Article

pubs.acs.org/IECR

Novel Deep Eutectic Solvent-Dissolved Molybdenum Oxide Catalyst

for the Upgrading of Heavy Crude Oil
S. M. Shuwa, R. S. Al-Hajri,* B. Y. Jibril, and Y. M. Al-Waheibi
Petroleum and Chemical Engineering Department, Sultan Qaboos University, P.O. Box 33, PC 123 Muscat, Oman
S Supporting Information
*

ABSTRACT: A MoO3/deep eutectic solvent (DES) catalyst precursor solution was prepared by dissolving molybdenum
trioxide in a DES based on choline chloride/urea. The catalyst precursor solution was characterized for its physical and chemical
properties. The characterization results showed almost no change in the DES properties after the addition of MoO3. The solution
was used in the catalytic upgrading reaction of heavy crude oil. The performance of the catalyst was analyzed by gas
chromatographymass spectrometry, Fourier transform infrared, and viscosity measurements of the heavy oil before and after
the reaction. The use of the catalyst in the catalytic aquathermolysis showed an increase in the oil viscosity. In the presence of
hydrogen and catalyst, the results showed a 43% reduction in the heavy oil viscosity, a 2.5 increase in the API gravity, and 32 wt
% sulfur reduction.

1. INTRODUCTION
Heavy oil and bitumen require energy-intensive operations for
their production, upgrading, and transportation to reneries for
subsequent production operations. Therefore, reducing the
viscosity of the heavy oil simultaneously with thermal enhanced
oil recovery has attracted a lot of attention in the past few years.
Moore et al. and Weissman et al. were among the rst to
propose the concept of in situ catalytic upgrading of heavy oil
during in situ combustion.13 Tian et al.4 used water-soluble
ammonium heptamolybdate and NiNO3 in upgrading residual
oil from the Petronas Renery in Malaysia. The upgrading
reactions were conducted in a batch mode under a pressure of 7
MPa of H2 and 340 C using a 300 mL high-pressure stirred
reactor. The catalyst increased the hydrogen-to-carbon ratio
from 1.46 to 1.86 (27.9% increment) with 62.2% viscosity
reduction. Molybdenum acetylacetonate and iron alkylhexanoate based oil-soluble catalysts oered about a three-fold
reduction in the viscosity, a 9 increase in the API gravity, and
46 wt % sulfur reduction.5 The experiments were conducted in
batch (Parr Instrument Company) stirred reactor of 1800 mL
capacity at a temperature of 400 C in a hydrogen atmosphere
of a nal pressure of 10.8 MPa, at a stirring speed of 1000 rpm,
catalyst loadings of 10 wt % with respect to oil, and a residence
time of 24 h.
The process in which the viscosity of heavy oil is reduced
with the aid of water is called aquathermolysis. Not all of the
catalysts reported having good catalytic activity on the heavy
oils. In some cases, the viscosities of reacted heavy oils
regressed rapidly after reaction.6,7 This is the reason why
researchers applied hydrogen or hydrogen-donor compounds
in heavy oil upgrading. The process that involves hydrogen in
aquathermolysis is called hydrothermolysis, which is a
terminology used to distinguish it from aquathermolysis.8
Chao et al. used a bifunctional catalyst, alkyl ester sulfonate
copper, which has not only a catalytic center but also a
hydrogen precursor structure. The catalyst showed good
activity in aquathermolysis of heavy oil in both eld and
2015 American Chemical Society

laboratory tests. The laboratory results showed 90.72%

reduction in the viscosity using 0.3 wt % catalyst at 240 C
and 24 h, with 10.12% conversion of heavy content to light
content.6 Mohammed and Mamora9 carried out an experimental study on the in situ upgrading of a local Venezuelan
(Jobo) heavy oil under steam injection at a temperature of 273
C and a pressure of 500 psig using an oil-soluble organometallic catalyst at a concentration of 750 ppm and tetralin as
the hydrogen donor. The results showed an increase in oil
recovery by 15% by adding 5 wt % tetralin above that of pure
steam injection. When the oil was mixed with tetralin, a catalyst
solution, and sand, about 20% higher oil recovery than that of
pure steam injection was observed. In another work,7 the eect
of a hydrogen-donor additive on the viscosity of heavy oil
during steam stimulation was investigated. The results showed
that the incorporation of tetralin (0.8%) as a hydrogen donor
led to a viscosity reduction of 80% after 24 h of reaction time at
a temperature of 240 C.
The shortcomings of water-soluble catalysts are a low surface
area-to-volume ratio, which leads to inecient contact between
the catalyst and feed, and the production of particles of bigger
sizes, which can lead to formation damage in the reservoir. Oilsoluble catalysts are expensive, which prompted researchers to
seek other alternatives. Recently, some researchers have
employed the services of ionic liquids to upgrade and enhance
the recovery of heavy crude oils. Nares et al. conducted a batch
reactor study of upgrading a heavy crude oil from the Gulf of
Mexico using ionic liquids elaborated with iron and
molybdenum. The upgrading experiments were conducted
using ionic liquids based on iron (10 wt %) and molybdenum
(2 wt %) compounds, in a liquid phase homogeneously mixed
with heavy crude oil in a batch reactor of 500 mL, at 400 C
Received:
Revised:
Accepted:
Published:
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March 23,
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28, 2014
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24 h. The pure DES, DES + H2O mixture (the mass ratio of

DES to water is 2:1), DES/MoO3 solution, and DES/MoO3 +
H2O (mass ratio of DES/MoO3 to water is 2:1) aqueous
mixtures were formed and characterized at dierent temperatures for density, viscosity, conductivity, and surface tension.
The density and API gravity measurements were performed
using an Anton Paar vibrating tube densimeter (DMA 4500).
The equipment measures periods of harmonic oscillation of a
built-in U-tube made of borosilicate glass containing the
sample. The temperature of the measuring cell is controlled by
an integrated Peltier thermostat. Before each measurement, the
cell was rinsed with deionized water and slowly evacuated to
avoid any trapped air in the system. Then the inlet valve was
opened and the sample introduced into the cell; at least 10 min
was allowed for the temperature to reach stability, and then
measurements were taken. The API gravity at 15 C was
measured using the API method developed in the instrument.
The instrument computed the API gravity automatically from
the specic gravity values at 15 C. The viscosity measurements
were carried out with an Anton Paar rheometer (Rheolab QC)
at a constant shear rate of 300 s1. The instrument had a builtin temperature sensor, and an external water bath was used for
temperature control. For every measurement, about 14 mL of
the sample was put into the sample cell with its spindles and
connected to the instrument. About 15 min was allowed for
temperature equilibration before measurements were taken.
The electrical conductivity was measured using a Metler
Toledo conductivity meter, which operates with an alternating
current of 60 Hz frequency. The conductivity meter was
calibrated using a KCl reference solution. The instruments had
a built-in temperature sensor, and variation of the temperature
was achieved with a water bath. For each measurement, 5 mL of
sample was used, the conductivity sensor was immersed in the
glass vials containing the samples, and the conductivity values
were displayed on the instruments digital screen. After every
measurement, the conductivity cell was washed with deionized
water and acetone to remove any adhering sample and dried
before using it in the next measurement.
The surface tension measurements were carried out using a
Kruss digital tensiometer (K10ST) by the Du Nouy ring
method.19 An external water bath was connected to the
tensiometer for temperature control. The platinumiridium
ring was cleaned by aming, and the glassware was rinsed
consecutively with acetone and distilled water before each
measurement. The equipment calibration was determined by
measuring the surface tension of pure water. After each
measurement, the glassware was cleaned thoroughly with water
and acetone before the next measurement.
Prior to these measurements, a solubility test of the metal
oxide in the DES was conducted. Amounts of 0.080.2 g of
MoO3 at 0.02 g intervals were dissolved in 10 mL of DES and
shaken in the thermoshaker for 24 h at 80 C. The mixtures
were then observed for the formation of clear homogeneous
solution of the oxide and DES. A clear homogeneous solution is
an indication of complete dissolution of the metal oxide in the
DES.
Thermal and structural studies were undertaken using
Fourier transform infrared (FTIR) and thermogravimetric
analysis (TGA) to see if there was any change caused to the
DES after the incorporation of MoO3 into the DES structure.
TGA of the DES and DES/MoO3 was conducted on a
simultaneous thermal analyzer (PerkinElmer, STA 6000). The
samples (1020 mg) were heated from 30 to 500 C at a

under a 10.8 MPa total pressure of hydrogen with residence

times of 24, 48, and 72 h. The oil was successfully upgraded
because there was substantial reduction in the viscosity and
sulfur content and increase in the API gravity.10 Fan et al.
investigated the potential of metal-modied ionic liquids in
upgrading Liaohe heavy crude oil, resulting in a good viscosity
reduction property and possibly leading to high oil recovery.11
Deep eutectic solvents (DESs) are types of solvents that
belong to the family of ionic liquids but with a special property
composition of two or three cheap and safe components that
are capable of self-association, often through hydrogen-bonding
interactions, to form a eutectic mixture with a melting point
lower than that of each individual component.12 DESs are
generally liquid at temperatures lower than 100 C and belong
to a category of green solvents that have vast applications in
catalysis, organic synthesis, electrochemistry, and material
chemistry.12,13 They are another form of ionic liquids that are
cheaper, greener, and easier to prepare compared with typical
ionic liquids.
Molybdenum is the basic constituent of the most active
hydroprocessing catalysts.1417 The major source of molybdenum is the mineral molybdenite (crystalline molybdenum
sulde, MoS2), which is roasted to produce molybdenum oxide
and puried by dissolution in aqueous ammonia to produce
molybdates such as ammonium heptamolybdate and ammonium dimolybdate, which are further puried by fraction
crystallization and ash evaporation at 100 C, respectively, to
obtain the water-soluble catalyst precursors. Thus, ammonium
heptamolybdate and ammonium dimolybdate are among the
major sources of water-soluble molybdenum catalysts.
Metal oxides can be introduced into the structure of some
DESs like choline chloride/urea through dissolution to form
catalyst precursor compounds. An active dispersed catalyst
precursor produced from this material in a simple process could
have low cost compared to oil-soluble catalyst precursors. It
could also solve problems associated with water-soluble
precursor compounds such as the generation of large catalyst
particle sizes, and the use of excess amounts of water in the
feedstock will be avoided, which is undesired in hydrocracking.
The main purpose of this work was to investigate the
performance of new catalysts based on DESs in the upgrading
of a heavy crude oil. The catalyst is expected to lead to a
reduction in the viscosity and sulfur content and an increase in
the API gravity of the original oil. The operation conditions for
the reaction were chosen to model typical reservoir conditions.
To our knowledge, the use of DES/molybdenum trioxide in
the aquathermolysis/hydrocracking reactions has not been
reported. It is the objective of this work to investigate its
potential in upgrading Omani heavy oils.

2. EXPERIMENTAL PROCEDURES
2.1. Catalyst Synthesis and Characterization. A sample
of DES was synthesized using choline chloride (ChCl) and urea
(molar ratio of 1:2). The synthesis was conducted in an
incubator shaker at 80 C. Appropriate quantities of the salts
were weighed, thoroughly mixed, put into the shaker, and
allowed to completely melt to a homogeneous colorless liquid.
Details of the synthesis have been reported elsewhere.18 In
order to form a solution of the DES and molybdenum trioxide
(MoO3), a known quantity of the oxide (to give 1000 ppm of
molybdenum with respect to the crude oil) was measured, put
in a sample vile containing the DES (10 wt % with respect to
the oil), and placed in the thermoshaker operated at 80 C for
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lm of prolene. The FTIR spectrum was obtained by placing a

drop of the samples between two sodium chloride cells and
then spreading on the surface of the cells. The cells were then
mounted on the equipment and the settings were as follows; 14
scans, at a resolution of 4 cm1, and wavenumbers from 400 to
4000 cm1. The GCMS spectrum was obtained using a Clarus
600 chromatograph (PerkinElmer) with a RTX-5MS column
(30 m 250 m 0.25 m). For nonvolatile polar
components of oil (asphaltenes and resins) removal, solvent
precipitation and column separation were rst conducted. This
is to prevent the components from damaging the column.
The solid precipitate recovered from run S3 was further
characterized using X-ray diraction (XRD) and scanning
electron microscopyenergy-dispersive spectroscopy (SEM
EDS) techniques. The diractogram was obtained with a
PanAnalytical (XpertPro) XRD machine. The SEM image and
elemental analysis of the samples were obtained with a JEOL
electron microscope with built-in EDS technology for
elemental determination.

heating rate of 10 C/min under a nitrogen atmosphere (30

mL/min ow rate) at a pressure of 3 bar.
2.2. Heavy Oil Upgrading Experiments. To investigate
the activity of the proposed MoO3/DES system, a heavy oil
sample from an Omani eld that has a viscosity of 13800 cP
was utilized.
Upgrading experiments of the heavy crude oil were carried
out using a 500 mL capacity batch-type laboratory reactor
(4575 series, Parr Instrument Company). The reactor vessel
was equipped with a magnetic stirrer for mixing samples in the
vessel, a dip tube for liquid and gas sample withdrawal from the
vessel, and a thermowell. The thermocouple was positioned
inside the reactor through the thermowell to monitor the
temperature of the samples inside the vessel. The temperature
and stirring speed are controlled automatically by a digital
controller (4848 series, Parr Instrument Company), while the
pressure was monitored with a pressure gauge mounted on the
reactor head connected to the reactor vessel. The following
constant reaction conditions were utilized: 300 C reaction
temperature, 11 bar initial hydrogen pressure, 24 h reaction
time, and 750 rpm stirring speed. The hydrocracking
experiments were conducted under a hydrogen atmosphere
by heating 100 g of a heavy oil sample in the reactor vessel with
and without catalysts, while the aquathermolysis runs were
conducted under a nitrogen atmosphere with a heavy oil
sample containing 30 wt % water (oil-to-water mass ratio of
70:30), i.e., 100 g of oil to 43 g of water.
The catalyst loading used was 1000 ppm (0.1 wt %
molybdenum) and 10 wt % DES with respect to the heavy
oil. Table 1 gives the breakdown of all of the runs and

3. RESULTS AND DISCUSSION

3.1. Characterization of Catalyst Precursor Solutions.
Physical properties like density, viscosity, refractive index, and
surface tension are important characteristics of DESs. To date,
few works are available in the open literature on this area of
interest.13,18,2025 It is imperative to know the characteristics of
the DES and its aqueous mixtures in order for them to be
applied in industrial and chemical processes. Because the DES
was mixed with molybdenum oxide and the fact that water is
one of the major components found in oil reservoirs, the DES
(pure) and DESs dissolved in MoO3 and diluted with water
were formulated and characterized. These characteristics could
provide information on the purity of the precursor solutions
and molecular interaction in the liquid.23 Table 2 gives the

Table 1. Experimental Runs and Conditions Employed

sample

H2

N2

H2O

catalyst (DES/
Mo)

S1
S2
S3
S4
S5
S6
S7

comments
control sample: fresh heavy
oil

Table 2. Retention Time of Standard Paranic

Hydrocarbons (C8C33)

C8
C9
C10
C11
C12
C13
C14
C15
C16

conditions employed for the reactions. Naphthalene was used

as the model oil along with water under a nitrogen atmosphere
to check for any thermal activity. Less than 4% naphthalene
conversion was noticed after 24 h and 300 C operating
temperature. The oil plus the catalytic precursor was then
mounted on the reactor assembly and the reactor purged
several times with nitrogen to remove air from the vessel.
Heating was then started from room temperature to the desired
reaction temperature. The reaction began when the desired
temperature was reached and stirring was initiated. The
temperature and pressure were monitored and recorded
continuously during the reaction.
After the reaction was completed, the reaction mixture was
cooled to around 70 C. For tests containing water, the water
was decanted rst and the liquid products from the runs were
recovered and analyzed for the density and API gravity using an
Anton Paar vibrating tube density meter and the viscosity using
an Anton Paar rheometer. The elemental sulfur content of the
runs was evaluated with an energy-dispersive X-ray uorimeter
(NEX QC+ Rigaku) using 32 mm single sample cup with a thin

2.658
3.049
4.249
5.65
7.09
8.471
9.781
10.942
12.177

C17
C18
C19
C20
C21
C22
C23
C24
C25

13.283
14.328
15.324
16.274
17.185
18.055
18.89
19.686
20.456

C26
C27
C28
C29
C30
C31
C32
C33

21.201
21.912
22.607
23.287
24.052
24.938
25.998
27.199

results of these characteristics with experimental errors at

dierent temperatures. The result of the solubility test showed
MoO3 dissolved in the DES, with 0.16 g of MoO3 soluble in 10
mL of DES; this is equivalent to 16000 ppm. A solution of
18000 ppm (0.18 g of MoO3 in 10 mL of DES) did not form a
clear homogeneous phase, which is an indication of the limited
solubility of the oxide in the DES at that condition. The 16000
ppm solution formed a clear homogeneous mixture, which
indicates complete dissolution of the oxide in the DES.
Figure 1 is a plot of the density as a function of the
temperature for all of the samples. From the graph, a decrease
in the density with temperature can be seen, as expected with a
linear relationship. However, the incorporation of molybdenum
oxide into the DES structure did not increase its density, but
rather a slight decrease was observed. The values are in
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structure, which led to an increase in the mobility of free

species within the DES.
Figure 3 shows variation of the surface tension as a function
of the temperature. Almost similar behavior and trend were

Figure 1. Densities of catalyst carriers (DES) and catalyst precursors

with and without water as a function of the temperature.

agreement with the values reported in the literature.22,23 The

reduction in the density due to the addition of water to pure
DES and DES/MoO3 at all temperatures was found to be
proportional.
Viscosity is an important property of DES and is a strong
temperature-dependent variable. Figure 2 displays the vis-

Figure 3. Surface tensions of catalyst carriers (DES) and catalyst

precursors with and without water as a function of the temperature.

observed with viscosity. The surface tension also depends on

the strength of intermolecular forces between the species in the
structure and, as a result, strongly correlates with the viscosity.
The addition of water to the DES led to a drastic reduction in
the surface tension. Conductivity is also an important property
of DESs. Because ChCl/urea consists of ionic species that are
dissociated in the liquid and are free to move independently,26
it is expected to have some degree of conductivity. Figure 4

Figure 2. Viscosities of catalyst carriers (DES) and catalyst precursors

with and without water as a function of the temperature.

cosities of the various solutions as a function of the

temperature. The incorporation of MoO3 in the structure of
the DES led to an increase in the viscosity. This is due to an
increase in the strength of hydrogen bonding between
components in the structure because the viscosity is known
to be associated with hydrogen-bonding interactions. A 2:1
eutectic mixture of urea with ChCl has ionic components of
choline cations and chloride anions while having hydrogen
bonding of the urea molecules. MoO3 binds to the urea
molecules or to the chloride anion. There is also the possibility
of forming an anion/metal/urea complex. The presence of a
strong coordinating anion is needed for the complexation of
metal oxide to form soluble species with a ChCl/urea
mixture.18 The addition of water led to a reduction in the
viscosity as expected because the viscosity is also a function of
the composition. This may be associated with distortion of
extensive hydrogen bonding between the components in the

Figure 4. Conductivities of catalyst carriers (DES) and catalyst

precursors with and without water as a function of the temperature.

displays this behavior. When water was added to the DES and
DES/MoO3 solutions, the conductivity increased as observed.
This can be attributed to the increase in the mobility of the
ionic species in the system, especially the chloride anion (being
the principle migrating species), which is more facile than the
choline cation or the urea anion. It can also be observed from
Figure 4 that the introduction of MoO3 into the DES led to a
slight decrease in the conductivity. It has been reported that
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DESs with high viscosity have low conductivity.12 Because the
viscosity correlates inversely with the conductivity, the increase
in the viscosity observed after adsorption of MoO3 into the
DES structure led to a reduction in the conductivity.
TGA for both pure DES and DES/MoO3 is shown in Figure
5. It is evident from the thermograms that the DES and DES/

molybdenum oxide. This peak could be assigned to the

hydrogen bond NH of urea in the DES, with the
chlorometalate complex species anion expected to have been
formed because of the presence of the metal oxide.29,30
It is assumed that there were hydrogen-bonding interactions
between MoO3 and the DES, as shown in the FTIR spectra.
The transmission bands at 3771 and 3825 cm1 are attributed
to hydrogen bonding between urea and the complex anion
expected to have been formed due to dissolution of the metal
oxide in the DES. Although there is no work in the open
literature carried out on dissolving MoO3 in ChCl/urea DES,
Abbot et al.18 dissolved V2O5 and CrO3 in ChCl/urea DES.
These two metals/metal oxides exhibit some common
similarities with MoO3. Molybdenum and chromium are in
the same group in the periodic table with many similar chemical
properties. They have high oxidation states (6+) in the two
oxides and, as a result, possess good catalytic activity. V2O5 also
exists in high oxidation state (5+) and possesses strong catalytic
activities like MoO3 and CrO3. All three metal oxides are
oxidizing agents. Considering the above-mentioned similarities
common to the three metal oxides, MoO3 dissolved in ChCl/
urea DES is expected to exhibit behavior similar to that of CrO3
and V2O5 in ChCl/urea DES. The FTIR spectra conrmed this
assertion by not showing any new bands apart from those
attributed to hydrogen-bonding interactions between the urea
and the complex anion species. It can be speculated that
dissolution of MoO3 in the DES led to the formation of a
complex anion species such as [MoO2Cl3] similar to
[CrO2Cl3] and [VO2Cl2] obtained when CrO3 and V2O5
were dissolved in ChCl/urea DES, respectively.18 The
oxidation state of molybdenum in the complex anion is 6+,
which means no reduction after dissolution. There is a
possibility that the oxide could be reduced in the dissolution
process; however, this was not observed because the solution of
the oxide in the DES remained colorless even after dissolution,
which is a characteristic of the metal in its 6+ oxidation state.
A similar characteristic was observed when CrO3 and V2O5
were dissolved in ChCl/urea DES18 and V2O5 in ionic liquid31
in spite of the fact that the two metal oxides are stronger
oxidizing agents than MoO3. Many metal oxides do not
undergo reduction after dissolution in ChCl/urea DES.32 This
points out that the major outcomes of dissolving metal oxide in

Figure 5. Thermogram of the samples.

MoO3 are thermally stable up to around 200 C. This agrees

with the observation reported in the literature.27,28 The
maximum decomposition temperature was found to be 295
C for the two samples analyzed. The presence of MoO3 in the
DES structure did not change the thermal stability of the
solvent or the maximum decomposition temperature, with only
a small dierence in the amount of residue left after
decompositions of the compounds at 295 C.
The IR spectrum was acquired to see if there was any change
in the structure of the DES after the introduction of
molybdenum oxide. Figure 6 shows the IR spectrum of the
pure DES and DES/MoO3. Upon comparion of the two spectra
in the gure, it can be seen that two new transmission bands
appeared at 3825 and 3771 cm1 in the spectrum of DES/
MoO3. This was not observed in the spectrum of pure DES,
indicating the interaction of pure DES with dissolved

Figure 6. FTIR spectrum of DES before and after the incorporation of MoO3.
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Figure 7. GCMS spectra of samples S2 and S3 (hydrocracking without water) in comparison with the fresh sample S1.

Figure 8. GCMS spectra of samples S4 and S5 (hydrocracking with water) in comparison with the fresh sample S1.

This may be attributed to the formation of more hydrogen

bonds between urea and ChCl because of the presence of
MoO3.35,36 Because the viscosities of ionic liquids and ionic
liquid analogues are governed essentially by hydrogen
bonding,37 it is reasonable to assume that an increase in the
hydrogen-bonding interaction and its strength is the reason
behind the increase in the viscosity when MoO3 was dissolved
in the ChCl/urea DES.
3.2. Compositional Changes. The GCMS study was
undertaken to evaluate changes in the hydrocarbon components in the oil samples before and after reactions under the
studied conditions. The results are presented in Figures 79.
The amounts of saturated hydrocarbons C8C33 (retention

ionic liquids and DESs are the formation of a complex anion in

situ, and the mechanism of interaction between the solutes and
solvents is hydrogen bonding.18,29,31,33,34 On the basis of the
foregoing discussions, it is expected that the oxide will be
reduced in situ by reacting with the sulfur compounds in the oil
to form molybdenum disulde (MoS2), which is the active form
of the catalysts. The presence of the complex anion containing
molybdenum in the 6+ oxidation state and hydrogen will pave
the way for reduction of molybdenum from the 6+ to 4+
oxidation state as in MoS2.
Also, the absorption bands at 2161 and 2331 cm1, which
appeared in the spectrum of pure DES, shifted to broader and
higher frequency bands at 2190 and 2336 cm1, respectively.
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Figure 9. GCMS spectra of samples S6 and S7 (aquathermolysis) in comparison with the fresh sample S1.

This must have been as a result of polymerization reaction of

the molecules in the fresh oil. The formation of high-molecularweight hydrocarbons can be explained through free-radical
chain reactions caused by the absence or presence of low partial
pressure of hydrogen in the reaction. Thermal cracking of
asphaltenes and resins can lead to the formation of reactive
species that can react with each other through polymerization
and condensation reactions to form bigger molecules.38 This is
the reason why there is a big dierence in the saturate contents
between S4 and S2 in which water was the only dierence
between the two starting reactive mixtures. Hydrogen present
in S2 was able to stabilize the reactive free radicals generated at
that condition, whereas the high partial pressures of water in S4
inhibit the free-radical stabilization. Because polymerization and
condensation reactions are proceeded by free-radical mechanisms, this can lead to the production of components heavier
than the feed, and as a result, low saturates will be formed
compared with S2.
In summary, S1 and S2 showed the signicant presence of
saturates because of the presence of hydrogen and catalyst (in
S3), which is the result of hydrogenation and cracking
reactions. S3 and S5 showed lower amounts of higher saturated
hydrocarbons (C23C33) because of their conversion to lowmolecular-weight hydrocarbons as a result of the presence of
catalyst and hydrogen. S4 displayed amounts of hydrocarbons
C28C33 higher than those of the fresh oil because of
condensation and polymerization reactions taking place in
which the presence of water aided the reaction. For S6 and S7,
even though there were low amounts of C28C33, hydrocarbons of higher carbon number were detected from the
product of the reaction. This can be attributed to the presence
of water, as in S4, and the absence of hydrogen, which is known
to inhibit polymerization reactions.
The FTIR spectra of the oil samples before and after
upgrading reactions were acquired to compliment GCMS
analysis. The results of FTIR analysis are represented in Figures
10 and 11. The transmission band at 3278 cm1, which is
assigned to alkynes and aromatic CH stretching vibra-

time shown in Table 2) increased for all of the samples

compared with the fresh oil sample (S1).
A remarkable behavior is displayed by S2 and S3 by showing
high amounts of saturates compared to other samples. S3
contains the highest amounts of saturates, followed by S2,
which has the amounts of hydrocarbons nearly equal to those
of S3 (Figure 7). See Table 3 for the total yields of the
saturates.
Table 3. Total Yield of Saturated Hydrocarbons (C8C33)
for All of the Samples
sample

yield (wt %)

sample

yield (wt %)

S1
S2
S3
S4

2.9
8.6
9.7
3.5

S5
S6
S7

4.2
4.8
5.4

The presence of a high partial pressure of hydrogen in S2 and

S3 aided the conversion of unsaturates present in the fresh
sample to saturated hydrocarbons (hydrogen addition) with
more of CC cleavage (carbon rejection or cracking) taking
place. The small increase in saturated hydrocarbons observed in
the other samples (S4S7) must be due to the cracking of
high-molecular-weight hydrocarbons in the fresh sample to
form saturates and light hydrocarbon gases. S3 showed higher
amounts of saturates compared to other samples due to the
conversion of bigger molecules to small hydrocarbons and even
to gases that were not monitored in the course of the reaction.
This is due to the presence of the catalysts in the reaction
medium. Although S4S7 displayed higher quantities of
saturates than S1, hydrocarbons of higher carbon number
were observed, as shown in Figure 9. In addition to the GC
chromatograms, Figure S1 in the Supporting Information (SI),
depicting columns showing peak areas of all of the reacted oil
samples from the runs, was plotted. A comparison between the
runs (S1S7) in terms of the peak areas from the raw total ion
chromatogram (TIC) can be easily made from the gure.
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Figure 10. FTIR spectra of oil samples S2S4 (hydrogen process) with fresh S1.

Figure 11. FTIR spectra of oil samples S5S7 (aquathermolysis) with fresh S1.

bands of a conjugate polyene CC (1600 cm1), which

signies the presence of an aromatic ring, became weaker in S2
and S3.6,3941 This may be due to hydrogenation, open-cycle,
and breaking reactions42
3.3. Change in the Physical Properties of Oil Samples
after Upgrading Reactions. The density, viscosity, and API
gravity measurements for the samples before and after reaction
are shown in Table 4. The change in the viscosity and API
gravity was calculated according to the following equation:

tions39,40 in unsaturated hydrocarbons, lost intensity and

became weaker in S2, S3, and S5. This is an indication of the
conversion of unsaturates to saturated hydrocarbons in the
presence of hydrogen. The bands at 2927 cm1 assigned to the
CH stretching vibration6,3941 found in saturated hydrocarbons obviously gained intensity and became stronger in S2
and S3 and lost intensity to become weaker in S4 and S7. Also,
the absorption bands at 1460 and 1376 cm1 attributed to C
H bending vibrations39,41 found in alkanes became stronger in
S2 and S3 and weaker in S4 and S7. This implies that the
saturate content in S2 and S3 increased as a result of the
hydrogenation of unsaturates and pyrolysis of long-chain
alkanes, while the weakening of the bands in S4 and S7
illustrates a reduction in the content of saturates due to
cracking to light hydrocarbon gases and/or condensation
reactions to form bigger hydrocarbons. The stretching vibration

M =

M0 M
100%
M0

where M is the change in the property [viscosity (mPa s, 30

C) or API gravity (at 15 C)], M0 is the initial property
(viscosity or API gravity), and M is the property of the sample
after reaction.
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error. This can be explained with the fact that the

aquathermolysis process involves breaking of the weak CS
bond, which results in sulfur reduction.6,8,41,45,46 Although the
process can lead to desulfurization, it is not eective like the
hydrocracking process. Viscosity reduction normally observed
in the process was not observed in this case.
It is clear from the runs that the presence of water in both
hydrocracking and aquathermolysis led to the formation of
components in reacted oil samples heavier than the original
sample, as demonstrated in S4S7. In addition to the products
of condensation/polymerization reactions, it can be presumed
that water hydrolyzes the sulfur and nitrogen compounds in the
oil such as sulfoxides, aliphatic suldes, and theophenic
aromatic suldes. The products of this hydrolysis reaction
that still retain the sulfur in their molecules are normally
sulfones, sulfoxides, and oximes. This may be the reason why a
small reduction in sulfur was observed in runs S4S7 compared
to S2 and S3; because the elemental sulfur analyzer (XRF) used
determines the sulfur content in the reacted liquid oil samples,
any sulfur compound other than H2S will remain in the
samples. The presence of these groups of compounds in the
reacted oil samples is expected to result in a highly structured,
higher viscosity oil.43
Water is also capable of hydrolyzing the aromatics in the oil
to phenols. The appearance of a weakly intense band at 1600
cm1 assigned to the stretching vibration band of conjugate
polyene CC, which indicates the presence of an aromatic
ring (higher intensity in S4S6), supports that argument. This
can be speculated based on the FTIR spectra of the oil samples
S4S6 compared to the fresh oil sample S1. Because these
compounds formed from hydrolysis of the sulfur- and nitrogencontaining species in the oil are more polar than the starting
materials (aliphatic suldes and naphthenic aromatic suldes
such as dibenzotheophene), they cannot be detected by GC
MS analysis. The reason is because all polar compounds were
removed by passing the dichloromethane-dissolved oil samples
through silica gel, which, in turn, separates them from other
nonpolar components of the oil samples. It can be observed in
Figure S1 in the SI that the total saturate contents (C8C33)
of samples S2 and S3 is higher than that of S4S7, as
demonstrated by their peak areas. Hydrocracking is known for
producing liquid distillates and as such not many heavy
molecules and gaseous products. The aquathermolysis runs
produced probably heavier components and other products
that can be linked to the hydrolysis reactions because of the
presence of water. As a result of all of these, the liquid distillate
products (represented by C8C33 in this case) of the
hydrocracking runs is expected to be higher than the
aquathermolysis runs, as demonstrated by the peak areas in
the GCMC results (Figure S2 in the SI).
For the polymerization/condensation reactions, the presence
of water under the condition studied can be presumed to favor
free-radical addition reactions to free-radical cracking reactions.
Because polymerization reactions proceed by free-radical
mechanisms as in ethylene to polyethylene plastics, this may
lead to the formation of heavier molecules in the reacted oil
samples. It is the free-radical cracking reactions that normally
lead to desulfurization and a reduction in the viscosity in the
aquathermolysis process; although sulfur reduction cannot be
rule out in this case (because a small reduction in sulfur and an
increase in the saturate contents observed support that), freeradical addition reactions are more pronounced. In short, the

Table 4. Physical Properties of the Oil Samples from the

Runs and the Fresh Crude Oil
sample

viscosity,
cP

change in the
viscosity, %

change in the API

gravity

density,
g/cm3

S1
S2
S3
S4
S5
S6
S7

13800
10683
7889
17098
14492
17062
14973

NA
22.59
42.83
+23.94
+5.02
+23.64
+8.5

12.75
+1.7
+2.4
0.85
+0.40
0.47
1.09

0.9800
0.9769
0.9761
0.9837
0.9783
0.9837
0.9827

In general, the results agreed well with those obtained using

GCMS and FTIR. The presence of hydrogen during S2 and
S3 resulted in a higher C8C33 content compared to that
presented in the fresh sample and, hence, a lower viscosity. The
addition of the catalyst enhanced hydrogenation and hydrocracking reaction and therefore resulted in an even lower
viscosity, 43%. The addition of water to samples S4S7
resulted in an increase in the viscosity, which corresponds well
with the relatively higher C28C33 content and other heavier
products formed because of free-radical addition reactions in
those samples. The liquid viscosity is reported to correlate well
with the molecular mass or apparent molecular mass due to
aggregation.43 Upon a comparison of S2, S4, and S5, it is clear
that the addition of water caused a reduction in the
hydrogenation/hydrocracking reactions with acceleration in
the reactions that led to the formation of much heavier
molecules. The addition of the catalyst in S5 enhanced the
hydrogenation reaction but with an end result of almost no
overall change in the oil viscosity. A similar trend can be
observed by comparing runs S6 and S7.
3.4. Sulfur Reduction. The elemental sulfur results of the
samples are represented in Table 5. The results showed a trend
Table 5. Results of Sulfur Analysis
sample

sulfur amount, wt %

percent desulfurization, %

S1
S2
S3
S4
S5
S6
S7

4.49
3.81
3.05
4.39
4.20
4.13
4.30

NA
15.14
32.07
2.23
6.46
4.23
8.02

similar to that of viscosity reduction. A 32% reduction was

achieved with S3, followed by S2 with 15% desulfurization. The
hydrogen addition process without water displayed the highest
desulfurization compared with the aquathermolysis process
without catalyst, 8% for S6, and with catalyst, 4% for S7. Upon
comparison of the hydrogen addition runs S2S4, it is evident
that the presence of water inhibits the desulfurization process.
Water is known to inhibit desulfurization reactions during
upgrading processes.44 The dierence in the percent desulfurization of the two runs S2 (15%) and S4 (2%) shows a clear
inhibition of the process by water. When a catalyst was used in
the presence of water in run S5, the desulfurization was
improved from 2% (S4) to 6% (S5). The aquathermolysis runs
S6 and S7 displayed low desulfurization with 4.2% for S6 and
8% for S7, indicating an improvement of about 4% when a
catalyst was added to run S6, although there is no meaningful
dierences for the aquathermolysis runs within experimental
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Figure 12. XRD patterns of the solid precipitate recovered from the reaction of S3.

Figure 13. High-resolution SEM image of the solid precipitate recovered from reaction S3 at dierent magnications: (a) 350 (10 m); (b) 1000
(10 m); (c) 6000 (1 m); (d) 37000 (100 nm).

known conventional desulfurization processes used in the

reneries for removal of sulfur in crude oil fractions. Sulfur can
be removed from thiophenes and mercaptans present in crude
oils in the form of hydrogen sulde, especially when catalysts
are used. This is unlikely to take place in aquathermolysis

loss in desulfurization is more likely due to the formation of

heavier products by radical addition reactions.
In summary, the runs with hydrogen showed higher
desulfurization than the aquathermolysis process. The hydrogen addition processes (like hydrodesulfurization) are the
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oxides, because many metals were also identied from the EDS
results. Some of the oxides like silica are inherent to the
reservoir. Another element with a high signal is nitrogen, which
is also present in the original crude oil because heavy
components contain nitrogen. This indicates that the upgrading
reactions conducted on the oil samples led to heteroatom
removal (oxygen and nitrogen). The DES (ChCl/urea) used is
also another source of nitrogen because of the urea present in
the reaction medium. Decomposition of the DES during the
reaction might lead to the formation of nitrogen-containing
compounds. The high signal of chlorine observed in the solid
precipitate from chemical analysis can also be traced to ChCl of
the DES. Some dissolved salts in crude oils contain chlorine in
the form of metal salts of chlorine. Iron and nickel can be
explained as originally present in the crude oil. Their presence
in recovered solid indicates a reduction of the heavy metal
content after the upgrading reactions. The molybdenum and
sulfur signals were also observed as expected. The overlapping
of the signals for the two observed in both zones (spectra 1 and
5) gives an indication of the interaction of the two as in MoS2.
Almost the same amounts of molybdenum were found in the
two regions (spectra 1 and 5), which is an indication of the
uniform distribution of the catalyst in the system.

because of the lack of hydrogen. Although hydrogen can be

produced in situ in aquathermolysis via a watergas shift
reaction, it is not present in large amounts to lead to
hydrodesulfurization.
3.5. Solid Precipitate Characterization. SEMEDS and
XRD were carried out on the solid precipitate recovered from
reaction sample S3. The yield of the solid product recovered
was 7.6 wt %. SEM is useful in exploring the morphology and
size of the catalytic particles, while EDS, being a semiquantitative technique, can be used for chemical analysis. XRD
can be used for phase identication and crystal structure
elucidation.
Figure 12 shows the X-ray diractogram of the solid particles.
Despite the noise observed in the spectrum, broader peaks can
be clearly seen, which indicates small crystal sizes. Although
broader peaks mean small crystal sizes, the XRD pattern
indicates the presence of stacking layers of slabs of MoS2
crystallites, which may indicate a high interplanar distance (d
spacing). The peaks at 2 = 33.02, 40.6097, 58.5848, and
58.7203 corresponding to the intensity counts of 149.66,
24.49, 143.26, and 108.43, respectively, are attributed to the
presence of MoS2.47,48 The peak at 2 = 23 indicates the
presence of MoO2, which might have been formed from the
reduction of MoO3.49 MoS2 is known to be an active form of a
molybdenum-based hydrotreating catalyst. Its presence in the
produced solid samples after the upgrading process is an
indication of its generation in situ. Many researchers have
reported that MoS2 can be transformed in situ from relevant
molybdenum precursors under conditions similar to those used
in this study, in sulfur-containing crude oils.16,48,5052 The
sulde was generated after decomposition of DES/MoO3 to
give dispersed and reactive MoO3, which was subsequently
sulded by the sulfur in the oil. The precise mechanism of this
transformation is still unclear, but direct reduction of the salt by
hydrogen sulde seems probable.14,17,51,52 The presence of four
dierent reections attributable to MoS2 versus one for MoO2
with no characteristic peak of MoO3 is an indication of the
good sulding behavior of the precursor. The identication of
one reection is not enough to conrm the presence of MoO2
because the reduction of MoO3 to MoO2 requires severe
operating conditions and high partial pressures of hydrogen.
Figures 13 and S2 and S3 in the SI show the SEM images
and results of chemical analysis from EDS. Figure 13a shows
the SEM image of the particles (350 magnication), while
Figure S3b in the SI was acquired at higher magnication
(1000). When a smaller image (1 m) was obtained at 6000
magnication, a spherical type particle was observed. Figure
13d shows the image (100 nm) at a magnication of 37000,
in which an estimation of the size of the particle was made. 1.37
m was found to be the average size of the particles of the
agglomerate formed after the reaction. The EDS results, images,
and chemical analysis are shown in Figures S2 and S3 in the SI.
The SEM image in Figure S2 in the SI shows ve dierent
spectra (15) in which spectra 1 and 5 were chosen for
chemical analysis using the EDS software. The reason is due to
the presence of a high concentration of metals in those zones.
The chemical analysis and image of spectrum 1 can be seen in
Figure S3 in the SI. The tables in the two gures represent the
results of chemical analysis. Carbon, chlorine, and oxygen
display high signals observed from the spectra. Oxygen and
nitrogen are originally present in the heavy crude oil in the
form of heteroatoms in constituents like asphaltenes. Oxygen
can also be attributed to the presence of oxides, especially metal

4. CONCLUSION
Catalytic upgrading of an Omani heavy crude oil was conducted
under dierent conditions simulating hydrocracking and
aquathermolysis processes. Some runs of the upgrading
reactions were carried out in the presence of catalyst formulated
by dissolving MoO3 in DES based on ChCl/urea. Results from
the catalyst characterization study show that the incorporation
of MoO3 in the DES did not signicantly change the structure
of the DES, but slight changes in some physicochemical
properties were observed. The best of all of the runs is the
hydrogenation run with catalyst in which water was not added.
It gave the best performance in terms of sulfur, viscosity, and
heavy metal reduction. XRD and SEMEDS analysis of the
solid recovered from this run showed the presence of MoS2, an
active form of the catalyst, suggestive of its in situ generation.
The presence of water in the reaction medium led to an
increase rather than a decrease in the viscosity. This negative
eect of water in the reaction medium involving this heavy oil,
in particular, made the aquathermolysis process (in the
presence of water) an undesired route in upgrading this
crude oil under the condition studied. Overall, the catalyst is
eective in upgrading the crude oil via the hydrogenation route;
also the hydrocracking runs performed better than the
aquathermolysis runs.

ASSOCIATED CONTENT

S Supporting Information
*

Results of physical property measurements and experimental

errors, bar chart comparison of the GCMS results between
the seven reacted oil samples and standards of saturated
hydrocarbons, and SEMEDS results of recovered solids. This
material is available free of charge via the Internet at http://
pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*Tel.: +968 2414 2557. Fax: +968 2414 1354. E-mail:

rashidh@squ.edu.om.
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The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors thank The Research Council of Oman for
providing nancial support to this work through Research
Grant RC/ENG/PCED/11/01. The authors are also grateful to
Sultan Qaboos University Oman for allowing use of their
facilities and other support oered.

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DOI: 10.1021/ie5050082
Ind. Eng. Chem. Res. 2015, 54, 35893601