Review

Cite This: Energy Fuels 2018, 32, 2840−2854 pubs.acs.org/EF

Zirconia-Based Nanocatalysts in Heavy Oil Upgrading: A Mini Review

Ahmad Masudi† and Oki Muraza*,‡
†
Department of Chemical Process Engineering, Malaysia-Japan International Institute of Technology (MJIIT), Universiti Teknologi
Malaysia Kuala Lumpur, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur, Malaysia
‡
Center of Research Excellence in Nanotechnology and Chemical Engineering Department, King Fahd University of Petroleum &
Minerals, Dhahran 31261, Saudi Arabia

ABSTRACT: Two main limitations in heavy oil are the recovery and upgrading process, which emphasizes aquathermolysis as
an alternative approach to reduce viscosity and increase oil quality simultaneously. In addition to facilitating solubilization of
asphaltene, hot water (subcritical and supercritical) injected into the heavy oil reservoir also serves as a hydrogen donor. The
main purpose of this article is to review catalytic aquathermolysis of heavy oil over zirconia, which is a robust oxide. Zirconia-
based nanocatalysts are promising due to their high oxygen storage capacity, acidity, and stability in sub- and supercritical water.
The article also elaborates on various methods to fabricate nanosized zirconia with different shapes and sizes by sol−gel, spray
pyrolysis, electrospinning, and hydrothermal techniques.

1. INTRODUCTION
The race for more oil to meet energy demands calls for
unconventional oil positions in the energy market. The
worldwide reserve of unconventional oil is approximately 6
barrels. Advance technology development is needed to increase
heavy oil production, which is only 500 billion barrels with
existing technology.1 Heavy oil has a larger viscosity than
conventional oil, namely, greater than 100 cP.2 This unconven-
tional oil mainly consist of asphaltenes, resins, and aromatics.
These compositions are associated with heavy metals such as
vanadium and nickel.3
The challenge for heavy oil recovery is its high viscosity. This
high viscosity hinders the movement of heavy oil from
reservoirs. Numerous technologies have been studied including
in situ combustion, steam assisted gravity drainage (SAGD),
and aquathermolysis. Among these technologies, aquathermol-
ysis has received growing interest in recent years. Aqua-
thermolysis is an alternative technique which involves the
injection of steam and water at an elevated temperature and
pressure into reservoirs.4,5 Steam injection breaks large organic
compounds into smaller fragments and helps ease the
solubilization of organic matter.6
Viscosity is proportional to the asphaltene content.
Asphaltenes, which comprise 7−20 wt % of heavy oil, are
large organic compounds with a molecular weight in the range
of 500−750 g·mol−1. The molecular structure of asphaltene
consists of polycyclic heteroatoms (S, O, N) with a diameter
25−30 nm.7,8 The main mechanism for aquathermolysis
reaction is the C−S breakage of asphaltenes, which tends to
decrease heavy oil viscosity. This mechanism was clarified
through interpreting a similar gaseous product from aqua-
thermolysis of different nitrogen compounds.9 The same
amount of H2S product with a wide range of sulfur content
from below 0.5 wt % until 2.5−5 wt % has confirmed that C−S
breakage originated from asphaltenes.10
Viscosity reduction must occur in a short period to minimize
the investment. Water behaves distinctly in near and super-
critical conditions. The study of Golombok and co-workers11
revealed that water below its critical point only showed a small
viscosity reduction. However, in the near supercritical state,
significant viscosity reduction was achieved (until ca. 90%).
This result was better than thermal pyrolysis. Other research
attempted to study the interaction between water and heavy oil
in a sequential increase of temperature and pressure. They
found that asphaltenes content decreased when aromatic and
aliphatic increased.12
Aquathermolysis performance increased in the presence of
catalysts.13,14 Therefore, the catalyst design was investigated
intensively including soluble catalysts and solid acid cata-
lysts.15−17 The first series of water-soluble catalysts, which was
reported by Clark et al.,14 were ruthenium and iron. This
experiment was conducted to process bitumen at 375−415 °C,
and the percentage of sulfur reduction was 21 and 18%,
respectively. Recently, Chao et al.18 employed 0.2 wt % of
copper aromatic sulfonic complex catalyst and was able to
decrease heavy oil viscosity until 95.5% by heating bitumen at
280 °C for 24 h. One of the most the promising oil soluble
catalysts is molybdenum oleate.19 The catalyst was tested at 240
°C for 24 h. By mixing 0.5 wt % of catalyst with heavy oil, the
viscosity of heavy oil decreased 90%. Furthermore, adding 0.1
wt % of an emulsifier to molybdenum decreased 90% of oil
viscosity at 200 °C in the same period.20 In another experiment,
equal viscosity reduction was achieved at a lower reaction
temperature, namely, at 180 °C using Ni- and Co-based
catalysts with petroleum sulfonate as emulsifier.21 However, the
catalysts’ instability at high temperature and pressure would
increase the industrial cost to recover and reuse.22−24 In
addition, the study of two kinds of soluble catalysts showed that
asphaltenes and resins were partly aggregated after aqua-
thermolysis.25
Amphiphilic catalysts, such as cobalt dodecylbenzensulfonate,
were thermally stable until 400 °C. The catalyst reduced the
Received: October 24, 2017
Revised: January 6, 2018
Published: January 7, 2018

© 2018 American Chemical Society 2840 DOI: 10.1021/acs.energyfuels.7b03264

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interfacial oil−water surface tension and improved the mixing
between water and oil. Upgrading performance over this
catalyst was studied using Shengli heavy oil at 250 °C for 24 h.
The viscosity reduction was 38%. This catalyst was promising
for heavy oil with high aromaticity and high oxygen content.26
Another alternative catalyst was an ionic liquid. One of the
ionic liquid catalysts consists of 10 wt % of iron, 2% wt % of
molybdenum, and an ionic liquid, namely, deep eutectic
solvent. The upgrading was performed at 300 °C for 24 h,
which was able to decrease 43% of oil viscosity and 32% of
sulfur content.27 However, the efficiencies of these amphiphilic
and ionic liquid catalysts were lower than the soluble catalysts.
Solid catalysts showed a higher stability at oil field condition
with a high efficiency.22,28,29 The earliest study of solid catalysts
was based on the superacid catalyst, namely, HF·BF3. The first
heavy oil sample was Alberta’s reservoir, which was processed at
170−190 °C for 1 h in the presence of hydrogen. This catalyst
was able to convert 56% of bitumen to volatile organic
compounds.30 However, as the recovery of the catalysts was
very difficult, their acid catalysts were explored; for instance, a
nanokeggin catalyst, namely, K3PMo12O40, showed a high
conversion up to 90% at 280 °C. The catalyst has both acidity
and redox activity, which demonstrated a synergetic effect to
upgrade heavy oil.31 This heteropoly solid acid exhibited low
tolerancy to water. It was established that incorporation of
metal could increase the catalyst tolerance to water.22,32,33 As
an example, doping cesium to the heterpoly acid could modify
catalyst surface hydrophobicity. From this experiment, the
highest water tolerance was achieved with doping 2.5 wt % of
cesium to the catalyst.34 On the other hand, the screening of
some metal oxides and their mixed oxides to water
tolerance28,35,36 showed that MoO3-ZrO2 and WO3-ZrO2
were the most stable mixed oxides in water. However, since
MoO3-ZrO237 showed better conversion to the esterification of
fatty acids, this catalyst was considered as one of the most
potential mixed oxides for upgrading heavy oil.38
Zirconia is widely used for solid oxide fuel cell,39 peat
pyrolysis,40 and cleanup gasification gas.41 For instance, in
biomass gasification, zirconia is more resistant to sulfur, while at
the same time, zirconia removes tar and ammonia.42 Moreover,
zirconia showed a good stability at high temperature and in sub-
and supercritical water.43 The article highlights state of art of
the synthesis methods and highlights the size and morphology
control of zirconia nanoparticles. The article also emphasizes
the potential use of zirconia-related catalysts for catalytic
aquathermolysis.
2. UPGRADING HEAVY OIL USING NANOSIZED
OXIDES
Since heavy oil has low H/C, this type of oil requires an
upgrading process before obtaining transportation fuel.
Generally, the upgrading process can be split into two
categories, namely, hydrogen addition and carbon rejection.
Sometimes, the research and technology developers combine
these two technologies to obtain the desired result.44
The use of nanoparticles for heavy oil upgrading is a
relatively novel approach. Nanomaterials with a size lower than
100 nm have good dispersibility and high activity due to their
high surface area to volume ratio. Moreover, nanoparticles
easily penetrate porous medium such as reservoir rock,45 hence
resulting in a more efficient contact with heavy oil.
Among nanoparticles, nano-oxides have gained a strong
interest over the past few years, with their capability to transfer
2841
Review
oxygen ions46 and to provide high affinity to asphaltenes.47
Nanosized CeO2 with controlled morphology has a large
oxygen storage capacity, which further cracks the asphaltenes.
Meanwhile, the study of adsorption properties of acid,
amphoter, and basic metal oxide to asphaltenes also showed
interesting results. This research revealed that surface
interaction is a dominant key in the reaction mechanism.
According to this study, the extracted asphaltenes were basic,
and hence it was easy to have a better affinity with an acidic
oxide.
Metal oxide from transitional elements also served as
potential catalysts. NiO which was prepared by coprecipitation
using ethylene glycol has an average size of 60−70 nm. This
oxide decreased 20% of oil viscosity.48 On the other hand,
hematite, α-Fe2O3, which is the most abundant iron source,
showed a high activity to break the C−S bond. This activity was
concluded from hematite reaction with thiopene with various
concentrations. From this experiment, incorporation of 0.1 wt
% of hematite decomposed 26.3% of thiophene at 120 °C. The
mechanistic reaction was also strengthened by the absence of
the C−S bond in infrared spectrometry. This reaction also
produced rich SO2 and CO2. The result could be an indication
that the C−S bond was cracked and confirmed the existence of
active oxygen in the catalyst. In this reaction, hematite was
reduced at the initial reaction and then reoxidized by the
presence of water.49 Meanwhile, another iron-based catalyst,
namely, Fe3O4 was also reported to upgrade heavy oil at 200 °C
for 6 h. This study showed that viscosity of heavy oil reduced
up to 71.3%.50
Finally, a series of metal oxides consisting of NiO, Co3O4,
and Fe2O3 were studied by Nassar et al.51 as nanocatalysts for
heavy oil upgrading. The average sizes of NiO, Co3O4, and
Fe2O3 were 12, 22, and 43 nm, respectively. The results
exhibited that percentage of viscosity reduction in 300 °C were
37, 20, and 30%, respectively. This result confirmed that affinity
of metal oxide to asphaltenes was one crucial criteria to achieve
significant viscosity reduction.
3. SYNTHESIS OF ZIRCONIA AND ZIRCONIA
NANOCOMPOSITES
There are many routes to prepare zirconia nanoparticles and its
composites. This article only focuses on the bottom-up
approach, namely, sol−gel, spray pyrolysis, electrospinning,
and hydrothermal as described in Figure 1.
3.1. Sol−Gel. Sol−gel is a common technique to prepare
bulk metal oxide. This technique is a simple way to obtain gel
from sol through hydrolysis and polycondensation. However,
this method has numerous challenges to produce nanosized
metal oxides. The major limitation is to control simultaneous
hydrolysis and condensation reaction, which leads to
agglomeration. The complexity is a result from a fast hydrolysis
reaction rate to the precursor. To solve the problem, a
nonaqueous medium is used due to its slower reaction as
consequences of the medium strength of the carbon bond.52,53
Generally, nonaqueous sol−gel synthesis can be assisted with
solvent or surfactant. A zirconia nanoparticle with a crystallite
size in the range of 10−36 nm was produced from the reaction
of zirconium alkoxide in presence of alcoholic solvent.54 In
addition, Suciu et al.55 clarified the effect of various solvents in
the precursor Zr(NO3)2. The solvents were glycerol, ethylene
glycol, citric acid, and sucrose pectin. The smallest crystallite
size of 33 nm was obtained from sucrose pectin. This method is
less toxic than surfactant and has a high surface purity.
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Figure 1. Synthesis of zirconia nanoparticle and zirconia nano-
composites.
However, surfactants facilitate an easier method to control
morphology, size, and size distribution. As example, different
zirconia properties were achieved with the same precursor as
reported by Nesamani et al.56 and Siddiqui et al.57 These two
experiments confirmed that properties of zirconia were highly
influenced by the surfactant source.
Zhan et al.58 produced composite of zirconia-silica from
alkoxide sources and ketones via aldol-like condensation.
Another composite such as yttria stabilized zirconia (YSZ)
also has received growing interest. The common precursors
were Zr(NO3)2, ZrOCl2, and ZrCl4 with an identical source of
yttria, namely, Y(NO3)3.59 In the process, the same organic
solvents such as sucrose pectin and citric acid−ethylene glycol
were used. From this experiment, a smaller crystallite size of
this composite as compared to pure zirconia was obtained.
Even, the crystallite size of zirconia was ca. 17 nm, while the
ratio of zirconia to sucrose was set in a range of 1−4. Another
composite, zirconia-scandia was obtained with large organic
surfactant, namely, acrylamide and N,N′-methylene-bis-
(acrylamide), ammonium persulfate. The average size of this
composite was 5−8 nm.60
One of the most important factors to control the shape and
the size of zirconia through sol−gel is the selection of the
precursor.57 The experiment showed a clear morphology
distinction from two different zirconia sources. ZrOCl 2
precursor produced rod shapes and Zr(SO4)2 favored flower-
like morphologies. Moreover, the product crystallite size
originating from ZrOCl2 was twice that of Zr(SO4)2.
3.2. Spray Pyrolysis. Spray pyrolysis is a route involving
gas or volatile solution, which is injected to a series of
chambers. Initially, atomization will occur with pneumatic,
electrostatic, or ultrasonic methods. This aerosol solution is
then evaporated and the solution is precipitated. Finally, the
droplet changes to dense solid through drying and sintering.62
The schematic illustration of this technique is presented in
Figure 2.
Nanomaterial zirconia was produced via spray pyrolysis of
ZrO(NO3)2 using two fluid nozzles as the atomizer. The
dominant phase of product was monoclinic with only 4%
tetragonal. To identify the impact of feed rate, other
experimental condition variables such as air pressure, hot
blower rate, and liquid density were maintained as constant.
From this experiment, the optimum condition was a feed rate
0.15 L h−1 with an average particle size of 30 nm and a surface
area of 280 m2 g−1 with a production rate of 3.6 g·h−1.63
2842
Review
A zirconia-alumina nanocomposite was achieved from nitrate
salt of zirconia and alumina. The ratio of zirconia and alumina
was 1:1. An ultrasonic homogenizer was used to completely mix
zirconia and alumina. The product has a crystallite size of 27.4
nm.64 Another composite, YSZ, was reported by Perednis et
al.65 The precursor was zirconium(IV) acetylacetonate and
yttrium(III) acetate. These solutions were dissolved in ethanol
with a constant stirring rate. The final composite was tetragonal
with crystallite size of 8−10 nm after calcination at 950 °C.
Meanwhile, composite zirconia-scandia with a low content of
manganese was prepared by mixing its nitrate solution and
produced a large particle diameter.66
Morphology control in the spray pyrolysis method was also
investigated recently. Two composites consisting of YSZ and
ceria from acetate solution were used as a sample. The YSZ
composite was spherical with a smooth surface. On the other
hand, ceria was bowl-like and bumpy. From this research, it was
considered that a large difference in solubility further
differentiated the morphology. The solubility of YSZ and
ceria was ca. 8000 and ca. 260 g/L, respectively.67
3.3. Electrospinning. Electrospinning is a method to
prepare fibrous material utilizing a high electric field in the
presence of certain polymers to prevent fiber structural
collapse, which may occur during calcination. Since nanofiber
has a large ratio of surface area to volume, this morphology is
attractive to various applications such as catalysis and
optoelectronic. This technique is an extensive approach to
prepare nanofiber ceramic with a high yield and low cost.69
Early electrospinning discoveries were commonly focused to
fabricate nanoporous polymer. Then, after the invention of
ceramic nanofibers, zirconia received great interest. Shao et al.70
reported the first study to prepare nanofiber zirconia through
electrospinning. Zirconia precursor and the polymer must be
mixed before being injected to electrospinning reactor. The
combination of zirconium oxy-chloride and polyvinyl alcohol
(PVA) produced pure tetragonal zirconia at 800 °C with a
diameter between 50 and 200 nm. Zirconia fiber was also
accomplished from zirconium acetate solution. However, the
diameter was bigger than previous reports, namely, 300−500
nm at 800 °C.71 Polyvinylpyrrolidone (PVP) that has a larger
building block than PVA was responsible for forming a larger
diameter. To improve catalytic properties, the building block
for electrospinning can be modified from a templating agent,
not limited to a polymer as reported by Yin et al.72 The
templating agent such as triblock copolymer (such as the
Pluronic series) were used to produce an average fiber diameter
in the range of 100−400 nm.
Zirconia composite such as YSZ was also achieved through
electrospinning.73 Yttria and zirconia precursor with a certain
ratio must be completely dissolved before mixing with the
polymer. The experiment used two stages of calcination until
1500 °C to obtain monoclinic 8YSZ. In another report,
crystallite formation of fiber NiO/ZrO2 was accomplished
through electrospinning with calcination at 550 °C. The
average fiber diameter was 106 ± 25 nm with the assistance of
PVA.74
3.4. Hydrothermal Synthesis. Hydrothermal route is a
simple approach to synthesize nanomaterials with a narrow size.
In this technique, crystal nucleation and growth occur
simultaneously at the liquid phase. By surpassing calcination,
the hydrothermal method was able to minimize agglomeration
and crystallize at relatively low temperature and pressure.
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Table 1. Synthesis of Zirconia and Zirconia Nanocomposite Using the Sol−Gel Technique

2843 DOI: 10.1021/acs.energyfuels.7b03264

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Table 1. continued
Figure 2. Schematic illustration of the spray pyrolysis technique.
Reprinted from ref. 62 with permission. Copyright 2012 Elselvier.
Zhang et al.75 produced nanosized zirconia using zirconium
oxychloride as precursor with cetyltrimethylammonium bro-
mide (CTAB) as the surfactant. After mixing with strong
agitation, ammonia solution was added as a precipitating agent.
The research showed that two phases of zirconia, namely,
tetragonal and monoclinic were obtained at a temperature
lower than 250 °C. Above this temperature, pure tetrahedral
phase was obtained with an average size of 22 nm after heating
for 18 h. In this study, CTAB was used not only to prevent
agglomeration of ZrO2, but also to facilitate a lower
temperature for tetragonal formation. In other research, a
smaller crystallite size of zirconia, namely, 1−20 nm, was
achieved with the same zirconia precursor, but the pressure was
much higher at 25 bar. However, the products were still a
combination of monoclinic and tetragonal.76
Other reported zirconia nanocomposites were La2O3/ZrO2,
TiO2/ZrO2, and CeO2/ZrO2.76 This article showed that
morphology of composites were monoclinic, amorphous, and
cubic solid solution with a surface area 77, 209, and 96 m2/g,
2844
Review
respectively. The experiment also exhibited that TiO2/ZrO2
was a potential mixed oxide for acid−base catalysis.
Mineralizer is often used to control size of zirconia with the
hydrothermal method. Type and concentration of mineralizer
were a highly influenced zirconia product. Mineralizers such as
NH4F produced better crystallinity of zirconia. A higher
concentration of NH4F also increased the crystallite size. To
identify the effect of mineralizer type, several mineralizers such
as NH4Cl, NH4Br, KF, and NaF were explored. The result
showed that mineralizer without F− resulted in products with
the same characteristics with pure zirconia. On the other hand,
the F− mineralizer promoted better crystallinity to zirconia.77
Doping zirconia is a method to stabilize zirconia at high
temperature. Another alternative was through particle size
stabilization. The particle size stabilization was achieved via the
hydrothermal method at high temperature and pressure with
supercritical water. Moreover, this technique was able to
produce a pure phase within a short period. Several factors such
as temperature, pressure, pH, and precursor concentration were
the keys to control zirconia size and morphology. The study of
hydrothermal mechanism revealed that the intermediate ion
was the key in directing the morphology. Zr(OH)22+ was an
intermediate ion to form monoclinic, which occurred at low
pH. Meanwhile, the tetragonal phase was produced via
Zr(OH)5, which appears with a high pH.78 Pure monoclinic
zirconia was reported by Becker et al.79 with a crystallite size of
ca. 5−6 nm, rapidly. A composite of zirconia such as ceria-
ziconia and yttria stabilized zirconia (YSZ) were also reported
elsewhere.80
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Table 2. Preparation of Zirconia and Zirconia Nanocomposites with Spray Pyrolysisa

precursor condition result ref
ZrO(NO3)2 -air pressure: 30−40 psi output: 72 ± 5% 63
-temperature: 773 K 96% monoclinic; 4%: tetragonal
-speed of hot blower: 1800 rpm average crystallite size: 18 nm
-liquid density: 1.031 g·cm−1 grain size of tetragonal: 26 nm
-operational: 10 h Feed rate effect:
0.10 L h−1: APS: 28 nm; SA: 283 m2 g−1
0.15 L h−1: APS: 30 nm; SA: 280 m2 g−1
0.20 L h−1: APS: 46 nm; SA: 195 m2 g−1
0.25 L h−1: APS: 93 nm; SA: 141 m2 g−1
0.30 L h−1: APS: 112 nm; SA: 98 m2 g−1
the optimum condition was 0.15 L h−1
Al(NO3)3; Zr(NO3)4 -ultrasonic homogenizer crystallite size: 27.4 nm 64
-deposited at SiO2 substrate at 300 °C the composite showed good stability
-heated 500 °C for 5 h
(C5H7O2)4Zr; (CH3CO2)3·YH2O in methanol -atomizer/collision nebulizer and airbrush size: 8−10 nm 65
-furnace: 950 °C 3% YSZ: tetragonal
Zr(NO3)2·xH2O, Sc(NO3)2·xH2O, Mn(NO3)2· -mixed equimolar citric acid and ethylene glycol to nitrate particle diameter: 0.67 μm 66
4H2O solution
-charred at 240 °C the material was promising for solid oxide
fuel cells
-calcined at 750 °C for 10 h
-atomizer: ultrasonic nebulizer
Zr(NO3)4·3H2O, La(NO3)3·6H2O, Gd(NO3)3· -mixed with citric acid and polyethylene glycol as solvent (La,Gd)2Zr2O7: 0.607 nm 68
6H2O
-atomizer: steel nozzle (ZrGd)O2: 0.261 nm
-pyrolized at 500 °C
-annealed product at 900−1400 °C for 10−24 h
a
APS: average particle size; SA: surface area.

4. ZIRCONIA-BASED CATALYSTS IN HEAVY OIL
UPGRADING
Zirconia is an amphoteric catalyst. However, zirconia can be
converted to a superacid solid catalyst with sulfate ion to
produce SO42−/ZrO2.81 The most frequent method to prepare
this catalyst was through sulfating zirconium hydroxide. The
sulfation induced acid site of Lewis and Brønsted on the surface
this mixed oxide as presented in Figure 3.37 Modified sulfated
zirconia catalysts with Ni2+ and Sn2+ for Shengli oil viscosity
reduction were studied intensively. These catalysts were
investigated at 240 °C and 3−4 MPa for 24 h. Doped
SO42−/ZrO2 with Ni2+ was a better viscosity reducer than Sn2+
with a conversion 57% and 20%, respectively. Nevertheless, the
conversion decreased from 57% to 20% in the presence of 5%
water due to solubilization of sulfate ion.82 A common method
to enhance durability due to sulfate leaching was the fabrication
of mixed oxide. The composite consisting of MoO3−Nd2O3
showed high resistance in water.83
Tungstate zirconia was also investigated for viscosity
reduction of heavy oil. The composite was prepared through
precipitation and impregnation with various ratios of tungsten
to zirconia. Number of acid sites and acid strength are highly
influenced by the tungsten percentage. Hydrothermal synthesis
produced better crystallized zirconia-tungsten that is more
acidic than with the impregnation method. This research
showed that the catalyst was able to lower the viscosity through
C−C breaking, which was identical to catalytic cracking. The
catalysts were evaluated at 220 °C and 2 MPa for 6 h. The best
viscosity reduction was reached (82%). This finding demon-
strated an alternative method to upgrade heavy oil with low or
no water content.85
2845
Recently, FeOx based catalyst, namely, CeO2-ZrO2-Al2O3-
FeOx, was applied as the catalyst to upgrade Canadian heavy oil
to evaluate the optimum condition to produce the most
dominant desired lighter fractions. In these experiments, the
ratio of mixed oxide was kept constant, CeO2/ZrO2/Al2O3 =
2.5%:7.5%:7%, respectively. The pressure of the reaction was
varied from 2.8 to 24 MPa to find the optimum pressure
condition. The optimum pressure was observed at 19 MPa.
Below this pressure, the amount of coke was greater than 22%,
which decreased the amount of vacuum gas oil (VGO) and gas
oil. Meanwhile, above this pressure, the desired lighter fraction
decreased from 70 wt % to 45 wt % due to the recombination
of lighter fraction at the catalyst surface, which was called the
“cage effect”. Therefore, the temperature of this reaction was
varied in the range of 350−420 °C, to evaluate its optimum
temperature. The feed of this reaction consisted of vacuum
residue of 65 mol % C of bitumen and some heavy component
with average molecular weight higher than 500 g/mol and 2000
g/mol, respectively. At the temperature above 400 °C, the
viscosity of bitumen decreased significantly above 400 °C to
300 g/mol. Hence, it eases the interaction with the catalyst
active site and produced a higher desired lighter fraction. From
this condition, the lighter component reached 70 wt %, while
carbonaceous residue decreased from 20 wt % to 10 wt %. In
this research, catalyst stability was evaluated by reacting
bitumen at its optimum condition,19 MPa and 420 °C for 6
h. The product of this condition consisted of 65% of lighter
component and 10% coke yield. The catalyst was then reused
after removing its surface through calcination at 500 °C for 2 h.
The amount of lighter fraction and carbonaceous residue is
similar with fresh catalyst. This result showed that the mixed
oxide has high stability and durability.86
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Table 3. Fabrication of Zirconia and Zirconia Nanocomposites with Electrospinning

2846 DOI: 10.1021/acs.energyfuels.7b03264

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Table 3. continued

Table 4. Hydyrothermal Synthesis of Zirconia and Zirconia Nanocompositesa

precursor experiment result ref
ZrOCl2·8H2O, CTAB -zirconia concentration: 0.1 M <250 °C: mix of tetragonal and monoclinic 75
-mixed with strong stirring at 298 via water >250 °C: tetragonal size: 22 nm
bath for 2 h
-added NH3 dropwise until pH 9
-heated at (150, 200, 250) °C for 18 h in
autoclave
ZrOCl2·8H2O; TiCl4; LaCl3·6H2O; -added NH4OH dropwise to precursor until ZrO2 = SA: 65 m2 g−1; mix of monoclinic + tetragonal; 10−20 nm 76
CeCl3·7H2O pH 10
Hydrothermal TiO2/ZrO2 = SA: 209 m2 g−1
220 °C; 25 bar for 4 h under stir Amorph: potential for acid-base catalysis
dry at 120 °C and calcined at 500 °C for 10 h CeO2/ZrO2 = SA: 96 m2 g−1; cubic solid solution
La2O3/ZrO2 = SA: 77 m2 g−1; monoclinic
Zr(NO3)4·5H2O, NH4F -mixed in DW with continuous stir the more NH4F, the bigger its crystallite size 77
-NH4F conc (0.125 M; 0.25 M; 0.3 M)
hydrothermal:
-autoclave 180 °C for 72 h
a
CTAB: cetyltrimethylammonium bromide. DW (demineralized water).

still challenging during the past decade. Therefore, the search

Figure 3. Production of Lewis and Brønsted acid site in zirconia
sulfate in ref 37 which was adapted from ref 84. Reprinted from ref. 84
with permission. Copyright 1994 Springer.
4.1. Stability of Zirconia in Subcritical Water. Hot water
is a cheap and safe solvent for heavy oil. Hot water eases the
interaction of large molecules with the catalysts surface.
However, the long-term catalyst activity in this medium is
2847
for a stable catalyst in hot water has become key stage which
would accelerate heavy oil global realization. Among the
catalysts, metal oxides are still the first option for catalyst
support at high temperature of hydrothermal conditions due to
their higher mechanical strength as compared to carbide
catalysts. Meanwhile, a catalyst promoter must be a metal oxide
with intermediate acid strength, which would be dissolved in
hot water. This conclusion was derived from electronegativity
of metal oxide which confirmed solubility of metal oxide or
hydroxide in water. Moreover, a pourbaix diagram which
displays a stable metal phase in varied pH and electrochemical
potential was used as a second criteria. On the basis of this
diagram, the stable metal oxides in hot water (200 °C) are only
zirconia, alumina, and titania. Zirconia and alumina are
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Energy & Fuels
transformed into its hydroxide form. Meanwhile, titania
sustained its oxide form. From these two criteria, zirconia is a
promising candidate as a support and promoter.87 A pourbaix
diagram of zirconia in hot water is presented in Figure 4.
Figure 4. Pourbaix diagram of zirconia. Reprinted from ref. 87 with
permission. Copyright 2015 Wiley.
4.2. Stability of Zirconia in Supercritical Water. Carbon
residue is serious problem for heavy oil catalytic upgrading.
Coke formation will poison the catalyst active site, and hence
its activity decreases drastically. In heavy oil, which mainly
consists of asphaltenes, the probability to yield carbon residue is
higher than in conventional oil. One strategy to decrease coke
formation is by reacting the heavy oil at high temperature and
pressure with sub- and supercritical water. Supercritical water
(SCW) is a promising solvent for heavy oil upgrading. Almost
all bitumen moieties dissolved in SCW at 440 °C, 29 MPa with
ratio of bitumen to SCW 1:2.5.88 The agglomeration
asphaltenes are also avoided because of their tendency to
form microemulsion which surpasses coke formation. 89
Furthemore, SCW produced more active in situ hydrogen
than hydrogen molecules.90
The stability of many ceramics in SCW was reported
previously; carbon, α-Al2O3, and zirconia were the only stable
materials in SCW. Zirconia showed the biggest fracture
toughness.91 According to Adam et al.,92 monoclinic is the
stable form of zirconia crystal. The same result was also shown
by other researchers.93,94 The stability of zirconia in SCW was
enhanced with metallic elements. The Ni/ZrO2 in SCW as
gasification catalyst was stable for 85 h and no further decrease
on surface area.43 Moreover, Ni/ZrO2 produced the highest
hydrogen yield in switchgrass gasification.92
Monoclinic zirconia has a lower surface area than the
tetragonal structure. Several researchers reported the method to
stabilize tetragonal zirconia in SCW. Zöhrer al95 added 1.77%
HfO2 and La2O3 9.7% to ZrO2. Matsui et al.96 added the
second stabilizer (Al2O3 or GeO2) in YSZ, and the composite
was stable until 4 years at 140 °C of hot water.
2848
Review
5. ACIDITY AND OXYGEN STORAGE PROPERTIES OF
ZIRCONIA-BASED CATALYSTS AND THEIR ROLES
IN HYDROTHERMAL (SUBCRITICAL AND
SUPERCRITICAL WATER) UPGRADING OF HEAVY
OIL
Upgrading heavy oil, which has a low H/C ratio, mainly
requires hydrogen addition or oxygen species. However,
providing hydrogen or oxygen from an external source is
expensive. Therefore, the technique and the material selection
to supply hydrogen and oxygen have become a crucial concern.
One method to provide internal hydrogen is to select material
with high acidity, which will easily transfer hydrogen. Among
acid compounds, tungstate zirconia showed the best perform-
ance for viscosity reduction.97
The type of acid cites in zirconia can be clarified with Fourier
transform infrared spectroscopy after pyridine adsorption. The
tetragonal form of nanosized zirconia has only Lewis acid sites,
while monoclinic has both Lewis and Brønsted sites. In
addition, monoclinic zirconia has a larger acid density which is
approximately double tetragonal zirconia. The number of acid
sites was proportional to the number of Zr4+ in its surface as
calculated by density functional theory (DFT).98
Zirconia is a bifunctional acid−base catalyst with Zr4+ as the
acid site and O2− as the basic site. Zirconia has a wide range
applications in the energy and chemical industries. Among the
process, zirconia was utilized for hydrogenation of benzoate
acid to benzaldehyde, which was commercialized by Mitsubshi
Kasei Corp. Many types of metal oxide including MgO, TiO2,
ZnO, γ-Al2O3, and zirconia were tested in the presence of
hydrogen. Zirconia showed the best performance with a
selectivity up to 97% and conversion of 53% at 400 °C.
Moreover, doping ultrasmall Cr2O3 to ZrO2 with a ratio Cr/Zr
0.05 enhanced the conversion significantly to 98% at 350 °C.99
The mechanism for direct decarboxylation is presented in
Figure 5.
Another industrial application of zirconia is in Meerwein
Pondorf Varley (MPV) reduction. This process aims to reduce
aldehyde, ketones, carboxylic acid, or ester with alcohol. The
study of direct reduction of levulinic acid to γ-valerolactone was
performed with Beta-zeolite containing zirconia. The best
catalytic performance was accomplished with Si/Zr 100 with
high conversion and selectivity, ca. 100 and 96%, respectively.
The reaction was investigated at reflux 118 °C using 2-pentanol
as a reactant. This best performance is due to its moderate
Lewis acid sites, which were contained in Zr-zeolite Beta.
Meanwhile, doping with Al, which is a Brønsted acid site to Zr-
beta zeolite decreased the selectivity to 71%.101
Natural zeolites102 were also investigated for bitumen
upgrading and cracking. The performance of a natural zeolite,
namely, chabazite, was better than commercial zeolite Y, which
was well-known as a fluid catalytic cracking catalyst. The use of
zeolite Y only showed a slight viscosity reduction of Athabasca
bitumen. Meanwhile, modified chabazite with Ca changed
viscosity until 97%.103 External surface acidity and crystallinity
of chabazite played an important role for heavy oil upgrading.
Ca-chabazite showed a high acid strength with both Hammet
indicator and ammonia temperature programmed desorption
(TPD), namely, −3.0 and (−5.6) and 3.66 mequiv/g. This
catalyst was able to reduce viscosity until 81% in the presence
of 3% water.104 Spectroscopic analysis is used to predict the
basic mechanism for viscosity reduction; the spectroscopic
measurement of chabazite at 350−650 °C confirmed that the
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Energy & Fuels Review

Figure 5. Mechanism for direct decarboxylation of benzoate acid to
benzaldehyde. Reprinted from ref. 100 with permission. Copyright
1999 Elselvier.
acid site was mainly Brønsted acid within framework and
nonframework.105 Meanwhile, the acid site of WOx/ZrO2
consists of Lewis and Brønsted. In addition, the study of
desulfurization confirmed that catalyst performance was in a
linear correlation with the Brønsted acid site.106 On the basis of
the theoretical aspect, the optimal zirconia performance is one
Lewis acid site with maximum Brønsted sites. The optimum for
converting viscosity is 20% of tungsten with a strong acid
amount, namely, 0.35 mmol/g and a Hammet indicator of
−14.5 and −16.1.107 Hence, it confirmed that the chabazite acid
site originated from its framework, while the acid sites in WOx/
ZrO2 originated from high dispersion of tungsten on zirconia.
Acid sites in zirconia-silica composite was scrutinized by an
experimental and theoretical approach. Characterization with
X-ray diffraction validated that the composite consisted of
tetragonal zirconia and amorphous silica. Acid strength
measurement with NH3-TPD showed that initially the heat
adsorption was high and then decreased when the surface area
became larger. Moreover, pyridine adsorption verified that only
the Lewis acid site existed on tetragonal zirconia. On the basis
of a theoretical approach, the lower heat of adsorption
originated from NH3-NH3 repulsion. In addition, strong acidity
in the early adsorption stage was attributed to the adsorbed
NH3 on Zr site with neighboring oxygen deficiency.108
A recent method to advance zirconia performance was
reported recently through impregnation to red mud with varied
Zr content. Red mud is comprised mainly of iron oxide and
alumina with a low content of silica and titania. The material
was evaluated in steam catalytic cracking of vacuum residue at
470 °C and 0.1 MPa for 2 h. The highest conversion and liquid
yield, namely, 85% and 35%, respectively, was reached over 3%
wt of Zr. Both conversion and liquid yield decreased
significantly, when the zirconia content was above 3 wt %.
Higher content of zirconia led to a lower catalyst surface area
and decreased catalyst active site. Hence, the amount of coke
and liquid yield also decreased. Meanwhile, the side product of
this reaction contained low carbon dioxide. Therefore, it was
confirmed that catalyst active site was not from oxygen lattice.
Meanwhile, the H/C ratio of product was relatively high (1.76).
This was an indication that catalyst donated some of hydrogen
to vacuum residue. Addition of zirconia increased the catalyst
acidity and facilitated more hydrogenation reaction. Moreover,
the catalyst showed a high durability after the second and the
third repetition with a slightly decrease of activity after the first
usage. Finally, this composite showed a better activity and
durability as compared to Al-FeOx catalyst.109
Another novel improvement of zirconia oxide compound for
heavy oil upgrading at superheated steam was reported recently.
First, titania-zirconia with varied composition was evaluated as
catalytic cracking of 10 wt % atmospheric residue (AR).
Therefore, the optimum composition was investigated for
catalytic upgrading Canadian Oil sand bitumen. Among the

Table 5. Acidity of Zirconia and Zirconia Nanocomposites

materials acidity comment ref

ZrO2 tetragonal Lewis acid sites the number of acid sites is proportional to number of Zr4+ on the surface 98
acid surface density: 1.7 NH3/
nm2
ZrO2 monoclinic both Lewis and Brønsted acid
site
acid surface density: 3.4 NH3/
nm2
10 WO3/ZrO2 0.36 mmol/g Both Brønsted and Lewis acid sites are confirmed. The high acid strength due to WO interaction at 97
ZrO2 to WO3
15 WO3/ZrO2 0.46 mmol/g
20 WO3/ZrO2 0.53 mmol/g
25 WO3/ZrO2 0.51 mmol/g
SO42−/ZrO2 Hammet indicator: −14.5 and 107
−16.1
Zr-Zeolite Beta 45 mol/g adding Brønsted acid will lower acid strength 101
100
chabazite Hammet Indicator:-3.0 and −5.6 104
NH3-TPD: 3.66 mequiv/g

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Energy & Fuels
variation, equimolar zirconia titania catalyst showed the best
performance with high lighter fraction and low carbon residue.
This compound has the highest acidity, namely, 0.3 mmol
NH3/ g, which mainly consisted of Lewis acid. The total acidity
of zirconia-titania was approximately a half of zeolite H-BEA
(Si/Al = 13.5) acidity. However, zeolite has a lower tolerancy to
carbon deposition at high temperature. Then, the composites
were evaluated to decompose 10% of Canadian oil sand
bitumen. The reaction was carried out at 470 °C and a modified
time factor 88 m2·h·g−1. The produced lighter fraction (VGO
and gas oil) and coke were 61% and 20%, respectively. The
product of this reaction mainly consisted of lighter hydro-
carbon, volatile, and olefin. Therefore, it was evidence that the
mechanism of this reaction occurred via carbon−carbon
breakage and polycyclic aromatic opening.110 This titania-
zirconia catalyst showed a high tolerancy to carbon residue in
superheated steam, and hence the composite was potential as a
catalyst in heavy oil upgrading.111
Another significant property in heavy oil upgrading was the
ability for a catalyst substance to produce internal oxygen. The
ability of ceria-zirconia to produce hydrogen and oxygen via
water splitting at 500 °C was reported recently.112 Zirconia is a
stable metal oxide, which cannot transfer oxygen species.
Doping zirconia lattice will lead to a crystal defect. More
positive ion in zirconia lattice with rapid charge transfer would
lead to an oxygen vacant condition to maintain electro-
neutrality. Hence, some nonstoichiometric oxygen species
would be produced. In a catalytic system of FeOx-ZrO2,
Fumoto et al. showed that ZrO2 produced labile oxygen
generated from H2O. Increasing the ZrO2 content at constant
FeOx increased the CO2 product.36 On the other hand, ZrO2-
FeOx was evaluated to transform 2-metoxy phenol to phenol
under steam conditions. The catalyst was investigated at 400 °C
and 0.1 MPa for 2 h. This catalyst yielded a low conversion of
15% without hydrogen addition.
Adding yttria also initiated anionic vacancy and stabilized
tetragonal phase. The amount of oxygen vacancy was
dependent on the yttrium oxide content. Even 1% of yttria
could generate O2−· and increased surface area. The optimum
range for the oxygen donor was 1−10% of yttria. In this narrow
range, 5% of yttria stored more Zr3+, and hence more labile
oxygen accumulated.113 Oxygen migration in YSZ was
evaluated with the DFT method. The result confirmed that
the cations in sharing edge were inversely proportional to the
oxygen migration barrier. The smaller cation in sharing edge,
the bigger oxygen energy migration barrier, which was achieved
through Zr4+−Zr4+ interaction.114
Another dopant, such as silica, also improved tetragonal
stability. Generally, anionic deficiency was formed to stabilize
the crystal. In the case of silica-zirconia, silica stabilized zirconia
crystal by limiting its growth. Finally, Del monte et al.
concluded that this composite cannot transfer oxygen
species.115
Incorporation of Zr4+ into a CeO2 lattice increased the
amount of oxygen storage capacity (OSC). Doping with 50%
Zr increased OSC to 122 μmol O2/g ceria.116 Meanwhile,
Meng et al. reported that Ce0.5Zr0.5O2 increased the OSC to 80
μmol O2/g.117 Ceria ability to produce oxygen vacancy
originated from the reduction reaction occurring from Ce4+
to Ce3+. Introduction of Zr4+ with cubic fluorite structure and
small size led to the formation of Ce3+ in the CeO2 lattice. This
hypothesis was strengthen with a computational method, which
confirmed that oxygen vacancy prefers to have a neighboring
2850
Review
position with a Zr site. The increase of the OSC resulted from
the Zr role to increase oxygen mobility. Moreover, according to
the thermodynamic aspect, doping ceria to zirconia decreased
both enthalpy and entropy redox reactions. At low Zr content
with 0−5 wt %, the percent of enthalpy decreased to around
17%.112
Enhancing OSC in ceria was also achieved through doping
with rare earth elements. Comparison of ceria modified with
lanthanum oxide and zirconia showed that the OSC difference
was 63 μmol O2/g with the OSC of lanthanum the largest.116
In addition, the preparation method also affected the OSC
properties. The OSC of Ce0.5Zr0.5O2 was 250 (ultrasonic
assisted membrane reactor, UAMR) and 164 μmol O2/g
(coprecipitation).117 The CeO2 cubic form with a particle size
of 8 nm, which was prepared in supercritical water, yielded the
OSC of 340 μmol O 2/g. Moreover, the synthesis of
Ce0.65Zr0.35O2 under supercritical water resulted in an OSC of
680 μmol O2/g.80
The role of zirconia in mixed oxides for heavy oil upgrading
in supercritical water was similar to the behavior of CeO2.46
The gaseous products of bitumen feed reacted with CeO2 in
the absence of hydrogen addition were investigated with gas
chromatography. The gaseous products consist of methane,
alkene, and others. After reacting with cubic CeO2, the product
mainly consisted of CO2, alkene, and a small amount of
hydrogen. The generation of rich CO2 was an indication that
CeO2 was able to produce active oxygen and oxygen from water
splitting. The water splitting phenomenon also strengthen by
the transformation of alkane to alkene. This process occurred
through ionic mechanism, and hence the formation of radical,
which tended to polymerize was minimized. In the case of
zirconia, the OSC amount of zirconia in mixed oxide was larger
than pure CeO2. Hence, the performance to crack asphaltene
and reduce viscosity was increased. The proposed mechanism
to describe the role of CeO2 nanoparticles in a reaction with
bitumen in supercritical water is presented in Figure 6.
Figure 6. Proposed mechanistic reaction of CeO2 nanoparticle to
bitumen in supercritical water (adapted from 46). Copyright 2013
ACS.
6. CONCLUSIONS AND OUTLOOK
Some challenges still remain in the upgrading of heavy oil.
Supercritical water, a promising solvent for heavy oil upgrading
due to its ability to suppress coke formation and to produce
active hydrogen, is currently being explored in combination
with robust catalysts. Despite a high pressure system required
to generate supercritical water, to meet industrial demand, the
investigation of the complex diagram of water−hydrocarbon,
the stable catalysts with the ability to crack hydrocarbon, and
the optimum condition to produce different middle distillates
with an existing market penetration are also essential for
efficient refineries. At last, knowledge of the functional
supercritical water devices is required.
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Energy & Fuels Review

Table 6. Redox Properties of Zirconia and Zirconia Nanocomposites

ceramic comment ref
ZrO2 Activated and transferred oxygen in H2O over ZrO2 surface. Therefore, it increased the possibility to oxidize organic compound. 36
ZrO2 Several nanosized (Fe2O3, Co3O4, NiO) and nanostructured metal oxides (Ni, Fe) were studied to upgrade heavy oil. The result revealed 51,
nanostructure that all materials can upgrade heavy oil in the absence of hydrogen. 118
ZrO2-Al2O3- Al2O3 improved ZrO2-FeOx catalyst activity and stability in steam environment. 35
FeOx
silica supported Short route in nanocrystal site enhanced the charge and mass transport. No report related to oxygen transfer in main open literature. 115
zirconia Meanwhile, Del Monte reported no oxygen vacancies in SiO2-ZrO2. Hence, the capability to upgrade heavy oil is doubted.
Ce−Zr Doping Zr into Ce created oxygen vacancies in Ce crystal. Bulk oxygen was then easily moved to other substances at low temperature. 116,
Thus, the usage for heavy oil upgrading is promising. 117
YSZ Ytria stabilized zirconia crystal even in high temperature. The presence of Y2O3 in ZrO2 lattice, enriched oxygen vacancies in this 113
composite. Consequently, more organic molecules are potentially oxidized.

Zirconium oxides and zirconia nanocomposites for heavy oil

upgrading can be fabricated with different methods. Successful
preparation of zirconia nanocomposites will open different
opportunities not only for heavy oil upgrading, but also for
biomass upgrading and waste valorization. Crucial aspects in
each manufacturing method must be studied to produce
zirconia-based catalysts in a economical way with desirable
composition, uniform morphology, and size.
As one of the most promising stable catalysts for heavy oil
upgrading, documented methods to produce zirconia are a
crucial. A number of preparation techniques such as sol−gel,
electrospinning, spray pyrolysis, and hydrothermal needs to be
investigated to establish the optimum conditions. Some factors
such as precursor source, concentration, and the type of metal
oxide must be considered to obtain the desired properties.
Zirconia still needs further enhancement before it can be
applied commercially as a heavy oil catalyst. Monoclinic
zirconia is stable in supercritical water. However, monoclinic
zirconia is a weak acid. Therefore, zirconia was modified with
tungsten, which tends to form a strong acid. The best
performance was achieved when tungsten was highly dispersed
in the zirconia surface. In addition, zirconia needs a stabilizer
such as rare earth to maintain its monoclinic form. Other acidic
modifications were reported in zirconia-titania and zirconia
modified with red mud. Meanwhile, zirconia with a high OSC
was fabricated rapidly by a hydrothermal method in super-
critical water. The potential composite was ceria-zirconia.
However, since the basic mechanism for heavy oil upgrading
with zirconia is still sought, further research to serve an acid site
with a high tolerancy in water and stable composite with high
OSC is still needed. Meanwhile, further studies are still required
to elaborate the optimum synthesis conditions and to improve
catalyst stability.
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2854 DOI: 10.1021/acs.energyfuels.7b03264

Energy Fuels 2018, 32, 2840−2854