Article

pubs.acs.org/EF

Supporting Tungsten Oxide on Zirconia by Hydrothermal and

Impregnation Methods and Its Use as a Catalyst To Reduce the
Viscosity of Heavy Crude Oil
Hao Wang,* Yan Wu, Li He, and Zhenwei Liu
School of Chemistry and Chemical Engineering, South West Petroleum University, Chengdu 610500, Peoples Republic of China

ABSTRACT: Tungsten oxide was supported on zirconia via hydrothermal and conventional impregnation methods and used as
a catalyst to reduce the viscosity of heavy crude oil without the addition of water. Their properties and viscosity reduction activity
were compared. X-ray diraction and the Rietveld method were used to characterize the crystal structure and determine the
phase composition. The properties of catalysts were also measured by N2 adsorptiondesorption, dierential scanning
calorimetry, a Hammett indicator, and ammonia temperature-programmed desorption. Compared with the impregnation
method, the hydrothermal method facilitates the formation of strong tungstenzirconia interaction and promotes the diusion of
tungstate on zirconia, hence leading to better-dispersed tungsten oxide, as well as more tetragonal zirconia and acid sites. Under
the reaction conditions of 220 C, 6 h, and 2 MPa, the catalysts prepared via the hydrothermal method exhibit higher viscosity
reduction activity than those prepared by impregnation. It is found the catalytic activity mainly depends on the acidity of the
catalyst. The catalyst containing 20 wt % tungsten prepared by the hydrothermal method can attain a viscosity reduction ratio of
82.2% and reduce the viscosity of oil from 5.74 Pa s (50 C) to 1.02 Pa s. Dierent from the widely used aquathermolysis
technique, the presence of water is not required and the viscosity of the treated oil will not regress, even over long periods of
time.

1. INTRODUCTION react with hot water to provide hydrocracking activity by

Crude oil with an American Petroleum Institute (API) gravity
smaller than 20 is called heavy oil.1 Heavy oil accounts for a
large proportion of the proven oil reserves. With the increasing
demand for oil and the shortfall of conventional oil, the
production of heavy oil has been gradually increasing in recent
years.2 However, heavy oil is dicult to explore and transport,
because of its high viscosity and low ow property;3 therefore,
the key factor to handling heavy oil is reducing the viscosity.
Thermal recovery is the most widely used way to produce
heavy oil, wherein heat is injected into the formation to reduce
the viscosity of the oil and enable heavy oil to ow through the
porous media of reservoirs. Hot uid injection, in situ
combustion, and steam stimulation are the thermal recovery
methods.4
During the steam injection process, besides the eect of high
temperature, it is believed that the chemical reaction between
steam and oil also makes a great contribution to viscosity
reduction by breaking large molecules into smaller ones. Hyne
et al.5 rst called this reaction aquathermolysis. The principal
aspect of aquathermolysis is cleavage of the CS bond in
asphaltene, because of the injected superheated water, which
causes a decrease in resins and asphaltenes and an increase in
saturates and aromatics. Many researchers have reported that
the presence of a catalyst could accelerate the aquathermolysis
reaction signicantly, as well as further upgrade the quality of
the heavy oil.610 Recently, progress in catalytic aquathermol-
ysis was well-reviewed by Maity et al.,11 who classied the
catalysts as mineral, water-soluble, oil-soluble, and dispersed
catalysts. Most catalysts contain salts of metals, such as Fe, Ni,
V, Mo, Co, Ru, and Al, which may strongly interact with
suldes in heavy oil to improve the rupture of the CS bond or
producing an acidic environment. In general, the catalytic
aquathermolysis was performed under the following conditions:
reaction temperature, 160280 C; pressure, 325 MPa; time,
12240 h; and water content, 240 wt %. The viscosity of
heavy oil can be reduced by 40%90%; moreover, if the
hydrogen donor is present, the viscosity reduction ratio can
reach above 90%.11 Therefore, catalytic aquathermolysis for
producing heavy oil is becoming an important research area.
Indeed, some heavy oils are waterless or have a lower water
content; therefore, it is hoped that the viscosity can be reduced
without adding water. In addition, to greatly decrease the
consumption of light oil used to dilute the waterless heavy oil,
an idea is generated: use the catalyst to reduce the viscosity of
heavy oil at lower temperature in an oil gathering station to
produce less-viscous oil and then return it to the well to dilute
the heavy oil. However, less attention has been paid on the
catalytic viscosity reduction of waterless heavy oil. It is accepted
that the CC bond in larger hydrocarbons can be broken down
at temperatures above 300 C, regardless of the presence of
water,11 which causes the cracking of heavy hydrocarbons and,
consequently, the decrease in viscosity. Introducing catalyst can
decrease the reaction temperature. Solid acids are widely used
catalysts to promote the cracking of hydrocarbons. Therefore, it
is hoped that solid acids can be used as catalysts to reduce the
viscosity of heavy oil via mild cracking at the relatively lower
temperatures. Solid superacid refers to an acid with a strength
corresponding to 100% H2SO4.12 Zirconia promoted by sulfate
Received: April 28, 2012
Revised: September 25, 2012
Published: September 26, 2012

2012 American Chemical Society 6518 dx.doi.org/10.1021/ef301064b | Energy Fuels 2012, 26, 65186527
Energy & Fuels
groups or metal oxides are commonly used solid superacids.
Because of the strong acidity, zirconia-based superacids even
can catalyze the alkane isomerization at near room temper-
ature.13 Accordingly, it is considered that superacids can be
used as catalysts to reduce the viscosity of heavy oil. Jing et al.14
used SO42/ZrO2 superacid doped with Ni2+ or Sn2+ as a
catalyst to reduce the viscosity of Shengli oil without adding
water, and they found that Ni2+- or Sn2+-modied SO42/ZrO2
decreased the viscosity of oil from 0.316 Pa s (50 C) to 0.135
Pa s and 0.163 Pa s, respectively. Tungsten oxide supported on
zirconia also behaves as a solid superacid that is more stable
than sulfate-modied zirconia.15 However, little literature is
available about the application of zirconia-supported tungsten
oxide for the viscosity reduction of heavy oil.
The activity of tungstenzirconia is greatly inuenced by the
preparation method.16 Many synthetic techniques, such as
conventional precipitation, impregnation, microemulsion, and
solgel, have been employed for the preparation of tungsten-
promoted zirconia.17 The hydrothermal method is also used to
prepare tungstenzirconia or zirconia. Armendariz et al.18
prepared WO3ZrO2 via the hydrothermal treatment of
amorphous mixed zirconiumtungsten hydroxide gels.
Cortes-Jacome et al.19 synthesized WO3ZrO2 by precipitating
the solutions of zirconium oxynitrate and ammonium
metatungstate with ammonium hydroxide via three precipitate
treatment routes: aging, reuxing, and hydrothermal conditions.
They found that the hydrothermally treated sample exhibited
the highest tungsten dispersion, which caused strong structural
deformation of the tetragonal ZrO2, which was responsible for
the strongest surface acidity. Pan et al.20 and Song et al.21,22
used hydrothermally synthesized zirconia as a support to
prepare Pt-SO42/ZrO2 and Pt/WO3ZrO2 via the conven-
tional impregnation method. They found that crystalline
zirconia was formed at higher hydrothermal temperatures and
the catalysts had more acid sites and a stable pore structure.
Moreover, recent research indicates that, because of the low
viscosity of water at high temperature and pressure, the
hydrothermal environment can promote the diusion of active
species onto the surface and into the pore of support; therefore,
the hydrothermal method not only can act as a method to
synthesize metal oxides, but also can be applied to load active
species onto the support, leading to the formation of highly
dispersed active species.2325 The hydrothermal method had
been used to prepare W/Al2O323 and NiW/Al2O324,25 catalysts
with high tungsten dispersion. However, to our knowledge,
using the hydrothermal method to support tungsten oxide on
zirconia has not yet been reported.
In the present work, tungsten oxide was supported on
zirconia via the hydrothermal and impregnation methods, and
their properties were characterized and compared; moreover,
they were used as catalysts to reduce the viscosity of heavy oil
without water.
2. EXPERIMENTAL SECTION
2.1. Catalyst Preparation. Hydrous zirconia support was
synthesized through coprecipitation by adding a 14.7 M ammonia
solution slowly into a 0.5 M zirconyl chloride (ZrOCl28H2O) solution
with stirring until the pH of the mother liquor reached 9. The slurry
was further aged statically at room temperature for 6 h and then
ltered, washed, and nally dried at 110 C for 12 h.
A series of zirconia-supported tungsten oxide (W/Zr) containing
various tungsten contents and calcined at dierent temperatures were
prepared via the impregnation (IM) and hydrothermal (HD) methods,
which were referenced as W/Zr-IM and W/Zr-HD, respectively. For
6519
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the IM method, the support was soaked by an ammonium
metatungstate solution whose pH was adjusted to 6 by an ammonia
solution. This pH was chosen according to Yoris nding:26,27 such a
pH value is lower than the isoelectric point (IEP) of Zr(OH)4 and can
make large-sized metatungstate species (W12O39)6 evolve into small-
sized (HW6O21)5. The slurry was kept at room temperature for 12 h,
dried at 110 C for 4 h, and calcined at 450750 C for 4 h. The
corresponding catalyst was designated as x-W/Zr-IM-y, where x and y
refer to the tungsten content and the calcination temperature,
respectively. For the HD method, zirconia and ammonium
metatungstate solution with a liquid-to-solid ratio of 5 mL/g were
added into a Teon-lined stainless steel autoclave, and then heated to
110180 C in a roller oven for 12 h. Prior to addition, the pH of
ammonium metatungstate solution was also adjusted to 6. After
cooling to room temperature, the product underwent the same
treatment as W/Zr-IM. This series of catalyst was similarly denoted as
x-W/Zr-HD-y.
2.2. Catalyst Characterization. X-ray diraction (XRD) patterns
were recorded on an XPert Pro diractometer (PANalytical, The
Netherlands) equipped with an XCelerator detector and Cu K
radiation, operating at 40 kV and 40 mA. The diraction data was
collected in the scanning angle (2) range of 1080 with a step size
of 0.02 and counting time of 12 s at each step. For the quantitative
phase analysis, XPert HighScore plus software (version 2.2d) with
Rietveld structural models based on the ICSD database was
applied.28,29 The crystallite sizes of tetragonal and monoclinic zirconia
were calculated using the Scherrer equation.
The specic surface area, pore volume, and pore size of the sample
were determined with a Quadrasorb SI analyzer (Quantachrome,
USA) at 195 C, using liquid N2. Before analysis, the sample was
degassed at 300 C for 6 h under vacuum.
Dierential scanning calorimetry (DSC) of the noncalcined sample
was carried out on a STA-449F3 (Netzsch, Germany) thermal analyzer
with a ramp rate of 10 C/min in an air ow.
The acid strength of the catalysts was examined by Hammett
indicator method, using nitrobenzene (pKa = 12.4), 2,4-dinitro-
uorobenzene (pKa = 14.5), and 1,3,5-trinitrobenzene (pKa =
16.1) as an indicator, respectively.30 Prior to measurement, the
sample was dried under vacuum at 120 C for 2 h. The amount of acid
sites was measured by temperature-programmed desorption (TPD) of
ammonia on an Autochem II 2920 chemisorption analyzer (Micro-
meritics, USA) equipped for thermal conductivity detector (TCD).
The measurement process is according to the literature.22 The total
amount of ammonia desorbed from the sample was estimated by the
standard curve obtained from chromatographic analysis,31 and the
percentages of weak, intermediate, and strong acids were calculated by
Gaussian deconvolution of the TPD curve.32
2.3. Catalytic Activity Assessment. Catalysts W/Zr were used to
reduce the viscosity of the heavy crude oil. The reaction was carried
out in a stainless steel autoclave (0.5 L) that was equipped with a
stirring paddle and a thermocouple. First, the powdered catalyst (0.4
g) was well-mixed with a heavy crude oil (200 g) under vigorous
stirring. Second, the mixture was transferred into the autoclave and
nitrogen was injected to make the initial pressure 2 MPa. Third, the
temperature was increased to 220 C and maintained for 6 h at the
given stirring speed. Finally, the autoclave was cooled to room
temperature and the oil product was collected and, simultaneously, the
product in gas was collected and analyzed using a gas chromatography
(Model GC-9790, Fuli, China) that was equipped with a TCD
detector and a ame photometric detector (FPD). The viscosity of oil
was measured on a rotation viscometer (Model DJ-8SN, Jingke,
China) equipped with a water bath apparatus to keep the sample at 50
C. Heavy crude oil used here is provided by the Liaohe oileld with a
viscosity of 5.74 Pa s at 50 C, a density of 0.9589 g/mL at 20 C, and
containing no water. The activity of catalyst is expressed in terms of
the viscosity reduction ratio, which is most widely used for the
viscosity reduction of heavy crude oil.611
Saturates, aromatics, resins, and asphaltenes (SARA) fractions in oil
were analyzed according to the industrial standard of China Petroleum
Chemical Industry (No. SH/T-0509). The composition of elemental
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C, H, S, and N in the oil was measured by an elemental analyzer
(Model Vario EL-III, Elementar, Germany). To evaluate the variation
of boiling range distribution of oil before and after reaction, true
boiling point (TBP) stimulated distillation was carried out on a gas
chromatography (Model GC-9890B, Renhua, China) that was
equipped with a CP-SimDist High Temp capillary column (Varian,
USA), according to ASTM D5307. The amount of coke formed during
the reaction was obtained by measuring the content of carbon
deposited on the recovered catalyst through the above elemental
analyzer. The catalyst was recovered via the following steps: rst, the
fresh catalyst was tabletted; second, after reaction, gasoline was added
to dilute oil and then the used catalyst was collected by settlement and
ltration; third, the catalyst was washed by gasoline and toluene in
turn, until the washed liquid became colorless, to verify the complete
removal of the residual oil and gasoline; nally, the catalyst was dried
at 120 C for 12 h to remove toluene. Coke yield during the reaction
was calculated by the relationship33
content of coke in catalyst mass of catalyst
coke yield =
mass of crude oil
3. RESULTS AND DISCUSSION
3.1. W/Zr-HD Prepared at Various Hydrothermal
Temperatures. To investigate the eect of hydrothermal
temperature on the structure and property of W/Zr-HD, four
15-W/Zr-HD-650 samples were prepared at temperatures of
110, 130, 150, and 180 C, respectively. The XRD patterns are
shown in Figure 1; the quantitative phase composition results
Figure 1. XRD patterns of 15-W/Zr-HD-650 prepared at dierent
hydrothermal temperatures (110 C (spectrum a), 130 C (spectrum
b), 150 C (spectrum c), and 180 C (spectrum d)). Herein, t and m
indicate tetragonal and monoclinic zirconia, respectively.
determined via the Rietveld method and the specic surface
areas are given in Table 1. Figure 2 shows a typical plot of the
Rietveld renement corresponding to the 15-W/Zr-HD-650
sample prepared at a hydrothermal temperature of 150 C.
As shown in Figure 1, all the samples appear to be a two-
phase mixture of tetragonal zirconia (International Centre for
Diraction Data (ICDD) PDF Card No. 79-1771) and
monoclinic zirconia (ICDD PDF Card No. 83-0942), wherein
the tetragonal phase is dominant. There are no free WO3
crystallites detected by XRD on any of the samples. It indicates
that the WO3 species are highly dispersed on zirconia and the
hydrothermal temperature has little inuence on tungsten
dispersion. The percentage of tetragonal zirconia increases
gradually with the increasing hydrothermal temperature and
reaches a maximum at 150 C, and then decreases (see Table
1). Song et al.21 also found a similar trend when Pt/WO3
ZrO2 was prepared using a hydrothermally synthesized zirconia
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Table 1. Quantitative Phase Analysis Results and Specic
Surface Areas of the 15-W/Zr-HD-650 Sample Prepared at
Dierent Hydrothermal Temperaturesa
composition (%)
hydrothermal specic surface area
temperature (C) ZrO2(t) ZrO2(m) WO3(t) (m2 g1)
110 76.5 23.5 58.2
130 86.6 13.4 80.2
150 91.3 8.7 76.0
180 86.0 14.0 107.5
a
ZrO2(m), ZrO2(t), and WO3(t) represent monoclinic (m) zirconia,
tetragonal (t) zirconia, and triclinic (t) tungsten oxide, respectively.
Figure 2. Rietveld renement plot of the 15-W/Zr-HD-650 sample
prepared at a hydrothermal temperature of 150 C. Black continuous
line corresponds to the experimental data, and the blue cross line
corresponds to the calculated data. The dierence between the
experimental data and the calculated data is also shown, as a
continuous red line.
as a support. The hydrothermal environment characterized by
lower viscosity and high temperature promotes the collision of
hydrated zirconia colloids and thus forms a gel network via
oxolation to stabilize the zirconia structure and nally retain a
high amount of tetragonal zirconia.20 With the increasing
hydrothermal temperature, the surface area of the 15-W/Zr-
HD-650 sample increases and exceeds 100 m2 g1 at 180 C,
because of the developed pore structure that formed during
hydrothermal treatment.20
Pan et al.20 and Song et al.21 reported that, before calcination,
crystalline zirconia was formed in the hydrothermally
synthesized hydrous zirconia at hydrothermal temperatures
above 130 C. However, in the present investigation, the
noncalcined 15-W/Zr-HD samples prepared at various hydro-
thermal temperatures were all X-ray amorphous (see Figure 3).
The transformation of amorphous zirconia to crystallized
zirconia is supposed to be similar to the conversion of -
alumina into well-crystallized boehmite upon hydrothermal
treatment. Stanislaus et al.34 suggested that the dissociative
adsorption of water onto the anion vacancies of alumina and
the subsequent diusion of the hydroxyl groups led to the
rehydration of alumina and, thus, the formation and
recrystallization of boehmite under hydrothermal conditions.
However, the coexistence of tungstate and zirconia may cause
some tungstate ions to occupy the anion vacancies and interact
with hydroxyl groups on zirconia, thus inhibiting the
crystallization of amorphous zirconia, which is close to the
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Figure 3. XRD patterns of noncalcined 15-W/Zr-HD samples
prepared at dierent hydrothermal temperatures: 110 C (spectrum
a), 130 C (spectrum b), 150 C (spectrum c), and 180 C (spectrum
d).
restraining eect of F or P on the recrystallization of alumina to
boehmite.34
Armendariz et al.18 found that pure zirconium oxyhydroxide
gel yielded a mixture of tetragonal and monoclinic zirconia
when hydrothermally treated at 145 C without calcination,
whereas, when tungstenzirconium oxides (15 wt % WO3)
were synthesized by hydrothermal coprecipitation at 145 C,
only amorphous zirconia was detected, because the crystal-
lization and phase transformation of zirconia were retarded by
tungsten. Nevertheless, they found that tungstenzirconium
oxides became progressively more crystalline with increasing
hydrothermal temperature (165 and 225 C), since high
hydrothermal temperatures favored the crystallization of
amorphous zirconia. Cortes-Jacome et al.19 also reported the
formation of well-crystallized WO3ZrO2 synthesized via
hydrothermal coprecipitation. However, crystalline zirconia is
absent on the 15-W/Zr-HD samples, even when the hydro-
thermal temperature exceeds 150 C. Consequently, this
observation suggests that the HD method may improve the
eect of tungsten on delaying the phase transformation of
amorphous zirconia.
3.2. W/Zr-IM and W/Zr-HD Samples Calcined at
Dierent Temperatures. A series of W/Zr samples loaded
with 15 wt % tungsten and calcined at dierent temperatures
were prepared via the IM and HD methods, respectively,
wherein W/Zr-HD samples were hydrothermally treated at 150
C to obtain more tetragonal zirconia. The XRD patterns are
shown in Figure 4, and quantitative phase analysis results and
specic surface areas are given in Table 2.
The characteristic diraction peaks corresponding to triclinic
WO3 (ICDD PDF Card No. 20-1323) are observed on the W/
Zr-IM samples that have been calcined at 450750 C;
moreover, the content of free WO3 increases with calcination
temperature, because of the poor tungsten oxide dispersion.35
Sohn et al.12 also observed triclinic WO3 in the W/Zr samples
loaded with 13 wt % tungsten prepared via the IM method and
calcined at 4001100 C. The diraction peaks of WO3 are
absent in the W/Zr-HD samples that have been calcined at
450650 C, while present at 750 C. With the increasing
calcination temperature, the surface tungsten oxide bonds
strongly with zirconia; therefore, some W atoms are trapped in
the zirconia lattice, eectively inhibiting the sintering of
zirconia, thus causing an increase in tetragonal zirconia.
Nevertheless, at higher temperature, the considerable sintering
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Figure 4. XRD patterns of the W/Zr-IM sample (spectrum a) and W/
Zr-HD sample (spectrum b) calcined at dierent temperatures.
Herein, the symbol w denotes triclinic WO3.
of zirconia will cause the tetragonal zirconia structure to
partially collapse and segregate WO3 crystallites.36
Compared to the W/Zr-IM samples, the better tungsten
dispersion and greater amount of tetragonal zirconia observed
in the W/Zr-HD samples may be attributed to the stronger
tungstenzirconia interaction caused by the reaction of
tungsten with hydroxyl groups of zirconia under the hydro-
thermal conditions. Moreover, the greatly decreased viscosity of
aqueous solution under the hydrothermal conditions can
promote the diusion of the tungstate species on the support
surface and into pore channels eectively, resulting in improved
tungsten dispersion23 and, hence, a better antisintering eect.
The crystallite sizes of tetragonal and monoclinic zirconia are
listed in Table 2. As the calcination temperature increases, the
crystallite sizes increase slightly but a rapid increase appears at
temperatures above 650 C, because of the serious sintering of
zirconia. The crystallite sizes of both tetragonal and monoclinic
zirconia in the W/Zr-HD samples are smaller than those in the
W/Zr-IM samples at the same calcination temperature,
conrming the better antisintering eect of tungsten in the
former.
As the calcination temperature increases, the surface areas of
the W/Zr samples decrease considerably. Below 750 C, the
surface areas of the W/Zr-HD samples are much higher than
those of the W/Zr-IM samples, because of the better tungsten
dispersion, more tetragonal zirconia, and smaller zirconia
crystallites.
Cortes-Jacome et al.19 synthesized WO3ZrO2 via the
hydrothermal coprecipitation method and found that it had a
higher tungsten dispersion and tetragonal zirconia concen-
tration than those coprecipitated at room temperature or with
reux aging. To compare the modication eects of the
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Table 2. Quantitative Phase Analysis Results, Zirconia Crystallite Sizes, and Specic Surface Areas of W/Zr Samples Calcined at
Dierent Temperatures
composition (%) crystallite size (nm)
sample ZrO2(t) ZrO2(m) WO3(t) ZrO2(t) ZrO2(m) specic surface area (m2 g1)
15-W/Zr-IM-450 70.8 28.3 0.9 16.4 16.2 90.4
15-W/Zr-IM-550 72.1 26.8 1.1 16.9 16.3 72.1
15-W/Zr-IM-650 75.3 23.2 1.5 16.6 17.6 55.4
15-W/Zr-IM-750 42.4 52.8 4.8 20.6 21.2 35.5
15-W/Zr-HD-450 79.3 20.7 14.9 13.7 106.7
15-W/Zr-HD-550 83.5 16.5 14.9 14.4 87.3
15-W/Zr-HD-650 91.3 8.7 15.2 14.7 76.0
15-W/Zr-HD-750 48.5 47.9 3.6 20.3 20.1 38.3
15-W/Zr-HCP-650 74.6 25.0 0.4 15.2 16.5 55.4

hydrothermal coprecipitation and HD methods on the tungsten
dispersion and phase composition, a sample containing 15 wt %
tungsten was prepared via a following hydrothermal copreci-
pitation (HCP) method. The solution of zirconyl chloride,
ammonium metatungstate, and ammonia was mixed together
and had a pH value of 910. After hydrothermal treatment at
150 C for 12 h, the product underwent the same thermal
treatment as the 15-W/Zr-HD-650 sample and was referred as
15-W/Zr-HCP-650. Figure 5a shows the XRD patterns of the
Figure 5. XRD patterns of (a) the 15-W/Zr-IM-650, 15-W/Zr-HD-
650, and 15-W/Zr-HCP-650 samples and (b) fragments of the XRD
patterns in the 2226 2 range for these samples.
15-W/Zr-IM-650, 15-W/Zr-HD-650, and 15-W/Zr-HCP-650
samples. The fragment of XRD data from 22 to 26 (2) is
shown in Figure 5b. The phase composition of the 15-W/Zr-
HCP-650 sample is listed in Table 2. Tetragonal zirconia
content (74.6%) in the 15-W/Zr-HCP-650 sample is close to
that (75.3%) in the 15-W/Zr-IM-650 sample, but much lower
than that (91.3%) in the 15-W/Zr-HD-650 sample, whereas the
free WO3 content in the 15-W/Zr-HCP-650 sample (0.4%) is
6522
slightly higher than that in the 15-W/Zr-HD-650 sample (0),
but lower than that in the 15-W/Zr-IM-650 sample (1.5%).
In addition, the 15-W/Zr-HCP-650 sample exhibits a much
lower surface area than that of the 15-W/Zr-HD-650 sample
but is similar to that of the 15-W/Zr-IM-650 sample (see Table
2). The research groups led by Armendariz18 and Cortes-
Jacome19 also found that WO3ZrO2 synthesized via hydro-
thermal coprecipitation shows similar surface areas with that
synthesized via conventional coprecipitation methods. The
average pore sizes of the 15-W/Zr-IM-650, 15-W/Zr-HD-650,
and 15-W/Zr-HCP-650 samples are 6.87, 7.02, and 20.50 nm,
respectively. It suggests that HCP leads to a more-remarkable
pore-enlarging eect caused by the recrystallization of zirconia
during hydrothermal treatment, and also conrms the lesser
amount of recrystallization occurring in the HD process, which
is attributable to the better inhibition eect of tungsten.
The main dierence between HCP and HD is the pH value
of initial solution. In HCP, the adsorption of tungstate and
precipitation of zirconyl chloride take place in a basic
environment (pH 910), whereas, in HD, the adsorption of
tungstate on zirconia occurs in an acidic environment (pH 6).
Tungstate anions require a positively charged support surface
to enable the adsorption. Zirconia derived from zirconyl
chloride has an IEP between 6 and 7.27 At pH values above 9,
although tungsten-containing anions are dominantly present in
smaller-sized WO42 species, the surface of the hydrous zirconia
is negatively charged and an electrostatic repulsion will exist
between the surface and the tungstate, so the adsorption of
tungstate on zirconia may be greatly inhibited and the
antisintering eect of tungsten is weakened.17 However, at
pH values near and lower than 6, (HW6O21)5 species <1 nm
in size are formed and the zirconia surface is positively
charged;26 both eects are convenient to the adsorption of
tungstate on zirconia and thus promote the antisintering eect
of tungsten on zirconia. Therefore, to retain more tetragonal
zirconia at the same tungsten content, HD may require milder
hydrothermal conditions than HCP. It can be supported by the
fact that, for the sample (15 wt % tungsten, calcined at 650 C)
prepared by HCP, given the further raised hydrothermal
temperature and prolonged period, the tetragonal zirconia
content increases to 81.5% (hydrothermally treated at 165 C
for 24 h) and 91.8% (hydrothermally treated at 185 C for 24
h); the latter is close to that of the 15-W/Zr-HD-650 sample
(150 C for 12 h).
3.3. W/Zr-IM and W/Zr-HD Samples Loaded with
Various Tungsten Contents. A series of W/Zr samples
loaded with various tungsten contents and calcined at 650 C
were prepared via the IM and HD methods, respectively. The
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XRD patterns are shown in Figure 6, and the phase
composition results and specic surface areas are listed in
Table 3.
than that in the 20-W/Zr-IM-650 sample. Free WO3 crystallites
are observed on the 15-W/Zr-IM-650, 20-W/Zr-IM-650, 25-
W/Zr-IM-650, and 25-W/Zr-HD-650 samples. The W/Zr-HD
samples have more tetragonal zirconia but less free WO3 than
do the W/Zr-IM samples. Poorly dispersed tungsten oxide in
W/Zr-IM acts as a less-eective inhibitor to antisinter and
stabilize the tetragonal zirconia, which is also responsible for
the lower surface area of the W/Zr-IM samples.
DSC curves of noncalcined W/Zr-HD and W/Zr-IM
samples containing various tungsten contents are shown in
Figure 7. The board endothermic peak below 150 C due to

Figure 6. XRD patterns of (a) W/Zr-IM samples and (b) W/Zr-HD

samples with various tungsten contents, calcined at 650 C.

Table 3. Quantitative Phase Analysis Results and Specic

Surface Areas of W/Zr with Various Tungsten Contents
Calcined at 650 C
composition (%)
specic surface
sample ZrO2(t) ZrO2(m) WO3(t) t/(m + t)a area (m2 g1) Figure 7. DSC curves of precursors of (a) W/Zr-IM samples and (b)
10-W/Zr- 73.1 26.9 73.1 57.9 W/Zr-HD samples loaded with various tungsten contents.
IM-650
15-W/Zr- 75.3 23.2 1.5 76.4 55.4 water elimination is present in all samples. For pure ZrO2, the
IM-650 DSC curve shows a sharp exothermal peak at 431 C, which is
20-W/Zr- 80.5 15.0 4.5 84.3 61.6 due to the crystallization of ZrO2 from amorphous to the
IM-650
25-W/Zr- 77.5 10.2 12.3 88.9 51.2
tetragonal phase.35 The addition of tungsten on zirconia causes
IM-650 this exothermic peak to shift toward higher temperatures
10-W/Zr- 76.6 23.4 76.6 64.2 remarkably, and this shift increases with tungsten content,
HD-650 because of the delaying eect of tungsten on the phase
15-W/Zr- 91.3 8.7 91.3 76.0 transition of zirconia.12 The temperature of the exothermal
HD-650
peak for the W/Zr-HD samples is higher than that for W/Zr-
20-W/Zr- 94.6 5.4 94.6 79.7
HD-650 IM samples with the same tungsten content, since the stronger
25-W/Zr- 98.3 1.7 100 72.3 tungstenzirconia interaction in the former causes the dicult
HD-650 rearrangement of Zr atoms in lattices and, hence, inhibits the
R-20-W/Zr- 92.7 7.3 92.7 phase transformation of zirconia more eectively.
HD-650 According to the color change of the Hammett indicators, it
a
The ratio of tetragonal zirconia to the total amount of tetragonal and is found that all of the W/Zr samples calcined at 650 C have
monoclinic zirconia. an acid strength (H0) between 14.5 and 16.1; these are
regarded as solid superacids.12 The amount of acid sites, as well
The tetragonal zirconia concentration increases with as the percentages of weak, intermediate, and strong acid sites
tungsten content, although it appears to decrease in the 25- measured via NH3-TPD, are listed in Table 4.
W/Zr-IM-650 sample; considering the tetragonal percentage of The amount of total acid sites in the W/Zr samples increases
the total zirconia (tetragonal plus monoclinic), it is still higher with tungsten content and reaches a maximum and then
6523 dx.doi.org/10.1021/ef301064b | Energy Fuels 2012, 26, 65186527
Energy & Fuels
Table 4. Acid Amounts and Viscosity Reduction Ratios of W/Zr Samples with Various Tungsten Contents
acid amount proportion (%)
sample total acid amount (mmol g1) weak intermediate
10-W/Zr-IM-650 0.34 13.6 21.8
15-W/Zr-IM-650 0.41 12.8 24.8
20-W/Zr-IM-650 0.38 15.2 23.3
25-W/Zr-IM-650 0.35 14.1 26.3
10-W/Zr-HD-650 0.36 13.3 24.4
15-W/Zr-HD-650 0.46 11.4 24.5
20-W/Zr-HD-650 0.53 12.3 22.4
25-W/Zr-HD-650 0.51 12.5 23.8
decreases, which is generally in agreement with that reported by
Sohn et al.12 The W/Zr-HD samples can produce more acid
sites than W/Zr-IM samples loaded with the same tungsten
content. For the sample with both more tetragonal zirconia and
well-dispersed tungsten (15-W/Zr-IM-650 and 20-W/Zr-HD-
650), the maximum acid amount is obtained. Free WO3
crystallites form an inactive layer covering on the surface of
the active monolayer,35 and tetragonal zirconia provides a
higher surface area to disperse more tungsten species than
monoclinic zirconia, tending to form more acid sites. The trend
of strong acid percentage is similar to the variation of tungsten
dispersion. As suggested by Cortes-Jacome et al.,19 the strong
acid sites in tungstenzirconium oxides were mainly related to
the high dispersion of tungsten oxide, because the strong
tungstenzirconia interaction not only improved the dispersion
of tungsten but also caused the strong deformation of the
crystalline structure of zirconia, facilitating the generation of
strong acidity.
3.4. Catalytic Activity of W/Zr-IM and W/Zr-HD
Samples with Various Tungsten Contents. Viscosity
reduction of heavy oil was used to evaluate the catalytic
activity of W/Zr-IM and W/Zr-HD samples with various
tungsten contents, calcined at 650 C. Before comparing the
activities of the catalysts, a preliminary experiment was
conducted to eliminate the inuence of mass transfer and
keep the reaction in the kinetics-controlled region. For liquid
solid heterogeneous catalysis reaction occurring in a batch
reactor, the external mass-transfer resistance to reaction and
internal mass-transfer resistance to reaction are directly related
to the stirring speed and particle size of catalyst, respectively.37
First, the reaction was performed at various stirring speeds (30,
40, 50, and 60 rpm) to determine the limitations of the external
mass-transfer resistance, using the 10-W/Zr-IM-650 sample as a
catalyst; the viscosity reduction ratio is shown in Figure 8. It is
found that the viscosity ratio increases with stirring speed and
almost remains constant at speeds above 50 rpm, indicating the
absence of external mass-transfer limitations above 50 rpm.
Second, the reaction was performed over the 10-W/Zr-IM-650
sample with particle sizes of 4060 mesh and ne powder,
respectively. The results show no dierence in viscosity
reduction ratio between the two catalysts; it conrms that the
limitations of internal mass-transfer resistance can be
neglected.38,39 Therefore, the following activity tests were
carried out under a stirring speed of 50 rpm and over nely
powdered catalysts to obtain a purely kinetic result.
The viscosity reduction ratios of catalysts with various
tungsten contents are also presented in Table 4. The viscosity
reduction ratio increases with increasing tungsten content up to
20 wt % for W/Zr-HD samples and 15 wt % for W/Zr-IM
samples, which are close to the variation of the amount of total
6524
Article
strong strong acid amount (mmol g1) viscosity reduction ratio (%)
64.6 0.22 66.4
62.4 0.26 72.1
61.5 0.24 69.3
59.6 0.21 64.7
62.3 0.22 68.9
64.1 0.29 77.5
65.3 0.35 82.2
63.7 0.32 80.4
Figure 8. Eect of stirring speed on the viscosity reduction ratio of the
10-W/Zr-IM-650 sample.
and strong acid sites in W/Zr. It reveals that the acidity of the
W/Zr samples plays a crucial role in viscosity reduction.
Because of their greater number of acid sites, W/Zr-HD
catalysts show higher activity than W/Zr-IM catalysts. More-
over, for heterogeneous catalytic reactions, the catalysts with
higher surface areas also benet the activity to some extent; for
example, the 10-W/Zr-HD-650 and 10-W/Zr-IM-650 catalysts
have similar small amounts of strong acid, while their activity
follows the order of surface area. Catalyzed by 20-W/Zr-HD-
650, the viscosity of heavy oil is reduced from 5.74 Pa s to 1.02
Pa s, and the viscosity reduction ratio reaches 82.2%.
To further understand the role of W/Zr catalysts in viscosity
reduction, a blank test was carried out under the same
conditions (50 rpm, 220 C, 6 h, 2 MPa) without a catalyst.
The viscosity reduction ratio is only 18.7%, which demonstrates
that the introduction of a W/Zr catalyst can signicantly
promote the viscosity reduction of heavy oil.
The 20-W/Zr-HD-650 catalyst was recovered after reaction;
its XRD pattern is shown in Figure 9, and the phase
composition is given in Table 3. After reaction, the catalyst
almost retains its crystalline structure and the concentration of
tetragonal zirconia decreases slightly, which might be attributed
to the long period of contact with hot oil.
The SARA compositions of the oil before and after reaction
over the 20-W/Zr-HD-650 and 15-W/Zr-IM-650 samples are
given in Table 5. After reaction, the contents of resins and
asphaltenes decrease but those of the saturates and aromatics
increase, which is responsible for the decrease in viscosity.
Catalyzed by superacids, the long alkyl side chains and
naphthene groups located on the polycyclic aromatics in resin
may cleave and open rings, leading to an increase in the
contents of saturates and aromatics, as well as a decrease in the
contents of resins and asphaltenes.6,40 Resin is reduced more
remarkably than asphaltene, because of the formers weaker
dx.doi.org/10.1021/ef301064b | Energy Fuels 2012, 26, 65186527
Energy & Fuels Article

decrease in sulfur content is related to the cleavage of the

CS bond, as conrmed by the presence of H2S in the gas
product. Figure 10 shows the change in boiling range of oil

Figure 9. XRD patterns of fresh 20-W/Zr-HD-650 sample (spectrum

a) and recovered 20-W/Zr-HD-650 sample (spectrum b).

Table 5. SARA Compositions of Crude Oil before and after

Reaction Catalyzed by 20-W/Zr-HD-650 and 15-W/Zr-IM- Figure 10. Boiling range distribution of crude oil before and after
650 reaction over 20-W/Zr-HD-650.
weight fraction (%)
after reaction
before over over measured by TBP stimulated distillation. Due to the occurrence
reaction 20-W/Zr-HD-650 15-W/Zr-IM-650 of cracking, the fraction below 500 C has been raised from
saturates 28.6 39.7 36.4 41.2% to 43.7% after reaction. Moreover, the fraction below
aromatics 19.1 22.3 21.6 150 C is changed slightly while the middle fraction at 200
resins 49.6 35.9 39.7 450 C increases, suggesting the mild cracking.
asphaltenes 2.7 2.1 2.3 The dierences in aquathermolysis and the cracking reaction
in this study are discussed. First, in aquathermolysis, water at
aromaticity and, thus, the higher cracking activity. This is high temperature or in the form of steam plays a crucial role. It
conrmed by the fact that almost 60%70% of the carbon in not only acts as a solvent, reactant, and hydrogen donor,40 but
the resins of Liaohe heavy oil corresponds to naphthenic and it also serves as a catalyst to produce acid sites through reacting
paranic carbon, which can be easily cracked.41 The 20-W/Zr- with mineral or catalytic metal anions, and to interact with C
HD-650 sample shows more active ability in decreasing the S, CN, CO bonds,9 therefore, the viscosity reduction eect
contents of resins and asphaltenes, as well as increasing the is rather low if water is absent.11 For instance, Chen et al.6
contents of saturates and aromatics, relative to the 15-W/Zr- found that the catalysts could enhance the changes of heavy oil
IM-650 sample. molecules only in the presence of water. Fan et al.7 reported
The gas product (over 20-W/Zr-HD-650) is composed of that, when water was absent in the catalytic aquathermolysis,
N2, H2, CO2, H2S, and light hydrocarbons (such as C1, C2, C3, the viscosity of heavy oil was almost unchanged. In this
and C4), wherein N2 accounts for 92.9%, H2 = 0.3%, CO2 = investigation, no water was added and the crude oil is waterless,
0.1%, H2S = 0.2%, C1 + C2 = 2.7%, and C3 + C4 = 3.8%, while the viscosity of oil can be reduced by above 80%. Second,
which is proof of the presence of a cracking reaction. The during the aquathermolysis process, the free radicals or active
elemental composition of the oil before and after reaction, over chains formed by the cleavage of CS and CO bonds will
20-W/Zr-HD-650, is listed in Table 6. The atomic ratio of integrate with each other and further polymerize to high
molecules,8,11 so, the viscosity of the reacted oil will regress
Table 6. Elemental Composition of Crude Oil before and rapidly, which may be resolved by adding hydrogen donor to
after Reaction Catalyzed by 20-W/Zr-HD-650 terminate the active chains.11 For instance, Liu et al.8 reported
that the viscosity reduction ratio was 63.4% after aquathermol-
composition (wt%) ysis but dropped to 50.8% after one day and retained a value of
C H S N H/C (atomic ratio) 46.4% after 5 days. However, in the present work, the viscosity
before reaction 86.63 11.47 0.90 1.00 1.59 of the reacted oil is not increased, even passing through a
after reaction 86.06 12.25 0.70 0.99 1.71 longer period of time: the viscosity of the reacted oil is 1.02 Pa
s for the 20-W/Zr-HD-650 catalyst sample and 1.29 Pa s for the
15-W/Zr-HD-650 catalyst sample, whereas after 75 days, the
elemental H to C (H/C) of oil increases after reaction, because values are 0.98 and 1.28 Pa s, respectively. This indicates the
of the cracking of heavy hydrocarbons. The formation of liquid absence of free radicals or active chains during reaction, and the
product with higher H/C ratios is invariably accompanied by reaction is supposed to proceed via an ionic mechanism, as
the generation of coke with lower H/C ratios, which is opposed to a free-radical mechanism in aquathermolysis. From
deposited on catalyst and can be observed by the color change the foregoing discussion, this implies that a W/Zr solid
of catalyst. By measuring the coke content on recovered 20-W/ superacid may reduce the viscosity of heavy oil mainly by
Zr-HD-650, the coke yield during the reaction is calculated to breaking down the unstable CC bond, which is similar to the
be 0.04%. Because of the lower reaction temperature, the catalytic cracking process of heavy fractions in renery
reaction for producing coke is eectively inhibited. The processes but is rather dierent from the conventional
6525 dx.doi.org/10.1021/ef301064b | Energy Fuels 2012, 26, 65186527
Energy & Fuels
aquathermolysis; therefore, the higher acidity of catalyst will
improve the cracking activity and viscosity reduction ability.
The viscosity reduction performances of the W/Zr-HD and
Ni- or Sn-modied SO42/ZrO2 catalysts reported by Jing et
al.14 are compared. First, it seems that the W/Zr-HD catalysts
show higher activity than SO42/ZrO2 doped with Ni2+ or Sn2+,
which attained a maximum viscosity reduction ratio of 57.7%
for Shengli oil with the viscosity of 0.316 Pa s (50 C) under
240 C, after 24 h, and without water. Second, they found a
decrease in the H/C ratio after reaction and, thus, attributed
the viscosity reduction to the rupture of CS, since the
combination of a metallic ion in the catalyst with the S atom in
the sulde lowered the CS bond energy, similar to that which
occurs in aquathermolysis. Nevertheless, the H/C ratio of
reacted oil over the 20-W/Zr-HD-650 sample is increased,
which results from the cracking of weak CC bonds in heavy
hydrocarbons induced by the interaction of acidic sites in the
catalyst and hydrocarbons, similar to that which occurs in
catalytic cracking. Third, the activity of Ni-modied SO42/
ZrO2 was strongly suppressed by the addition of water; when
the water content reached 5%, the viscosity reduction ratio
decreased remarkably, by 60%, i.e., from 57.7% to 22%,
which was explained by the considerable loss of SO42 on the
catalyst surface in the presence of water. However, at the same
water content, the viscosity reduction ratio of the 20-W/Zr-
HD-650 sample decreases by 9.6% (i.e., from 82.2% to 74.3%),
since the long period of exposure in a hot moist environment
leads to a decrease in tetragonal zirconia. The result indicates
the better stability of W/Zr catalysts in water-containing
atmospheres than that of Ni-modied SO42/ZrO2. A Ni-
modied SO42/ZrO2 was also prepared using Jings method14
and used for the present oil and under the present reaction
conditions. It only attains a viscosity reduction ratio of 54.2%
for waterless oil, the H/C ratio of reacted oil slightly decreases
from 1.59 to 1.58, and sulfur content decreases from 0.90 to
0.66; moreover, the viscosity reduction ratio decreases to 35.6%
for oil with 5% water, in agreement with Jings nding.14
Further investigation reveals that the viscosity reduction ratio of
the 20-W/Zr-HD-650 sample remains almost unchanged when
the water content is no more than 1%, which demonstrates the
catalyst has better applicability for waterless or low-water-
content oil.
4. CONCLUSIONS
Tungsten oxide was supported on zirconia via the hydrothermal
and impregnation methods, respectively, and their properties
and catalytic activity for reducing the viscosity of heavy crude
oil were compared.
Compared with the impregnation method, the hydrothermal
method can strengthen the tungstenzirconia interaction and
promote the diusion of tungstate on zirconia; thus, it improves
the dispersion of tungsten oxide, increases the concentration of
tetragonal zirconia, and leads to the formation of more acid
sites. In comparison with the hydrothermal coprecipitation
method for preparing tungstenzirconium oxides, the relatively
lower pH in the present hydrothermal method may favor the
adsorption of tungstate anions on electropositive zirconia
supports, thereby causing better antisinter ability of tungsten
and more tetragonal zirconia under the milder hydrothermal
conditions.
Zirconia-supported tungsten oxide can be used as a superacid
catalyst to decrease the viscosity of heavy oil without water
through mild cracking of heavy hydrocarbons. The reactivity
6526
Article
mainly depends on the acidity of catalyst; therefore, catalysts
prepared by the hydrothermal method show better activity than
those prepared by the impregnation method. The catalyst
loading of 20 wt % tungsten prepared by the hydrothermal
method can reduce the viscosity of Liaohe heavy oil from 5.74
Pa s to 1.02 Pa s under reaction conditions of 220 C, 6 h, and
2 MPa. The present reaction is likely to follow the ionic
mechanism, which is dierent from the free radical mechanism
in conventional aquathermolysis; therefore, the regress in
viscosity of reacted oil is inhibited. Summarily, the zirconia-
supported tungsten oxide catalyst and the hydrothermal
preparation method developed here will provide an attractive
way to facilitate the exploration of heavy oil without water or
with a low water content.
AUTHOR INFORMATION
Corresponding Author
*Tel.: 86-28-83037335. Fax: 86-28-83037305. E-mail:
wanghaoswpu@hotmail.com.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
The authors acknowledge the nancial support from the
National Natural Science Foundation of China (No. 20906075)
and Foundation of State Key Laboratory of Oil and Gas
Reservoir Geology and Exploitation (No. PLN0907).
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