pubs.acs.

org/EF Article

Catalytic Aquathermolysis for Altering the Rheology of Asphaltic

Crude Oil Using Ionic Liquid Modified Magnetic MWCNT
M. A. Betiha,* Ahmed E. ElMetwally, A. M. Al-Sabagh, and Tahany Mahmoud*

Cite This: Energy Fuels 2020, 34, 11353−11364 Read Online

ACCESS Metrics & More Article Recommendations

ABSTRACT: The use of asphaltic crude oil resources as an alternative to offset light oil supplies over the next years has attracted oil
field attention. However, its high viscosity greatly impedes the production of asphaltic crude oil from wells and constitutes an
obstacle, especially during transportation and refining operations. Thus, catalytic aquathermolysis has been introduced as an
attractive and green technique for upgrading the asphaltic crude oil at elevated temperatures by reducing the asphaltic crude oil
viscosity. In this study, magnetic multiwalled carbon nanotubes (MWCNTs) were prepared and modified with 1-ethyl-3-(3-formyl-
4-hydroxybenzyl)-1H-imidazol-3-ium acetate (EFHIA). The results revealed the rheology results revealed that the viscosity of crude
oil was reduced by 75.9% when compared to thermally treated blank at the same degree after 2 h of operation using Fe3O4/
MWCNT@EFHIA as a catalyst. The asphaltene, resin, and sulfur measurements revealed that the percentages of these compounds
were reduced to 37%, 43%, and 47%, respectively, upon using 0.2% Fe3O4/MWCNT@EFHIA as a catalyst at 200 °C for 2 h.

1. INTRODUCTION Using high steam quality and high circulation rate led to
The quest of different countries to develop different aspects of slowing the initialization rates, irregular temperature in the
life to improve the well-being of their people has led to an space between the injection point and the production wells,
increase in demand for different sources of energy. One of the and the possibility of steam penetration at the heel.
most important challenges is oil, which is the main source of Steam has been reported to improve the quality of crude oil
energy, and this source has always been associated with the and reduce its viscosity for the first time by Hyne et al.,8 and
need to work to provide and use it in better ways to this process is called aquathermolysis.9 During the process of
compensate for lack of reserves. Therefore, research has aquathermolysis, a chemical bond is often broken between
expanded on the exploitation of unconventional oil (especially carbon and sulfur or nitrogen, producing small chains of light
heavy), which is promising in serving as a good proportion of hydrocarbons and removing some inorganic gases, which
energy sources.1,2 However, the highly viscous crude oil that reduces oil viscosity. However, the low viscosity is almost
ranges between 100 to 100 000 cP limits our efforts to exploit temporary due to the occurrence of polymerization,9,10 and
it effectively.3,4 The asphaltene and resin components are the therefore some additives have been studied for this technique
main cause of high crude oil viscosity, as these compounds to achieve permanent viscosity reduction. To achieve this,
chemically or physically held together with bonds such as many chemical compounds have been used, which are
hydrogen, acid−base, π−π stacking, or coordination bonds.5 classified as follows; water-soluble metal salts like Ni sulfate
For this reason, weakening these bonds can lead to a reduction (NiSO4);11 metal complexes such as molybdenum oleate
in the viscosity of crude oil and hence improves oil extraction. (C72H136MoO8);12 ferric oleate (C54H99FeO6), nickel oleate
One of the most effective solutions for increasing heavy oil (C36H68NiO4), cobalt oleate (C36H66CoO4), iron acetylaceto-
recovery is steam-assisted gravity drainage (SAGD), which has nate (C15H21FeO6),13−15 and amphiphilic catalysts, which are
drawn the attention of researchers in the oil field. In the SAGD soluble in water and oil.16−19 Iron chelate-aromatic sulfonic
process, two parallel wells are drilled horizontally at a has been used by Chen et al.16 as amphiphilic catalysts
previously estimated distance. The lower-well is used to (aromatic sulfonic acid as an anion and iron as a cation) for
produce the crude oil while steam is injected through the viscosity reduction of extra-heavy oil at 200 °C. The apparent
upper-well, which is already connected to the steam chamber. viscosity of crude oil was reduced by 90.7%, which is attributed
The heat is transferred from the upper well to the reservoir, to the stability of the catalyst at water−oil interface.20 Chao et
which results in a decrease in the viscosity of the crude oil, and
as a result, the oil is driven toward the production well.6 The
effect of vapor quality, vapor circulation rate, vapor penetration Received: June 20, 2020
of oil-bearing rock, and the pressure difference between Revised: August 2, 2020
injection and production point and temperature uniformity in Published: August 20, 2020
the reservoir were studied using discretized wellbore model by
Yuan and McFarlane.7 The researchers found that there is a
relationship between the steam quality and circulation rates.

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.energyfuels.0c02062

11353 Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

al.18 examined a bifunctional catalyst (alkyl ester sulfonate butyl-3-methylimidazolium chloride (BmimA, ≥98), and potassium
copper) in the aquathermolysis of super heavy oils (1.81 × 105 acetate (≥99%) were purchased from Sigma-Aldrich. A carbon
mPa s at 70 °C). They found that by using 0.3% of the alkyl nanotube was obtained from the Egyptian nanotechnology center of
ester sulfonate copper catalyst, the viscosity of the heavy oil EPRI. Crude oil used was obtained from the General Petroleum
Company (Egypt); the physicochemical properties of it are shown in
was reduced by 90.7% after aging for 24 h at 240 °C and
Table 1.
approximately 10.12% of the heavy crude was converted into a
light crude. Fan et al.21 have obtained very important
laboratory conclusions, as they have proven that the reservoir Table 1. Physicochemical Properties of Crude Oil Used in
This Study (General Petroleum Company)
minerals in the presence of steam (240 °C) have a catalytic
effect. The synergistic effect of reservoir minerals and steam crude oil properties
has reduced the viscosity of heavy oils as well as reduced the method value property
average molecular weight of heavy oil and asphaltene. Lin et
ISO 3675 0.939 density, (kg/m3) at 15 °C
al.22 reported catalytic aquathermolysis of heavy oil using
ASTM D-4052 13 API, gravity @ 60 °F
nanoFe3O4 (13.3 nm) deposited at HZSM-5 at 280 °C. The
IP-143 12.21 asphaltene content, (wt %)
authors concluded that the acidity of the catalyst is not the
UOP-64 1.83 wax content, wt %
main reason for reducing the viscosity of the oil and that the
ASTM D-97 6 pour point, °C
presence of Fe3O4 led to a break in the bond between carbon
ASTM D-7041 23 500 sulfur content, (ppm)
and sulfur atoms.
In addition, heterogeneous catalysts such as minerals and 2.2. Preparation of Ionic Liquid Modified Magnetic
zeolites are also used in aquathermolysis of heavy crude oil and MWCNT. 2.2.1. Preparation of 1-Ethyl-3-(3-formyl-4-hydroxyben-
are characterized by their availability and ease of preparation. zyl)-1H-imidazol-3-ium Acetate Ionic Liquid (EFHIA). The 5-
Monin and Audibert23 demonstrated the heterogeneous chloromethyl salicylaldehyde compound was fabricated by inserting
mineral promoting cracking of crude oil, and the results a group of chloromethyl into a salicylaldehyde compound using zinc
showed a significant reduction in viscosity of heavy oil.24 It has chloride as a catalyst in an acidic medium.28 In summary, 15.2 mmol
(1.856 g) salicylaldehyde, 33.3 mmol (1.0 g) paraformaldehyde, 20
also been found that porous materials such as zeolite, for mL of concentrated hydrochloride acid, and 1.467 mmol (0.2 g) zinc
example, have an effect on reducing the viscosity of crude oil chloride were charged into a bottle connected to a source of hydrogen
by adsorbing undesirable materials, and the acidity of these chloride gas. The mixture was stirred at 30 °C for 3 days, and the
materials also acts to saturate the cracked products resulting material was extracted with diethyl ether and washed with
(olefins).25,26 The use of strong acids, such as HF·BF3, is 0.5% sodium bicarbonate aqueous solution until pH reaches 6.8. After
one of the most important catalysts with an ability to reduce that, an amount of 5-chloromethyl salicylaldehyde compound is
crude oil viscosity by depolymerization and hydrogenation dissolved in dry toluene, and an equal molar quantity of ethyl
simultaneously to produce volatile organic compounds and imidazole is added very slowly. The mixture is left under stirring at 50
benzene derivatives.27 °C for 8 h under nitrogen gas flow. By the cooling system, the product
(1-ethyl-3-(3-formyl-4-hydroxybenzyl)-1H-imidazol-3-ium chloride,
Herein, we provide a new strategy to enhance the catalytic EFHIC) is separated from toluene where it is washed several times
aquathermolysis of heavy asphaltic crude oil through the with toluene and diethyl ether and finally dried under vacuum at room
development of a supported ionic liquid heterogeneous temperature.
catalyst. In particular, magnetic MWCNT was prepared and Finally, the chloride ions are replaced by acetate ions by stirring
characterized. Next, two different ionic liquids, 1-butyl-3- equimolar of 1-ethyl-3-(3-formyl-4-hydroxybenzyl)-1H-imidazol-3-
methylimidazolium acetate (BmimA) and 1-ethyl-3-(3-formyl- ium chloride or 1-butyl-3-methylimidazolium chloride (BmimA)
4-hydroxybenzyl)-1H-imidazol-3-ium acetate (EFHIA) were with potassium acetate in the acetone at −5 °C for 3 h, and the
prepared, immobilized on the prepared magnetic MWCT and mixture is refluxed for further 8 h. The product is separated from the
mixture by filtration, washed with diethyl ether, and dried in a vacuum
characterized using FTIR, 1H NMR, Raman spectroscopy,
oven at room temperature.29,30
XRD, TGA, SEM, and HR-TEM. The prepared materials were 2.2.2. Preparation of Magnetic MWCNT. The multiwalled carbon
tested in the catalytic aquathermolysis of heavy asphaltic crude nanotubes are purified by stirring the MWCNTs in concentrated
oil, and the effect of different ionic liquids on catalytic nitric acid for a period of 12 h at a temperature of 60 °C. After that,
aquathermolysis was elaborated. Moreover, the effect of ionic the MWCNTs were separated by filtration, washed with water, and
liquid modified magnetic MWCNT on the rheological dried at 110 °C. Ultrasonic assisted preparation of magnetic
behavior of heavy crude oil was studied. The design of the MWCNT was prepared according to the method described in our
prepared catalyst, containing Fe3O4 and ionic liquid, plays a previous report.31 MWCNTs were sonicated in deionized water (DI)
major role in reducing the heavy oil viscosity by breaking the under nitrogen atmosphere for 15 min to get rid of any dissolved
oxygen. Then, the anhydrous ferric chloride and ferrous sulfate
bonds between carbon and sulfur and reducing the content of heptahydrate were added to the suspension in a ratio of 2:1, and the
asphalt and resins. Based on the obtained results, the suspension was sonicated for 15 min. Next, NH4OH was added
mechanism of catalytic aquathermolysis using ionic liquid dropwise to the suspension under sonication until the pH reached 10,
modified magnetic MWCNT was proposed. and then the suspension was kept under ultrasonic irradiation for 30
min. The obtained precipitate was centrifuged, washed with DI water
2. EXPERIMENTAL SECTION and dried at 100 °C for 24 h.
2.2.3. Preparation of Fe 3O 4 /MWCNT@EFHIA and Fe 3O 4 /
2.1. Materials. Iron(III) chloride (FeCl3, 97%), iron(II) sulfate MWCNT@BmimA. Incipient wetness impregnation technique was
heptahydrate (FeSO4·7H2O, ≥99.0%), ammonium hydroxide solution used to prepare the Fe3O4/MWCNT@EFHIA. The EFHIA (0.5 g)
(28.0−30.0% NH3 basis), salicylaldehyde (98%), paraformaldehyde was dissolved in an appropriate volume of water and then added to
(powder, 95%), hydrochloric acid (37%), sodium chloride (≥99.5%), Fe3O4/MWCNT (2.0 g) under stirring. The EFHIA/Fe3O4/
sulfuric acid (95.0−98.0%), sodium bicarbonate (99.5%), sodium MWCNT catalyst was aged for 2 h, and the water was evaporated
acetate (≥99.0%), 1-ethyl-1H-imidazole, diethyl ether (anhydrous, under stirring to soak the ionic liquid inside the Fe3O4/MWCNT
≥99.0%), anhydrous ferric chloride, ferrous sulfate heptahydrate, 1- pores. After that, Fe3O4/MWCNT@EFHIA was washed with water to

11354 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

Scheme 1. Schematic Diagram of Ionic Liquid Modified Magnetic MWCNT Structureas a Representative Example

Figure 1. FTIR spectra of EFHIA, Fe3O4/MWCNT@BmimA, and Fe3O4/MWCNT@EFHIA.

Figure 2. 1H NMR and 13C NMR of EFHIC compound.

remove the unadsorbed ionic liquid species. On the other hand, ionic liquid modified Fe3O4/MWCNT was conducted using a NOVA
Fe3O4/MWCNT@BmimA was prepared according to the same 3200e (Quantachrome, U.S.A.). The desorption process was
method with BmimA. Next, the impregnated samples were dried at conducted at 100 °C for 3 h before performing the analysis. The
100 °C for 24 h, as shown in Scheme 1. FTIR, proton NMR, and 13C NMR spectra of EFHIA, Fe3O4/
2.3. Characterization. The XRD patterns of the prepared Fe3O4/ MWCNT@EFHIA, Fe3O4/MWCNT@BmimA were obtained using
MWCNT and ionic liquid modified Fe3O4/MWCNT were acquired Bruker Tensor-37 FT-IR spectrophotometer, Bruker Avance DRX200
using a Philips powder diffractometer with Cu Kα radiation. The (200 MHz for 1H) and Bruker Avance DRX500 (500 MHz for 13C)
morphology of Fe3O4/MWCNT and ionic liquid modified Fe3O4/ spectrometer, respectively.
MWCNT were studied using JEOL JEM-2100 and SEM JEOL 5410 2.4. Catalytic Aquathermolysis Experiment. The thermal
(Japan) that were adjusted at 200 and 30 kV, respectively. The aquathermolysis and catalytic aquathermolysis were performed in Parr
thermal stability and amount of ionic liquid impregnated on Fe3O4/ Inconel-made autoclave Teflon lined reactor of 400 mL with an
MWCNT were identified by TGA (STD Q600 instrument) operated autoclave temperature control unit Parr 4848 (Parr Instruments Co.)
at a heating rate of 10 °C min−1 under N2−flow. Texture analysis of The reactor was filled with an amount of oil estimated at 150 mL and

11355 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

10% water. In the case of using a catalyst, the catalyst was dispersed in the imidazole ring, respectively. The singlet at ∼5.2 ppm is
the same percentage of water, and the reaction conditions were assigned to CH2 of chloromethyl attached to ammonium
adjusted by changing the temperature, time, and amount of the group, the peak at ∼7.4 ppm is a fingerprint for the benzene
catalyst. Bearing in mind that all experiments were conducted at 150 ring, and near 8 ppm is for imidazole protons. The peak at 9.5
rpm. The products of the aquathermolysis reaction were identified
using GC chromatography (Agilent Technologies-6890 N equipped ppm is assigned to the aldehydic group, while those at 10.3 and
with HP-1 column), total sulfur ratio (XRF analyzer, Spectro-Phoenix 10.4 ppm are due to proton of hydroxyl and hydrogen bond
II), and the rheological of crude oil was measured by Brookfield PVS hydroxyl group, respectively. The 13C NMR shows peaks at δ
Rheometer (U.S.A.). 13.7, 32.2, 51.5, 118.2, 123.5, 124, 126.8, 129.1, 136.5, 136.9,
161.1, and 190.4 ppm.
3. RESULTS AND DISCUSSION The XRD patterns of bare MWCNT and the prepared ionic
3.1. Characterization of the Prepared Materials. The liquid modified magnetic MWCNT are presented in Figure 3.
FTIR spectra of BmimAl EFHIC and Fe3O4/MWCNT@ It is obvious that the XRD pattern of the bare MWCNT shows
two peaks at 26.5°and 42.9° that are typical diffraction peaks
for pure MWCNT. On the other hand, the pattern of both
ionic liquids modified magnetic MWCNT exhibit additional
peaks at 2θ = 30.5°, 35.8°, 43.2°, 53.8°, 57.3°, and 62.9° that
are ascribed to the magnetite nanoparticles.34 The pattern also
shows that the structure of MWCNT was not altered by the
harsh preparation conditions.35 Moreover, the lower intensity
of these peaks may suggest a good dispersion of the magnetic
iron oxide on the MWCNT surface.
To study the dispersion of magnetic iron oxide on the
MWCNT surface and also to studying the stability of the
MWCNT morphology after impregnation, both SEM and HR-
TEM were conducted (Figure 4). The MWCNTs image shows
that there is no agglomeration after treatment with nitric acid,
and the diameter of MWCNTs is about 25 nm. After the
Figure 3. XRD of MWCNT, Fe3O4MWCNT@BmimA, and Fe3O4/ impregnation process, it appears that the magnetic iron oxide
MWCNT@ EFHIA materials. appears in the cluster (a spherical shape with an average
particle size of 3.5 nm), and by comparing the inner diameter
of the virgin MWCNT and the bearing MWCNT BmimA, a
EFHIA materials are shown in Figure 1. The spectrum of decrease in the diameter from 25 to 17 nm, which indicates
Fe3O4/MWCNT@BmimA exhibits various overlapping bands that there is an amount of magnetic iron and ionic liquid has
such as the bands appear at 2888 and 2950 cm−1 that are been deposited inside the MWCNT material (Figure 4a,b).
ascribed to the stretching vibration of C−H for both MWCNT The SEM images show that liquid and magnetic iron have
and BmimA. The spectrum exhibits a major band at 1716 cm−1 been dispersed on the MWCNT surface in a spherical shape,
that is assigned to the stretching vibration of CO of BmimA. and there is a single magnetic iron that is not bound on the
The band appears at 1400 cm−1 is assigned to the stretching MWCNT. That extra quantity of iron oxide has clumped
vibration of C−O of BmimA, while that appears at 1337 cm−1 together and formed a cluster with fine size (Figure 4c,d).
is assigned imidazole C−N vibration. The broadband centered The adsorption−desorption isotherm of the prepared
at 3401 cm−1 is assigned to OH stretching vibration. The Fe3O4/MWCNT@BmimA exhibits a Type IV isotherm,
EFHIC compound shows O−H stretching broad vibration which usually appears with mesoporous material, and Type
band at 3434 cm−1, C−H stretching aromatic band at 3086 H-4 desorption loops, indicating the sample contains micro/
cm−1, C−H stretching ethyl group band at 2960 and 2853 mesopores36 (Figure 5a). The surface area of the Fe3O4/
cm−1, weak doublet C−H stretching band at 2830 cm−1 MWCNT@BmimA material was found to be 115 m2 with
(−CHO), strong CO stretching band at 1716 cm−1, strong bimodal pore diameter at 1.5 nm (predominant) and 2.1 nm
C−Cl stretching band at 821 cm−1. The stretching band of the (lowest; Figure 5b), and this agrees well with HR-TEM results.
imidazole band is seen at 1466 cm−1.32 The Fe3O4/ Barrett−Joyner−Halenda [BJH] method was used to obtain
MWCNT@EFHIA catalyst shows similar bands; however, the pore size distribution curve of the prepared ionic liquid
O−H stretching broad vibration band at 3434 cm−1 shows a modified magnetic MWCNT, as presented in Figure 4b. The
blue shift by 50 cm−1 due to the formation of a hydrogen curve shows two peaks appear at 13 and 19 Å for ionic liquid
bond.33 The bands of the C−H stretching (ethyl group band) modified magnetic MWCNT.
at 2972 cm−1 and the C−H stretching vibrations of the The thermal stability of the prepared catalyst was tested to
aromatic ring appear at 3028 cm−1. A large shift occurs for the make sure that the prepared nanocomposite can endure the
1466 cm−1 band (imidazolium ring) by 32 cm−1, which elevated temperature. The TGA curve of the prepared Fe3O4/
indicates that the interactions of imidazolium ring and acetate MWCNT@BmimA reveals that the prepared catalyst can
anion became weaker after the impregnation process. The withstand elevated and severe reaction conditions, as displayed
intensity of the carbonyl group band was also reduced after in Figure 6a. The curve shows that the onset and start
impregnation, indicating the physisorption of carbonyl group temperatures of 1-butyl-3-methylimidazolium acetate are 265
on Fe3O4/MWCNT. and 214 °C, respectively. The TGA curve of the prepared
The 1H NMR and 13C NMR of EFHIC are shown in Figure Fe3O4/MWCNT@EFHIA catalyst reveals that the catalyst is
2. The multiplet at 1.3 and 4.2 ppm is assigned to the methyl detected to withstand heat conditions up to 239 °C; after that,
group protons in CH3 and CH2 of the ethyl group attached to the ionic liquid begins to decompose until 284 °C (Figure 6b).
11356 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

Figure 4. HR-TEM and SEM analysis of MWCNT and MWCNT BmimA materials as a representative example.

Figure 5. (a) N2 adsorption−desorption isotherm and (b) pore size distribution curve of Fe3O4/MWCNT@BmimA as a representative example.

The remaining constituents of the catalyst do not affect by heat 3.2. Effect of Ionic Liquid Modified Magnetic MWCNT
until 500 °C. Thus, it can be concluded that the composite is Catalyst on the Rheological Behavior of Heavy Crude
able to tolerate the elevated temperature and can be used many Oil. To demonstrate the effectiveness of Fe3O4/MWCNT@
without any structural changes. EFHIA and Fe3O4/MWCNT@BmimA in the aquathermolysis
11357 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

temperature (70 °C) and even at a higher temperature (180

and 220 °C), as listed in Table 2 and Figure 7a−d.
The data in Table 2 and Figure 7a−d show that the
reduction in viscosity using Fe3O4/MWCNT@EFHIA is
better than that for Fe3O4/MWCNT@BmimA catalyst.
Using only 0.1 wt % Fe3O4/MWCNT@EFHIA catalyst, the
viscosity of the crude oil decreased by 0.2%, 23.1%, 52.3%, and
62.1% after aquathermolysis reaction for 2 h. It is worth noting
that the addition of a catalyst reduces the viscosity of the crude
oil by a little value, as shown in Table 2. This result may reflect
the ability of the catalyst to disperse the asphaltene molecules
as it comprises chemical groups that can bind to asphaltene.
Subramanian et al.37 stated that the asphaltenes molecules
show a different set of chemical bonds, such as noncovalent
interactions (π−aromatic−π−aromatic rings, which cause
Figure 6. Thermal stability (TGA test) of (a) Fe3O4/MWCNT@ stacking), Lewis acid−base interactions (such as nitrogen
BmimA and (b) Fe3O4/MWCNT@EFHIA materials. atom relates to asphaltene with transition metals), electron-
donor−acceptor complex and hydrogen bonding interaction,
process, the outputs were compared in the absence of a catalyst and these bonds induce the asphaltene molecules to collect or
(thermal cracking) and in the presence of the prepared aggregate and thus increase the viscosity of the crude oil.
catalysts at temperatures of 70 (near reservoir temperature), Whereas Fe3O4/MWCNT@EFHIA catalyst has moieties that
200, and 250 °C with 10% water content for 2 h. The viscosity are capable of binding asphaltene molecules with premen-
of crude oil was measured at the same temperature to identify tioned bonds, for example, the carboxylic group has the ability
the difference between the viscosities in both cases (at time = to bind to asphalt through hydrogen bonds, and MWCNT
adsorbs the asphaltene by π−bonds and the imidazole ring is
0, whether it is thermal or catalytic and after the able to complex with the transition metals in asphaltene
aquathermolysis process) and to avoid the effect of the molecules. In addition to the Lewis acid sites, Fe(III) can
amount of added water. Without using a catalyst, the data promote the reaction involving carbonyl groups via the
reveal that the viscosity of crude oil remains steady at low formation of a complex with oxygen and nitrogen atom of

Table 2. Effect of Aquathermolysis Reaction on Viscosity and Sulfur Reduction of Heavy Oil at Different Tempratures Using
0.1, 0.2, and 0.3 wt % Fe3O4/MWCNT@EFHIA and Fe3O4/MWCNT@Bmim[OAc]

catalyst dosage reaction temperature viscosity viscosity reduction rate sulfur reduction
heavy oil (wt %) (°C) (cP) (%) (%)
untreated 70 15220.3
180 10146.3
200 5340.2
220 4135.6
treated with Fe3O4/MWCNT@EFHIA 0.1 70 15180.3 0.2 4
180 7804.8 23.1 18
200 2542.2 52.3 27
220 1579.1 62.1 33
0.2 70 15100.3 0.8 11
180 3547.6 65 35
200 1588.9 70.2 37
220 1230.5 73.1 43
0.3 70 15000.3 1.4 15
180 2217.3 72.1 42
200 1134.9 74.7 45
220 1030.8 75.9 47
treated with Fe3O4/ 0.1 70 15195.4 0.16 1.3
MWCNT@Bmim[OAc] 180 9037.5 10.9 6
200 3900.4 26.9 9
220 3001.7 27.4 11
0.2 70 15150.8 0.45 4.4
180 7965.8 21.5 14
200 3054.9 42.8 14.8
220 2677.4 35.3 17.2
0.3 70 15060.8 1.04 7.9
180 5741.5 43.4 22
200 2433.8 54.4 23.6
220 2037.6 50.7 25

11358 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

Figure 7. Relation between viscosity and shear rate for untreated and treated heavy crude oil using Fe3O4/MWCNT@EFHIA catalyst at
temperatures (a) 70, (b) 180, (c) 200, and (d) 220 °C at different ratios.

11359 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

Table 3. Effect of Aquathermolysis Reaction Time on

Viscosity Reduction Rate of Heavy Oil at 200 °C Using 0.2
wt % Fe3O4/MWCNT@EFHIA
reaction time viscosity viscosity reduction rate
temperature (h) (cP) (%)
200 °C 0.5 6165.2 10.9
1 3923.8 44.4
1.5 2261.5 69.1
2 1588.9 70.2

asphaltene.38 The formation of such chemical bonds between

the catalyst and asphaltene prevents the aggregation of
asphaltene particles, or at least the growth of the asphaltene
clusters.39 The data show that the viscosity of crude oil
decreases with increasing the reaction temperature as listed in
Table 2. The viscosity of crude oil declined to 65%, 70.2%, and
73.1% using Fe3O4/MWCNT@EFHIA (0.1 wt %) as a catalyst
at 180, 200, and 220 °C, respectively. Such decline can be
attributed to the catalytic aquathermolysis phenomenon, in
which a considerable amount of hydrogen sulfide, methane,
carbon dioxide, and hydrogen molecules are liberated
according to Hyne’s proposal.40 This proposal suggests that
the sulfur-containing compounds are involved in this reaction,
where the organosulfur compounds react with water to
produce an alcoholic compound, mercaptans, and hydrogen
sulfide. The alcohol is converted to aldehydes, which are
decomposed to CO and hydrocarbon. The CO is oxidized in
the presence of water to CO2 and H2, and the remaining sulfur
in mercaptan moieties is converted to hydrogen sulfide and Figure 8. Chromatogram of crude oil before and after the
light hydrocarbon.41 After conducting an aquathermolysis aquathermolysis process using 0.2% Fe3O4/MWCNT@EFHIA
reaction, the sulfur content in crude oil decreased to catalyst.
approximately 33% when the reaction was conducted at a
temperature of 220 °C, and this percentage decreased to 18% concentration of 0.3 wt % was used at a temperature of 220 °C,
when the reaction was carried out at 180 °C. The reduction in and these results approximate the results achieved using the 0.2
sulfur content suggests that the bonding of the two asphaltene wt % dosage at 200 °C. This behavior can be attributed to
molecules through π-bonds became weaker, and this is deemed increasing the formation of π−π interactions between the
an effective way to prevent the aggregation of asphaltene aromatic groups of the catalyst and crude oil. Moreover, the
molecules, which finally reduces the crude oil viscosity.2 change in crude oil viscosity was studied overtime at a
It is also noted from the results recorded in Table 1 that, temperature of 220 °C using a catalyst dosage of 0.2 wt %, and
with an increase in the amount of catalyst from 0.1 to 0.3 wt %, the obtained results are listed in Table 3. It became clear that
the viscosity of crude oil decreases, and there is also a the viscosity of crude oil decreased by 10% during the first 30
correlation between this decrease in the viscosity of crude oil min, then it reached its climax after 1.5 h (69.1%), and beyond
and the decrease in the sulfur content. However, the reduction it, the viscosity became steady. By measuring the ratio of sulfur
extent, whether in viscosity of crude oil or sulfur content was (wt %) in asphaltene and resin of crude oil before conducting
much better at 200 °C, especially when considering the aquathermolysis experiments, it became clear that the sulfur
economic factor. The reduction of crude oil viscosity and content in asphaltene and resin was 5.24% and 6.72%,
sulfur content upon increasing the catalyst concertation can be respectively (Table 4). After conducting catalytic aquather-
attributed to the increase of available active sites. For instance, molysis experiments, this ratio for asphaltene decreased by
the best value for the reduction of crude oil viscosity (75.9%) 12%, 18%, and 21%, while that for resin decreased by 5.5%,
and sulfur content (47%) was obtained when a catalyst with a 6%, and 9%. It is worth noting that the ratio of extracted

Table 4. Reduction in Sulfur Content (wt %) of Crude Oil, Asphaltene, and Resin after Aquathermolysis Process at 200°C for
2h
process E Aa SAb E Rd SRc total TRSe
crude oil 12.21 ± 0.25 5.24 19.35 ± 0.15 6.72 7.0523
aquathermolysis @180 10.74 ± 0.26 5.036 18.23 ± 0.1 ∼6.432 ∼4.582 ∼35
aquathermolysis @200 10.12 ± 0.28 4.95 18.142 ± 0.22 ∼6.3382 ∼4.441 ∼37
aquathermolysis @220 9.65 ± 0.5 4.72 17.563 ± 0.3 ∼6.1975 ∼4.018 ∼43

a
Ea is extracted asphaltene (wt %). bSA is sulfur related to asphaltene. cSR is sulfur related to resin. dER is the extracted resin (wt %). eTRS is the total
reduction in sulfur (wt %) calculated as, TRS = 100 − ( 7.05 − total sulfur after the experiment
total sulfur before the experiment )
× 100 .

11360 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

Table 5. Mole Fraction Percentages of Blank Crude Oil and Crude Oil after Aquathermolysis Reaction Using 0.2% Fe3O4/
MWCNT@EFHIA Obtained from GC Analysis
mol %
compound blank 180 °C 200 °C 220 °C
ethane 0 0.021378048 0.034978663 0.031991918
propane 0 0.250959688 0.449725667 1.767974406
i-butane 0 0.427560951 0.649603742 0.968176461
n-butane 0 0.464740164 0.629615934 2.093786833
i-pentane 0 0.51121418 0.649603742 0.799797946
n-pentane 0 0.641341426 0.629615934 0.047145984
n-hexane 0.033257317 0.622751819 0.729554971 0.844418252
me-cyclo-pentane 0.002375523 0.009294803 0.005996342 0.151540663
benzene 0.041571646 0.743584262 0.93942695 0.347701633
cyclohexane 0.142531357 0.817942688 1.119317216 0.005051355
n-heptane 0.285062714 0.883006311 1.339183098 1.75282034
total 0.504798556 5.393774341 7.17662226 8.810405792
me-cyclo-hexane 0.534492588 0.132915687 0.159902459 0.134702812
toluene 0.831432915 1.375630885 1.768920958 2.062636808
C8 1.116495629 1.738128213 2.088725877 2.43306954
ethyle benzene 1.579722539 2.258637196 2.25862224 2.012123253
m,p-xylene 1.876662866 1.914729475 2.628396678 2.453274962
o-xylene 2.446788293 1.67306459 2.328579566 1.718302745
total 8.385594831 9.093106044 11.23314778 10.81411012
n-nonane 2.787675789 4.628812031 3.997561487 3.444182522
TMB 3.349486887 0.585572606 0.929433046 0.918504799
n-decane 3.990877993 7.418182494 6.66593378 9.379525173
n-undecane 4.715412391 9.294803275 8.794635272 8.56457316
n-dodecane 6.045705055 10.42505135 11.85676737 10.38390301
n-tridecane 7.835661345 10.23357841 10.89735261 10.0024714
n-tetradecane 8.314329152 9.70377462 9.306323143 8.942582926
n-pentadecane 7.375997719 8.774294292 7.595366826 8.878599091
total 44.41514633 61.06406908 60.04337354 60.51187069
n-hexadecane 6.41391106 7.249946555 6.178231279 6.584441825
n-heptadecane 5.534967693 5.570375603 4.779084758 5.155750126
n-octadecane 4.359083998 3.387026314 2.682363758 3.101532244
n-nonadecane 3.67018244 2.243765511 1.63900021 1.120559017
n-icosane 3.123812239 1.211112867 1.079341602 0.918504799
total 23.10195743 19.66222685 60.04337354 16.88078801
total of n-henicosane to n-tetracontane 23.59250285 4.864115 3.896495 2.794545

Table 6. Comparison between the Catalytic Aquathermolysis Performance over Different Catalyst
catalyst oil catalyst amount T (°C) viscosity reduction ref
Fe3O4 nanoparticles extra-heavy oil 6.25% 280 85.0% 44
aromatic sulfonic acid/NiCl2 Shengli Oilfield of China 0.5% 200 96.26% 45
Cu(C7H7O3S)2 Sheng2Re7 0.203% 200 95.18% 46
(Fe(C7H7O3S)3 Sheng2Re7 0.203% 200 92.27% 46
Fe3O4 heavy oil 0.56% 120 30.0% 47
Ni0.3Fe2.7O4 heavy oil 0.56% 120 17.0% 47
Fe3O4/heulandite extra-heavy oil 6.25% 280 85.0% 22
NiWMo NPs Athabasca Bitumen 0.452% 340 23.2% 48
Fe3O4/MWCNT@EFHIA extra-heavy oil 0.3% 220 75.9% this work
Fe3O4/MWCNT@BmimA extra-heavy oil 0.2% 220 54.4% this work

asphaltene is proportional to the ratio of sulfur remaining in compounds did not reach the same extent as that for the
the asphaltene compound. For instance, when the ratio of asphaltene compound. Several mechanisms have been
asphaltene decreased by 12%, 18%, and 21%, the reduction in proposed by Wang et al.,42 including pyrolysis, depolymeriza-
sulfur (wt %) of asphaltene molecules was of 4, 5.5, and 10 wt
tion, hydrogenation, isomerization, ring-opening, and recon-
%, suggesting the sulfur bonds that link the parts of asphaltene
molecules were broken down, and some of the alkyl chains struction. All these mechanisms suggested the pyrolysis of
were also cleaved. The same trend has also been observed for resins and asphaltenes side chains, forming saturated or
the resin compound, but the removal of sulfur from the resin unsaturated hydrocarbons. Also, some aggregations of
11361 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

Scheme 2. Possible Mechanism of the Upgrading of Heavy atures, which demonstrates the difficulty of breaking such
Crude Oil by Using Fe3O4/MWCNT@EFHIA Catalyst compounds. Moreover, it was found that when an aqua-
thermolysis reaction was conducted, the molar percentage of
long-chain paraffins (n-hexadecane to n-icosane) decreased
from (blank) to 24.05, 17.97, 15.56, and 14.94 mol %, when
conducting aquathermolysis experiments at 180, 200, and 220
°C, respectively.
The increase in aromatics and some kinds of paraffin was
observed by Cui et al.,43 and they attributed this behavior to
the decomposition of a portion of the resin and asphaltene into
their corresponding alky chains and simple aromatic and
polycondensed aromatic species that were then released in the
system. Furthermore, the total molar percentage of the
compounds listed between n-henicosane and n-tetracontane
compounds decreased from 24.57 mol % (blank) to ∼18.61
mol % after conducting the catalytic reaction at 180 and 200
°C, and this molar ratio decreases with increasing the reaction
temperature to 220 °C of the catalytic process to 16.56 mol %.
polycyclic aromatic hydrocarbons are depolymerized to their The decrease in the molar percentage of long-chain hydro-
corresponding fragments. carbons is mainly due to the change in crude oil composition
The resultant low molecular weight hydrocarbon can help to and the difficulty of cracking the short-chain hydrocarbons
dissolve the heavy fractions, and consequently, the viscosity is than the longer ones.
reduced. The chromatographic analysis (GC) shows the Table 6 shows a comparison of the performance of Fe3O4/
change in crude oil after catalytic aquathermolysis using MWCNT@EFHIA and Fe3O4/MWCNT@BmimA relative to
Fe3O4/MWCNT@EFHIA after treatment for two hours at some heterogeneous and amphiphilic catalysts. It appears that
temperatures of 180 °C, 200 and 220 °C (Figure 8 and Table the use of catalyst Fe3O4/MWCNT@EFHIA led to a decrease
5). After conducting aquathermolysis experiments, the total
in the viscosity of heavy crude oil by 75.9%, which is
mole percent of compounds (ethane-n-heptane) has increased
considered promising for the petroleum industry to facilitate
from 0.525 mol. % to 3.43, 4.53, and 6.23 mol. % at a
due to the reasonable cost preparation and the temperature at
temperature of 180, 200, and 220 °C, respectively. The molar
ratio of the compounds that are listed between methyl-cyclo- which this efficiency appears.
hexane and o-xylene shows the same trend. Nevertheless, there It should be noted that the Fe3O4 nanoparticles dispersed on
is a reasonable increase in the amount of toluene, and this MWCNT have a high oxygen storage capacity (OSC) along
increase may be due to the decrease in methyl-cyclo-hexane. with an adequate oxidation−reduction property (redox).49
This confirms that there is a dehydrogenation process through These properties make Fe3O4 able to oxidize hydrocarbons
the formation of olefins, and consequently, the chance of molecules by releasing hydrogen species from water.49 Thus, it
aromatic formation increases. The highest molar percent of can be inferred that the outstanding performance of Fe3O4/
aromatics was obtained at 220 °C, and that explains the MWCNT@EFHIA as a catalyst can be ascribed to the synergy
considerable reduction in viscosity at this degree. between the catalyst components in enhancing the aqua-
It is obvious that the total molar percent of the compounds thermolysis process. Particularly, MWCNT absorbs the
listed between n-nonane and n-pentadecane increased from asphaltene molecules via π bonds, and the ionic liquid acts
45.01 mol % (blank) to ∼53 mol % after conducting the as a dispersing agent for asphaltene and resin aggregations and
experiments and it is clear that there is a slight difference thus facilitates the entrance of these molecules into catalyst
between the molar percentages obtained at different temper- pores.

Scheme 3. Possible Mechanism of the Cracking of Aromatic Sulfur by Using Fe3O4/MWCNT@EFHIA Catalyst

11362 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels

■
pubs.acs.org/EF Article

Hosseinpour et al.50 demonstrated that the lattice oxygen of AUTHOR INFORMATION

a metal oxide and the active proton of water molecule are the Corresponding Authors
main active species in aquathermolysis process. Thus, we M. A. Betiha − Egyptian Petroleum Research Institute, Enhanced
believe that the proposed mechanism is based on the redox Oil Recovery Unit, Nasr City, Cairo 11727, Egypt; Faculty of
cycle of Fe3+/Fe2+ species within the magnetite nanoparticles. Nanotechnology, Cairo University, Giza 12588, Egypt;
First, the lattice oxygen reacts with hydrocarbons, which then Email: [email protected]
reduce the ferric ions species to ferrous ions (Fe3+ → Fe2+) at Tahany Mahmoud − Egyptian Petroleum Research Institute,
the catalyst surface. Next, the dissociation of water molecules Enhanced Oil Recovery Unit, Nasr City, Cairo 11727, Egypt;
on the catalyst surface reoxidizes the surface vacancies, and orcid.org/0000-0002-5040-5669;
consequently the ferric ions are retained (Fe2+ → Fe3+). The Email: [email protected]
water molecules dissociate over the catalyst surface to produce
hydrogen and oxygen, which are then adsorbed on the catalyst Authors
surface. In particular, hydrocarbons react with adsorbed oxygen Ahmed E. ElMetwally − Egyptian Petroleum Research Institute,
molecules to produce aldehydic or ketones species while the Nasr City, Cairo 11727, Egypt; Department of Chemistry,
unsaturated compounds are hydrogenated via the generated University of Miami, Coral Gables, Florida 33146, United
hydrogen. Hosseinpour50 summarized the aquathermolysis in States
the following equation: A. M. Al-Sabagh − Egyptian Petroleum Research Institute,
Enhanced Oil Recovery Unit, Nasr City, Cairo 11727, Egypt
hydrocarbons, CmH n Complete contact information is available at:
O2 −adsorbed on the catalyst https://pubs.acs.org/10.1021/acs.energyfuels.0c02062
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ CmHn − 2O + H 2O
+ 2surface vacancy + 4e− Notes
The authors declare no competing financial interest.

■
H 2O + 4e + 2surface vacancy → 2O2 − + H 2
cracking REFERENCES
CmHn − 2O ⎯⎯⎯⎯⎯⎯⎯→ Cm − 1Hn − 2 + CO
(1) Agency, I. E. Resources to Reserves 2013: Oil, Gas and Coal
CO + H 2O → H 2 + CO2 Technologies for the Energy Markets of the Future; International Energy
Agency: 2013.
Meanwhile, portions of asphaltene or resin heteroatom (S or (2) Xu, Y.; Ayala-Orozco, C.; Chiang, P.-T.; Shammai, M.; Wong,
N) can interact with the surface vacancies (Lewis acid sites) to M. S. Understanding the role of iron (III) tosylate on heavy oil
form a complex as presented in Scheme 2. It is well-known that viscosity reduction. Fuel 2020, 274, 117808.
the ionic product of water (Kw) increases with increasing the (3) Speight, J. G. Introduction to enhanced recovery methods for heavy
oil and tar sands; Gulf Professional Publishing: 2016.
temperature where the water pH reaches 6.14 at 100 °C. Thus, (4) Hinkle, A.; Shin, E.-J.; Liberatore, M. W.; Herring, A. M.; Batzle,
we believe that the protonation of basic atom-like sulfur or M. Correlating the chemical and physical properties of a set of heavy
nitrogen can take place. Clark et al.41 reported that the positive oils from around the world. Fuel 2008, 87 (13), 3065−3070.
charge could be delocalized to the neighboring carbon atom (5) Li, J.-J.; Wang, X.; Tang, X.-D.; Wang, F.; Qing, D.-Y. Effect of
via sigma-bond, and consequently, hydrogen sulfide is Transition Metal Polymers with Varying Side Alkyl Chain on
eliminated, and the subsequent rearrangement leads to the Viscosity Reduction of Crude Oil and Aggregation Behavior of
formation of olefins (Scheme 3). Asphaltene. Energy Fuels 2015, 29 (12), 7771−7780.
(6) Mohammadi, K.; Ameli, F. Toward mechanistic understanding
of Fast SAGD process in naturally fractured heavy oil reservoirs:
4. CONCLUSION Application of response surface methodology and genetic algorithm.
Fuel 2019, 253, 840−856.
In summary, a new strategy to enhance the catalytic
(7) Yuan, J.-Y.; McFarlane, R. Evaluation of Steam Circulation
aquathermolysis of heavy asphaltic crude oil has been Strategies for SAGD Startup. Journal of Canadian Petroleum
developed by introducing an ionic liquid modified multi- Technology 2011, 50 (01), 20−32.
component nanocatalyst. The prepared Fe3O4/MWCNT@ (8) Hyne, J.; Greidanus, J.; Tyrer, J.; Verona, D.; Rizek, C.; Clark, P.;
EFHIA showed an outstanding performance in the catalytic Clarke, R.; Koo, J. Aquathermolysis of heavy oils. Revista Tecnica
aquathermolysis of heavy asphaltic crude oil. The results Intevep 1982, 2 (2), 87−94.
showed that the reduction in viscosity using Fe3O 4/ (9) Maity, S. K.; Ancheyta, J.; Marroquín, G. Catalytic Aqua-
MWCNT@EFHIA was better than that for Fe 3 O 4 / thermolysis Used for Viscosity Reduction of Heavy Crude Oils: A
Review. Energy Fuels 2010, 24 (5), 2809−2816.
MWCNT@BmimA. The outstanding performance of Fe3O4/ (10) Guo, K.; Li, H.; Yu, Z. In-situ heavy and extra-heavy oil
MWCNT@EFHIA as a catalyst can be ascribed to the synergy recovery: A review. Fuel 2016, 185, 886−902.
between the catalyst components in enhancing the aqua- (11) Rivas, O.; Campos, R.; Borges, L. Experimental evaluation of
thermolysis process. The redox cycle of the Fe3+/Fe2+ species transition metals salt solutions as additives in steam recovery
within the Fe3O4 nanoparticles plays a vital role in the processes, SPE Annual Technical Conference and Exhibition; Society
oxidization of hydrocarbons molecules. Thus, we believe that of Petroleum Engineers: 1988.
the prepared Fe3O4/MWCNT@EFHIA can act as an effective (12) Wen, S.; Zhao, Y.; Liu, Y.; Hu, S. A study on catalytic
aquathermolysis of heavy crude oil during steam stimulation.
and sustainable catalyst for upgrading the asphaltic crude oil by
International symposium on oilfield chemistry; Society of Petroleum
reducing its viscosity. The prepared catalyst has the advantage Engineers: 2007.
of low cost with the possibility of application in industrial (13) Li, Y.-R.; Li, Q.-Y.; Wang, X.-D.; Yu, L.-G.; Yang, J.-J.
fields, including the possibility of industrial exploitation in the Aquathermolysis of heavy crude oil with ferric oleate catalyst. Pet. Sci.
field of heavy oil. 2018, 15 (3), 613−624.

11363 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364
Energy & Fuels pubs.acs.org/EF Article

(14) Zhao, F.; Liu, Y.; Wu, Y.; Zhao, X.; Tan, L. Study of catalytic (33) Kotov, N.; Š turcová, A.; Zhigunov, A.; Raus, V.; Dybal, J.
aquathermolysis of heavy oil in the presence of a hydrogen donor. Structural Transitions of 1-Butyl-3-methylimidazolium Chloride/
Chem. Technol. Fuels Oils 2012, 48 (4), 273−282. Water Mixtures Studied by Raman and FTIR Spectroscopy and
(15) Galukhin, A. V.; Erokhin, A. A.; Nurgaliev, D. K. Effect of WAXS. Cryst. Growth Des. 2016, 16 (4), 1958−1967.
Catalytic Aquathermolysis on High-Molecular-Weight Components (34) Zhao, T.; Ji, X.; Guo, X.; Jin, W.; Dang, A.; Li, H.; Li, T.
of Heavy Oil in the Ashal’cha Field. Chem. Technol. Fuels Oils 2015, Preparation and electrochemical property of Fe3O4/MWCNT
50 (6), 555−560. nanocomposite. Chem. Phys. Lett. 2016, 653, 202−206.
(16) Chen, Y.; Wang, Y.; Wu, C.; Xia, F. Laboratory Experiments (35) Suwattanamala, A.; Bandis, N.; Tedsree, K.; Issro, C. Synthesis,
and Field Tests of an Amphiphilic Metallic Chelate for Catalytic characterization and adsorption properties of Fe3O4 /MWCNT
Aquathermolysis of Heavy Oil. Energy Fuels 2008, 22 (3), 1502− magnetic nanocomposites. Materials Today: Proceedings 2017, 4 (5),
1508. 6567−6575.
(17) Chen, Y.; Yang, C.; Wang, Y. Gemini catalyst for catalytic (36) Thommes, M. Physical Adsorption Characterization of
aquathermolysis of heavy oil. J. Anal. Appl. Pyrolysis 2010, 89 (2), Nanoporous Materials. Chem. Ing. Tech. 2010, 82 (7), 1059−1073.
159−165. (37) Subramanian, D.; Wu, K.; Firoozabadi, A. Ionic liquids as
(18) Chao, K.; Chen, Y.; Liu, H.; Zhang, X.; Li, J. Laboratory viscosity modifiers for heavy and extra-heavy crude oils. Fuel 2015,
experiments and field test of a difunctional catalyst for catalytic 143, 519−526.
aquathermolysis of heavy oil. Energy Fuels 2012, 26 (2), 1152−1159. (38) Organic Transformations Promoted by Lewis Acid Iron
(19) Wu, C.; Su, J.; Zhang, R.; Lei, G.; Cao, Y. The Use of Catalysts. In PATAI’S Chemistry of Functional Groups; 2011.
Amphiphilic Nickel Chelate for Catalytic Aquathermolysis of Extra- (39) Hashmi, S. M.; Zhong, K. X.; Firoozabadi, A. Acid−base
chemistry enables reversible colloid-to-solution transition of asphal-
heavy Oil under Steam Injection Conditions. Energy Sources, Part A
tenes in non-polar systems. Soft Matter 2012, 8 (33), 8778−8785.
2014, 36 (13), 1437−1444.
(40) Hyne, J. Aquathermolysis: A Synopsis of Work on the Chemical
(20) Desouky, S.; Betiha, M.; Badawi, A.; Ghanem, A.; Khalil, S.
Reaction Between Water (steam) and Heavy Oil Sands During Simulated
Catalytic aquathermolysis of Egyptian heavy crude oil. International
Steam Stimulation; AOSTRA Library and Information Service, 1986.
Journal of Chemical and Molecular Engineering 2013, 7 (8), 638−643. (41) Clark, P. D.; Hyne, J. B.; Tyrer, J. D. Chemistry of
(21) Fan, H.-F.; Liu, Y.-J.; Zhong, L.-G. Studies on the Synergetic organosulphur compound types occurring in heavy oil sands:: 1.
Effects of Mineral and Steam on the Composition Changes of Heavy High temperature hydrolysis and thermolysis of tetrahydrothiophene
Oils. Energy Fuels 2001, 15 (6), 1475−1479. in relation to steam stimulation processes. Fuel 1983, 62 (8), 959−
(22) Lin, D.; Feng, X.; Wu, Y.; Ding, B.; Lu, T.; Liu, Y.; Chen, X.; 962.
Chen, D.; Yang, C. Insights into the synergy between recyclable (42) Wang, Y.; Chen, Y.; He, J.; Li, P.; Yang, C. Mechanism of
magnetic Fe3O4 and zeolite for catalytic aquathermolysis of heavy Catalytic Aquathermolysis: Influences on Heavy Oil by Two Types of
crude oil. Appl. Surf. Sci. 2018, 456, 140−146. Efficient Catalytic Ions: Fe3+ and Mo6+. Energy Fuels 2010, 24 (3),
(23) Monin, J.; Audibert, A. Thermal cracking of heavy oil/mineral 1502−1510.
matrix systems. SPE International Symposium on Oilfield Chemistry; (43) Cui, J.; Zhang, Z.; Liu, X.; Liu, L.; Peng, J. Studies on viscosity
Society of Petroleum Engineers: 1987. reduction and structural change of crude oil treated with acoustic
(24) Ovalles, C.; Vallejos, C.; Vasquez, T.; Rojas, I.; Ehrman, U.; cavitation. Fuel 2020, 263, 116638.
Benitez, J. L.; Martinez, R. Downhole upgrading of extra-heavy crude (44) Lin, D.; Zhu, H.; Wu, Y.; Lu, T.; Liu, Y.; Chen, X.; Peng, C.;
oil using hydrogen donors and methane under steam injection Yang, C.; Feng, X. Morphological insights into the catalytic
conditions. Pet. Sci. Technol. 2003, 21 (1−2), 255−274. aquathermolysis of crude oil with an easily prepared high-efficiency
(25) Junaid, A. S. M.; Rahman, M. M.; Rocha, G.; Wang, W.; Fe3O4-containing catalyst. Fuel 2019, 245, 420−428.
Kuznicki, T.; McCaffrey, W. C.; Kuznicki, S. M. On the Role of Water (45) Wu, C.; Lei, G.-L.; Yao, C.-J.; Sun, K.-J.; Gai, P.-Y.; Cao, Y.-B.
in Natural-Zeolite-Catalyzed Cracking of Athabasca Oilsands Bitu- Mechanism for reducing the viscosity of extra-heavy oil by
men. Energy Fuels 2014, 28 (5), 3367−3376. aquathermolysis with an amphiphilic catalyst. Journal of Fuel Chemistry
(26) Junaid, A. S. M.; Street, C.; Wang, W.; Rahman, M. M.; An, W.; and Technology 2010, 38 (6), 684−690.
McCaffrey, W. C.; Kuznicki, S. M. Integrated extraction and low (46) Li, J.; Chen, Y.; Liu, H.; Wang, P.; Liu, F. Influences on the
severity upgrading of oilsands bitumen by activated natural zeolite Aquathermolysis of Heavy Oil Catalyzed by Two Different Catalytic
catalysts. Fuel 2012, 94, 457−464. Ions: Cu2+ and Fe3+. Energy Fuels 2013, 27 (5), 2555−2562.
(27) Strausz, O. P.; Mojelsky, T. W.; Payzant, J. D.; Olah, G. A.; (47) Nugraha, M. I.; Noorlaily, P.; Abdullah, M.; Khairurrijal, K.;
Prakash, G. K. S. Upgrading of Alberta’s Heavy Oils by Superacid- Iskandar, F. Synthesis of NixFe3-xO4 nanoparticles by microwave-
Catalyzed Hydrocracking. Energy Fuels 1999, 13 (3), 558−569. assisted coprecipitation and their application in viscosity reduction of
(28) Betiha, M. A.; El-Henawy, S. B.; Al-Sabagh, A. M.; Negm, N. heavy oil. Mater. Sci. Forum; Trans Tech Publ: 2013; pp 204−208.
A.; Tahany Mahmoud. Experimental evaluation of cationic-Schiff base (48) Hashemi, R.; Nassar, N. N.; Pereira Almao, P. In Situ
surfactants based on 5-chloromethyl salicylaldehyde for improving Upgrading of Athabasca Bitumen Using Multimetallic Ultradispersed
crude oil recovery and bactericide. J. Mol. Liq. 2020, 316, 113862. Nanocatalysts in an Oil Sands Packed-Bed Column: Part 1. Produced
(29) Eshaq, G.; ElMetwally, A. E. Bmim[OAc]-Cu2O/g-C3N4 as a Liquid Quality Enhancement. Energy Fuels 2014, 28 (2), 1338−1350.
multi-function catalyst for sonophotocatalytic degradation of meth- (49) Yeletsky, P. M.; Zaikina, O. O.; Sosnin, G. A.; Kukushkin, R.
ylene blue. Ultrason. Sonochem. 2019, 53, 99−109. G.; Yakovlev, V. A. Heavy oil cracking in the presence of steam and
(30) Al-Sabagh, A. M.; Yehia, F. Z.; Eissa, A.-M. M. F.; Moustafa, M. nanodispersed catalysts based on different metals. Fuel Process.
E.; Eshaq, G.; Rabie, A.-R. M.; ElMetwally, A. E. Glycolysis of Technol. 2020, 199, 106239.
Poly(ethylene terephthalate) Catalyzed by the Lewis Base Ionic (50) Hosseinpour, M.; Fatemi, S.; Ahmadi, S. J. Deuterium tracing
Liquid [Bmim][OAc]. Ind. Eng. Chem. Res. 2014, 53 (48), 18443− study of unsaturated aliphatics hydrogenation by supercritical water in
18451. upgrading heavy oil. Part II: Hydrogen donating capacity of water in
(31) Al-Sabagh, A. M.; Yehia, F. Z.; Harding, D. R. K.; Eshaq, G.; the presence of iron(III) oxide nanocatalyst. J. Supercrit. Fluids 2016,
110, 75−82.
ElMetwally, A. E. Fe3O4-boosted MWCNT as an efficient sustainable
catalyst for PET glycolysis. Green Chem. 2016, 18 (14), 3997−4003.
(32) Betiha, M. A.; Negm, N. A.; El-Sayed, E. M.; Mostafa, M. S.;
Menoufy, M. F. Capability of synthesized sulfonated aromatic cross-
linked polymer covalently bonded montmorillonite framework in
productivity process of biodiesel. J. Cleaner Prod. 2020, 261, 120995.

11364 https://dx.doi.org/10.1021/acs.energyfuels.0c02062
Energy Fuels 2020, 34, 11353−11364