, rheology
522 D. Subramanian et al. / Fuel 143 (2015) 519–526

 
Table 2 E
Total acid number (TAN) and total base number (TBN) of the crude oils. g ¼ g0 exp ; ð2Þ
kB T
Name TANa (mg/g) TBNb (mg/g)
Mexican heavy oil 35 4.1 where g is the viscosity, g0 is a constant, E is the activation energy,
(±0.008) (±0.13)
kB is Boltzmann’s constant, and T is temperature.
Canadian bitumen 3.30 4.5 In order to investigate the effect of alkyl tail length on the vis-
(±0.04) (±0.12)
cosity of the crude oils, imidazolium ionic liquids with tail lengths
Venezuelan bitumen 5.0 5.9 C2, C4, C6, C8, C10, and C12 are tested. Chloride is maintained as
(±0.12) (±0.16)
the anion. Fig. 4a shows the normalized viscosity of the Mexican
a
As per ASTM D664. heavy oil containing toluene (1 wt.%) and 1 ppm (w/w) of the var-
b
As per ASTM 2896. ious ionic liquids. Since the Mexican heavy oil is observed to be
heterogeneous, normalized viscosity is shown here (normalization
is done with respect to the viscosity of heavy oil, 60 Pa s.). Fig. 4b
Table 3 shows the effect of adding 5 ppm of the imidazolium chlorides
Critical (reverse) micelle concentration (CMC) of ionic liquids in various solvents.
with varying alkyl tail lengths on the viscosities of the Canadian
Name Toluene (ppm) HepTola (ppm) and Venezuelan bitumens (toluene concentration is maintained
1-Octyl-3-methyl- 550 170 at 10 wt.%).
imidazolium chloride Next, the effect of the anion charge density of the ionic liquid on
1-Decyl-3-methyl- 420 60 the viscosity of the crude oil is determined. Fig. 5 shows the nor-
imidazolium chloride
malized viscosity of heavy oil, containing the 1-butyl-3-methyl
1-Dodecyl-3-methyl- 170 15
imidazolium chloride imidazolium cation with anions of varying charge densities, chlo-
Dodecylpyridinium chloride 110 10 ride, thiocyanate, and tetrafluoroborate (anion radii given in
a
Table 4). The temperature is maintained at T = 25  C and toluene
Equivolume mixture of heptane and toluene.
concentration is maintained at 1 wt.%.
The effect of the cation head group on the viscosity reduction of
experiments are carried out in the low shear regime, where the oils the crude oils is investigated next. Fig. 6 shows the effect of adding
exhibit Newtonian behavior. 5 ppm of dodecyl chloride with varying head groups, imidazolium,
Toluene, which acts as a carrier fluid for the functionalized mol- pyridinium, and thiazolium, on the viscosity of the Canadian and
ecules, has a dilution effect on the viscosity of the crude oils. Fig. 2 Venezuelan bitumens, at three different temperatures. Experi-
shows the effect of toluene on the viscosity of the crude oils, at ments are also carried out by adding 1 ppm of dodecylpyridinium
T = 25  C, measured over a fixed shear range, where Newtonian chloride to the Mexican heavy oil but no change in viscosity is
behavior is observed. The concentration of toluene chosen in this observed.
work is such that it facilitates a homogeneous mixing of the addi- The effect of concentration of the ionic liquid on the viscosity
tive and the crude oil. The toluene concentration in the Mexican reduction of the oils is also probed. Fig. 7 shows the effect of C8
heavy oil is maintained at 1 wt.%, while it is 10 wt.% in the Cana- and C10 imidazolium chlorides, at varying concentrations on the
dian and Venezuelan bitumens. viscosity of the Canadian bitumen, at T = 25  C.
Fig. 3 shows the effect of temperature on the viscosity of the
crude oils. The temperature dependence of viscosity seems to fol-
low an Arrhenius law,
10 3

3
10
10 2

10 1
Viscosity (Pa.s.)
Viscosity (Pa.s.)

10 0
2
10

10 −1

10 −2
Venezuelan Bitumen
Canadian Bitumen
Mexican Heavy Oil
Venezuelan Bitumen
Canadian Bitumen
Mexican Heavy Oil
10 −3
1
10 −2 10 −1 10 0 10 1 10 2
10
Toluene (w.%)
10 −3 10 −2 10 −1 10 0 10 1 10 2 103
Shear Rate (1/s) Fig. 2. Viscosity of heavy oil and bitumens, in mixtures of toluene, at T = 25  C. The
shear rate has been maintained constant at a value where the oils exhibit
Fig. 1. Viscosity of heavy oil and the bitumens as a function of shear rate at Newtonian behavior. The average viscosity of the Venezuelan bitumen, Canadian
T = 25  C. At low shear rates the oils behave like Newtonian fluids, while at higher bitumen, and the Mexican heavy oil, without any toluene, is about 460 Pa s.,
shear rates, they seem to be shear thinning. 240 Pa s., and 60 Pa s. respectively.
 D. Subramanian et al. / Fuel 143 (2015) 519–526 523

7 (a) 1
Venezuelan Bitumen
6 Canadian Bitumen 0.9
Mexican Heavy Oil

0.8
5

0.7

Normalized Viscosity
4
Ln(viscosity)

0.6
3
0.5
2
0.4
1
0.3

0
0.2

−1 0.1

−2 0
2.6 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4 3.5 0 2 4 6 8 10 12 14
1000/T (1/K) Alkyl Tail Length

Fig. 3. The temperature dependence of the viscosity of the three oils studied in this
work. Viscosity is measured in SI units. The shear rate is maintained at a constant (b) 8.0

value where the oil exhibits Newtonian behavior. The solid lines are a fit to Eq. (2).
7.5

7.0
4. Discussion
6.5
Viscosity (Pa.s.)

In this work, the effect of ionic liquids on the viscosity reduction

of heavy and extra-heavy crude oils is explored. In order to
6.0
interpret the results, we first need to understand the various
interactions occurring in the system. As stated earlier, a primary 5.5
contributor to the high viscosity of heavy oils and bitumens is
the asphaltene [4,8,9]. Asphaltenes are defined as the fraction of 5.0
crude oil, which are soluble in aromatics such as toluene and insol-
uble in aliphatics such as heptane [4,8]. They have a polyaromatic 4.5
core consisting of fused benzene rings, surrounded by aliphatic
chains [8]. Asphaltenes contain heteroatoms such as nitrogen, oxy- 4.0
gen, and sulfur on the periphery, and transition metals such as iron,
vanadium, and nickel on porphyrin-like structures [8]. Fig. 8 shows 3.5
the schematic of hypothetical asphaltenes. 0 2 4 6 8 10 12 14
Asphaltenes exhibit a wide variety of interactions, ranging from Alkyl Tail Length
p–p interactions between the polyaromatic cores, aliphatic inter-
actions between the side-chains, acid–base interactions involving Fig. 4. (a) Normalized viscosity of the Mexican heavy oil, containing 1 wt.% toluene
and 1 ppm (w/w) of ionic liquid. Data are normalized with the viscosity of heavy oil,
heteroatoms such as nitrogen in pyridine or pyrrolic form, hydro- 60 Pa s. (b) Viscosity of Venezuelan bitumen (triangles) and Canadian bitumen
gen-bonding interactions exhibited by carboxyl or hydroxyl group, (circles), containing 10 wt.% toluene and 5 ppm (w/w) of ionic liquids. The solid
and possibly charge-transfer interactions involving metals [8,20– lines represent the viscosity with only toluene. The ionic liquids added are
23]. These interactions are responsible for the aggregation of imidazolium chlorides with varying alkyl tails, from ethyl (C2), butyl (C4), hexyl
(C6), octyl (C8), decyl (C10), to dodecyl (C12). The temperature is maintained at
asphaltenes, which affects the viscosity of the crude oil [8,24].
T = 25  C, and the shear rate is maintained at a range where the oil exhibits
In order to reduce the viscosity of the heavy oil and bitumens, Newtonian behavior.
we have chosen functionalized molecules such that they would
interact with the asphaltenes via p–p, aliphatic, acid–base, or
charge-transfer interactions. As a result, the size of the asphaltene standing the mechanism of interactions within the system. Exper-
aggregate could decrease, which would in turn lower the viscosity. imental and simulation studies show that p–p interactions
With this viewpoint in mind, ionic liquids, which exhibit aromatic, amongst the polyaromatic cores of asphaltene molecules are a pri-
aliphatic, acid–base, and charge-transfer interactions [25], are mary cause of asphaltene aggregation [20,24,21]. However, if the
chosen. asphaltene molecules or the externally added functionalized
Viscosity reduction ranging up to 35% (with reference to the oil molecules contain aliphatic side chains, then these side chains
containing toluene) is observed for the crude oils tested in this can create a steric hindrance to the p–p stacking of asphaltene
work. Favorable properties of the ionic liquids, which lead to a molecules that inhibit the growth of asphaltene aggregates
higher viscosity reduction, are identified. Fig. 4 indicates a non- [21–23]. The trend observed in Fig. 4 indicates that at small tail
monotonic relation between the tail length of the ionic liquid lengths (less than C8), the strength of the alkyl tails of the ionic
and viscosity reduction. Ionic liquids with larger tail lengths (C8– liquids are not strong enough to cause steric hindrance to the
C12) are more effective at viscosity reduction than those with p–p stacking of asphaltene molecules, while at higher alkyl lengths
smaller tail lengths (C2–C6). This trend can be explained by under- (C8–C12), the tails of the ionic liquid seem to inhibit the p–p inter-
524 D. Subramanian et al. / Fuel 143 (2015) 519–526

1 8
(a) 25 °C
0.9
7
0.8

0.7
Normalized Viscosity

Viscosity (Pa.s.)
0.6

0.5 5

0.4
4
0.3

0.2
3
0.1

0 2
1 1.5 2 2.5 3 3.5 4 Imidazolium Pyridinium Thiazolium
Ionic Radius
2.4
Fig. 5. Normalized viscosity of heavy oil + 1 wt.% toluene + 1 ppm (w/w) of 1-
butyl-3-methyl imidazolium ionic liquids with increasing anion size, ranging from
(b) 40 °C
Chloride, Thiocyanate, to Tetrafluoroborate. The solid line represents the normal- 2.2
ized viscosity of heavy oil with 1 wt.% toluene. Data are normalized with the
viscosity of heavy oil, 60 Pa s.
2.0
Viscosity (Pa.s.)

Table 4
Ionic radii of various anions. 1.8

Name Radius (Å)

1.6
Chloride (Cl) 1.67a
Thiocyanate (SCN) 2.20b
Tetrafluoroborate (BF4) 3.44c
1.4
a
Ref. [17].
b
Ref. [18].
c
Ref. [19]. 1.2

1.0
actions between asphaltene molecules by creating a steric interfer- Imidazolium Pyridinium Thiazolium
ence. This seems to lead to smaller aggregate sizes and thus higher
viscosity reduction. The recent findings of Jian et al., who have 0.70
studied the effect of tail length on asphaltene aggregation via (c) 60 °C
molecular dynamics simulations [22], can further corroborate 0.65
these findings. They show that there is indeed a non-monotonic
0.60
relationship between the length of the side chain and the amount
of asphaltenes aggregated. 0.55
Next, we comprehend the effect of the counter-ion (anion)
Viscosity (Pa.s.)

charge density on the viscosity of crude oils. Fig. 5 indicates that 0.50
anions with higher charge density, such as chloride, seem more
0.45
effective at viscosity reduction as compared to anions with lower
charge density, such as tetrafluoroborate. Anions with smaller 0.40
charge density may exhibit weaker interactions with the asphal-
tene molecules and do not associate strongly with the electron 0.35
deficient regions of the asphaltene molecules. Thus, weaker anions
do not hinder asphaltene self-association, and therefore do not 0.30
cause viscosity reduction. Similar evidence is seen in the work of
0.25
Swatloski et al. wherein they have solubilized cellulose in imidazo-
lium ionic liquids with increasing anion charge density [26]. 0.20
Subsequent to the effect of the anion, we look at the effect of the Imidazolium Pyridinium Thiazolium
cation head group on the viscosity reduction of crude oils. From Fig. 6. The viscosity of Canadian (circles) and Venezuelan (triangles) bitumens
Fig. 6, we see that the ionic liquid with pyridinium head group containing 10 wt.% toluene and 5 ppm (w/w) of dodecylchlorides with varying head
causes higher viscosity reduction in the bitumens as compared to groups: imidazolium, pyridinium, and thiazolium. The solid line represents the
the ionic liquids with imidazolium and thiazolium head groups. viscosity of bitumen + 10 wt.% toluene. (a) 25  C, (b) 40  C and (c) 60  C.
 D. Subramanian et al. / Fuel 143 (2015) 519–526 525

7.0 observed that the TBN of the Mexican heavy oil is much higher
than its TAN, while the TAN and TBN values of the Canadian and
6.5 Venezuelan bitumens are of the same order of magnitude. It is also
seen that pyridinium ionic liquid causes the most change in the pH
of DI water, while thiazolium causes the least change. These results
6.0
explain the inefficacy of the pyridinium ionic liquid to reduce the
viscosity of the Mexican heavy oil, as well as the effectiveness of
Viscosity (Pa.s.)

5.5 the pyridinium and imidazolium ionic liquids on the viscosity

reduction of the bitumens. The results further indicate that the
5.0 higher viscosity reduction observed in the bitumens by using the
pyridinium ionic liquid could be attributed to the stronger acid–
base interactions occurring in the system, as compared to the sys-
4.5
tem containing imidazolium or thiazolium ionic liquids.
Another interesting feature to note here is the effect of concen-
4.0 tration of the ionic liquid on the viscosity reduction of the heavy oil
and bitumens. Fig. 7 indicates that adding 100 ppm of the C8 and
3.5 C10 imidazolium chlorides to the Canadian bitumen increases
the mixture viscosity, rather than decreasing it. To comprehend
3.0 this, we investigate whether the ionic liquids exhibit self-associa-
0 2 4 6 8 10 100 tion, as has been suggested in the literature [27]. This could pre-
Concentration (ppm) vent them from interacting with the asphaltenes and causing
viscosity reduction. We carry out static light scattering experi-
Fig. 7. The viscosity of Canadian bitumen containing 10 wt.% toluene and various ments to determine the critical (reverse) micelle concentration,
concentrations of C8 (triangles) and C10 (squares) imidazolium chloride, at
CMC, of the ionic liquids in solvents toluene and heptol (1:1 by vol-
T = 25  C. The solid line represents the viscosity of bitumen + 10 wt.% toluene.
ume of heptane and toluene). The results from Table 3 show that
This effect is seen at all the temperatures studied. To comprehend the larger the tail length, the smaller the CMC. Results also indicate
this trend, we investigate the acid–base interactions between the that the CMC in heptol is smaller than the CMC in toluene. This
ionic liquids and the crude oils. Table 2 indicates the acidity and suggests that the weaker solvent leads to a lower CMC. These
basicity of the crude oils, while Table 5 indicates the change in results confirm that at higher concentrations (>10 ppm w/w), the
pH of DI water on the addition of 1 wt.% of the ionic liquid. It is ionic liquids could self-associate and may no longer interact with

OH

NH

Fig. 8. Structure of hypothetical asphaltenes. Asphaltenes have a polyaromatic core surrounded by aliphatic side-chains. They may also have heteroatoms, such as nitrogen,
oxygen, and sulfur on the periphery. Petro-porphyrins containing transition metals such as iron, nickel, and vanadium, also constitutes asphaltenes.
526 D. Subramanian et al. / Fuel 143 (2015) 519–526

Table 5 further light on the mechanism of interaction between the ionic

Change in the pH of DI water on the addition of 1 wt.% of ionic liquid. liquids and the asphaltenes, and could help us design optimally
Name D pH functionalized molecules.
Dodecylthiazolium chloride 1.5
1-Dodecyl-3-methylimidazolium chloride 1.8 Acknowledgements
Dodecylpyridinium chloride +2.4
This research was funded by the member companies of R.E.R.I.
research consortium. We would also like to thank Ms. Nora May
the asphaltenes. Low concentrations of the ionic liquid (below the for her help in carrying out light scattering and titration
CMC) are thus preferable for the viscosity reduction of the crude experiments. D.S. thanks Dr. Sara Hashmi, Dr. Seyma Aslan, and
oils. Mr. Siddharth Senthilnathan for helpful discussions.
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