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Catalysis Today xxx (2015) xxx–xxx

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Vacuum residue upgrading through hydroprocessing with subcritical

water
Hong Kyu Ahn a , Sung Hyeon Park a , Sajid Sattar a , Seong Ihl Woo a,b,∗
a
Department of Chemical, Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea
b
Graduate School of EEWS, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea

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

Article history: Vacuum residue upgrading reactions were carried out with subcritical water and catalyst. Experiments
Received 1 July 2015 were performed in the autoclave batch reactor at the various reaction conditions (i.e. temperature
Received in revised form 30 August 2015 change, catalyst amount, reaction time, and water amount). The maximum liquid product conversion
Accepted 21 September 2015
was 55.5 wt.% at 400 ◦ C, 50 g of VR, 0.5 g of MoNaph catalyst, 6 h of reaction time, and 20 g of water
Available online xxx
amount. For evaluation of liquid products, C/H atomic ratio, aromaticity, aromaticity condensation, and
boiling point distribution was measured by elemental analysis (EA), 1 H nuclear magnetic resonance (1 H
Keywords:
NMR) and gas chromatography simulated distillation (GC-SIMDIS). Results showed that water converts
Vacuum residue
Subcritical water
the vacuum residue to the liquid product, and its conversion yield is comparable to that of the hydrogen
Upgrading gas process. Moreover, synthesized MoS2 nanosheet catalyst was used to compare the liquid product
Liquid product conversion.
Conversion © 2015 Elsevier B.V. All rights reserved.
Hydroprocessing

1. Introduction
Today, 30–40% of total energy is generated from the petroleum
crude oil resources [1]. About 50% of this crude oil becomes primar-
ily useful energy products like gasoline and diesel through refinery
processes; however, the rest remains residue which is difficult to
handle. The firstly gathered residual components have very high
viscosity, so they cannot be used directly in its natural state. Vac-
uum residue (VR), which is distilled at 80 mmHg pressure and over
500 ◦ C temperature, is the most viscous material among residual
components. Residue upgrading, especially vacuum residue, has
become very important study thanks to the large amount of residual
portion. There are many techniques for heavy oil upgrading such
as solvent deasphalting [2], delayed coking [3], visbreaking [4], FCC
[5] and catalytic hydroprocessing [6]. Catalytic hydroprocessing is
widely investigated because of its relatively high productivity and
selectivity within the processes [7].
Many studies for treating VR focus on catalytic hydrocracking
reactions that produce lighter products [8–13]. Generally hydro-
gen gas is used for hydrocracking reactions, and experimental
conditions are within 400–450 ◦ C and 5–15 MPa [14–17]. High tem-
perature and pressure are essential to break the VR. Hydrogenation
∗ Corresponding author at: Graduate School of EEWS, Korea Advanced Institute
of Science and Technology, Daejeon 305-701, Republic of Korea.
E-mail address: siwoo@kaist.ac.kr (S.I. Woo).
could be the main reaction, and other reactions such as pyrolysis,
desulfurization, and ring opening also present.
However, catalytic hydrocracking reactions are very danger-
ous and even further with the presence of hydrogen. Many safety
issues including environmental problems have been intensively
researched in hydrocracking area. Therefore, a new approach for
vacuum residue upgrading is of great need. In crude oil wells, trans-
porting residual components is an important part for petroleum
industry. Reduction of the viscosity is required to ease the trans-
portation of residue. Techniques such as “aquathermolysis” use
steamed water as reactant to reduce the viscosity of heavy oil.
Many researches revealed that steamed water injection can reduce
viscosity of vacuum residue [18]. Catalytic aquathermolysis exper-
iments were performed with various catalysts such as minerals,
metal ions, solid acid salts, aromatic sulfonic compounds, surfac-
tants, and metallic chelates [19–24]. These studies showed that
water can affect vacuum residue even though their relation is
between oil and water.
Aquathermolysis just focuses on viscosity reduction in low tem-
perature and long reaction time. There are few researches for
direct production of liquid product from vacuum residue with
water. In the condition of high temperature and pressure, water
exists in subcritical state. Moreover, it is reported that subcriti-
cal state water has solubility for organic compounds [25,26]. This
could be adaptable to hydrocracking of vacuum residue. In this
study, direct liquid conversions via catalytic upgrading reactions
with deionized (DI) water of subcritical state were performed.

http://dx.doi.org/10.1016/j.cattod.2015.09.038
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Table 1
Properties of vacuum residue feedstock obtained from SK Innovation Company.

Properties Value

CCRa (wt.%) 22.90

Total nitrogen (wt.%) 0.48
Total sulfur (wt.%) 6.97
Nickel (wppm) 44.50
Vanadium (wppm) 145.10
C5 asphaltene (wt.%) 18.00
C7 asphaltene (wt.%) 10.00
Specific gravity 1.04
CT /HT (atomic ratio) 0.65
a
Conradson carbon residue.

Water was used for safe and cheap alternative material to hydro-
gen. To observe conversion changes, several variables of reaction
temperature, catalyst amount, reaction time and water amount Fig. 1. Pressure profile as a function of reaction time (50 g of VR, 0.5 g of MoNaph
were set as variables. Liquid products were analyzed using ele- catalyst, and 20 g of water).
mental analysis (EA), nuclear magnetic resonance (NMR), and gas
chromatography simulated distillation (GC-SIMDIS) analysis were
2.3. Liquid products conversion and analysis
carried out for analysis of liquid product components. For compari-
son, synthesized MoS2 nanosheet catalyst was used for direct liquid
Liquid product conversion was calculated by the following equa-
production.
tion.

Liquid product conversion (wt.%)

2. Experimental
= liquid product (g)/VR (50 g) × 100 (1)
2.1. Materials
Elemental analysis of liquid products was performed by analyzer
Vacuum residue obtained from SK Innovation Corporation was
1 (EA1110-FISONS, CE Instruments) for C, H, N, and S and analyzer
used. The properties of VR are shown in Table 1. Vacuum residue
2 (Flash EA 1112, Thermo Finnigan) for determination of O in the
was kept at 100 ◦ C in an oven for fluidity before reaction. Commer-
products. 1 H Nuclear Magnetic Resonance (NMR) spectrometer was
cial molybdenum naphthenate (MoNaph, 10 wt.% of Mo, Shepherd
operated with the AMX-500 (Bruker Corp.) under the condition
Chemical Company) and synthesized MoS2 nanosheet were used
with chloroform-d solvent (1 vol.% of dilution), 500.14 MHz of fre-
for catalysts. Deionized water (purified by Milli-Q, Millipore) was
quency. Gas Chromatography Simulated Distillation (GC-SIMDIS)
included as reactant.
was performed with the Agilent HT750A-7890M.

2.2. Cracking reactions of the vacuum residue with MoNaph 2.4. Cracking reactions of the vacuum residue with MoS2
catalyst and water nanosheet catalyst and water

VR cracking reactions with MoNaph catalyst were carried out
in the high pressure autoclave batch reactor (350 ml inner volume,
made by Hanwoul Engineering Corporation). Magnetic drive stir-
ring system, temperature and pressure monitoring program via
personal computer, and gas vent valve line were included in this
system.
Vacuum residue (50 g) was used as feedstock in each experi-
ment. Only one variable was altered within amount of catalyst,
amount of water, reaction temperature, and reaction time while
the other variables were fixed. VR (50 g), DI water (0, 10 and 20 g)
and MoNaph catalyst (0, 0.1 and 0.5 g) were placed in the auto-
clave reactor. After purging the reactor with He gas for 30 min by
100 ml/min, the autoclave was sealed. Cooling water line was con-
nected to magnetic drive stirring system and the temperature was
increased. Temperature was linearly increased from room temper-
ature to purposed reaction temperatures (300, 350, 400 and 450 ◦ C)
at a rate of 5 ◦ C/min. When the temperature reached 100 ◦ C, the
mixture was stirred at 500 rpm. After reaching designated tem-
perature, the reaction system was maintained for 2, 3, 6 and 8 h
of reaction time. During the experiment, temperature and pres-
sure were recorded simultaneously by personal computer program.
After the reaction, the autoclave reactor was naturally cooled down
to room temperature. From the mixture, the liquid product was
separated from the solid residue, and the unreacted water was
removed using silica beads.
For comparison, VR cracking reactions with synthesized MoS2
nanosheet catalyst were carried out in the same batch reactor. MoS2
nanosheet catalyst was synthesized based on Peng et al. [27].
One variable was altered within amount of catalyst, and reac-
tion temperature while the other variables were fixed. VR (50 g), DI
water (5, 10, 20 and 30 g) and MoS2 catalyst (0.5 g) were placed in
the autoclave reactor. After sealing the autoclave, cooling water line
was connected to magnetic drive stirring system and the tempera-
ture was increased. Temperature was linearly increased from room
temperature to purposed reaction temperatures (400, 410, 420 and
430 ◦ C) at a rate of 5 ◦ C/min. When the temperature reached 100 ◦ C,
the mixture was stirred at 500 rpm. After reaching designated tem-
perature, the reaction system was maintained for 6 h of reaction
time. After the reaction, the autoclave reactor was naturally cooled
down to room temperature. From the mixture, the liquid product
was separated from the solid residue, and the unreacted water was
removed using silica beads.
3. Results and discussion
3.1. Reaction pressure profile as a function of reaction time
Fig. 1 shows the autoclave pressure profile as a function of reac-
tion time at 50 g of VR, 0.5 g of MoNaph catalyst, and 20 g of water
at 400 ◦ C. The maximum pressure was 113.2 bar at the end of the

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Fig. 2. Liquid product conversion with the conditional change of temperature (a), catalyst amount (b), reaction time (c), and water amount (d) (fixing other experimental
conditions).

Table 2
Liquid product conversions with various reaction conditions.

Reaction temperature (◦ C) Catalyst amount (g) Reaction time (h) Water amount (h) Maximum pressure (bar) Liquid product conversion (wt.%)

300 41.9 0
350 73.3 0
0.5 6 20
400 113.2 55.5
450 197.0 18.8
0 109.8 39.5
6 20
0.1 109.7 43.2
2 98.0 23.9
400 0.5 3 20 102.0 36.3
8 – 54.9
0 37.5 31.9
0.5 6
10 73.4 44.9

reaction time. Panariti et al. [28] reported that the lowest pressure
is achieved at the end of the reaction in hydrocracking reaction
with hydrogen. Pressure is reduced by consumption of hydrogen
gas. In this study, however, pressure became the highest at the end
of the reaction time. This tendency occurred in all the experiments
of this study. The opposite tendency is explained by the produc-
tion of lighter compounds by hydrocracking. Cracking of larger
compounds generate smaller compounds that have low boiling
point.
At the high pressure and temperature range of this study, water
becomes to its subcritical state. Carr et al. [25] reported that sub-
critical state water has solubility for organic compounds. Polarity
of water is decreased at subcritical state, and solubility for organic
compounds is increased. Generated H+ and OH− in subcritical state
are favorable to the cracking reactions of VR. Cheng et al. [29]
reported that supercritical water have both solvent effect and dis-
persion effect. In this study, our catalyst was dispersed on the
vacuum residue and water mixture. Organic compounds including
the reactants and the products are dissolved in the water. Water
was included as the hydrogen donor during the VR upgrading reac-
tion.
3.2. Liquid product conversions
In this study, collecting product and analyzing were focused on
liquid product because of strong adhesiveness of solid product and
negligible dead volume of gas product. Fig. 2(a) shows the results of
liquid product conversions with various reaction temperatures. At
300 and 350 ◦ C, liquid product conversions were almost zero, which
means VR did not react with water and catalyst. In both cases, visu-
ally transparent liquids were collected and analyzed using EA. H/O
atomic ratio results of collected liquid after reactions at 300 and
350 ◦ C were 2.19 and 2.21, respectively. Through this analysis, it can
be implied that negligible amount of water reacted under 350 ◦ C.
Cheng et al. [29] published the research that light product conver-
sion is decreased under 380 ◦ C. It means that vacuum residue had

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Table 3
Elemental analysis of liquid products with water amount changes at 400 ◦ C (50 g of VR, 0.5 g of MoNaph catalyst, and 6 h of reaction time).

Sample Water (g) N (wt.%) C (wt.%) H (wt.%) S (wt.%) O (wt.%) C/H atomic ratio

VR (solid) – 0.46 80.82 10.38 6.97 1.82 0.65

0 2.05 84.41 11.61 2.18 0.98 0.61
Liquid 10 1.80 79.89 12.55 2.01 3.75 0.53
20 1.73 78.41 12.94 2.23 4.24 0.51

Table 4 Table 6
Assignment of protons in the 1 H NMR spectrum. GC-SIMDIS results of liquid products with water amount changes at 400 ◦ C (50 g of
VR, 0.5 g of MoNaph catalyst, and 6 h of reaction time).
Parameter Type of protons Chemical
shift (ppm) Sample Accumulated mass (wt.%)

HA Aromatic hydrogen 6.0–9.0 <350 ◦ C 350–500 ◦ C <500 ◦ C total

H␣ Aliphatic hydrogen on C␣ to aromatic 2.0–4.0
rings Vacuum residue 0.7 4.5 5.2
H␤ Aliphatic hydrogen on C␤ and the CH2 , 1.0–2.0 0 g water 27.0 11.9 38.9
CH beyond the C␤ to aromatic rings 10 g water 37.5 17.5 55.0
H␥ Aliphatic hydrogen on C␥ and the CH3 0.5–1.0 20 g water 40.0 21.2 61.2
beyond the C␥ to aromatic rings

of water. Panariti et al. [28,31] reported that distillate production

insufficient activation energy for liquid production under 350 ◦ C, in
this study.
Liquid product conversion decreased to 18.8 wt.% at 450 ◦ C,
whereas liquid product conversion at 400 ◦ C was 55.5 wt.%. Large
amount of unreacted water was detected in collected liquid prod-
uct at 450 ◦ C. 197 bar of maximum pressure was observed at the
end of reaction with 450 ◦ C. Zhao et al. [30] reported that high pres-
sure is not helpful for radical cracking of hydrocarbons. Suppressing
“cage effect” of dense water is formed under high pressure condi-
tions. Grimaldo et al. [17] reported that both gas and solid phase
fractions were generated larger at over 400 ◦ C, which means liquid
phase fraction became smaller. Decrease of liquid product conver-
sion at 450 ◦ C is affected by suppressing effect of high pressure
with gas and coke formations. The optimized condition of reaction
temperature was set by 400 ◦ C from the results.
Fig. 2(b) exhibits that liquid product conversions with 0, 0.1 and
0.5 g of catalyst amount were 39, 43.2 and 55.5 wt.%, respectively.
Liquid product conversion with no catalyst was 39.5 wt.%. Thermoc-
racking reactions occurred with the absence of catalyst. With the
change of catalyst integration from 0.1 to 0.5 g of catalyst, the liquid
product conversion increased.
Liquid product conversions with 2, 3, 6, and 8 h of reaction
time were 23.9, 36.3, 55.5 and 54.9 wt.%, respectively, as shown in
Fig. 2(c). With increasing reaction time, conversion yield became
larger; however, the reaction reached to its saturation point after
6 h and was set as the optimum reaction time.
In Fig. 2(d), the liquid product conversions depending on
the amount of water (0, 10 and 20 g) were 31.9, 44.9 and
55.5 wt.%, respectively. Liquid product conversion with no water
was 31.9 wt.% which means that thermal self decomposition reac-
tions of VR occurred. When larger amount of water was injected,
liquid product conversion increased. Higher pressure for subcritical
state is achieved by larger amount of water.
The integrated results of liquid product conversions were tabu-
lated in Table 2. According to the results, maximum liquid product
conversion was 55.5 wt.% at 50 g of VR, 400 ◦ C of reaction tem-
perature, 0.5 g of MoNaph catalyst, 6 h of reaction time, and 20 g
yields of MoNaph catalytic hydrogenation reactions with 8–16 MPa
of hydrogen gas at 400–460 ◦ C were 45–80 wt.%.
To compare liquid product conversion, additional vacuum
residue upgrading experiment with hydrogen gas was performed.
Experimental condition was same as the optimized condition at
50 g of VR, 400 ◦ C of reaction temperature, 0.5 g of MoNaph cata-
lyst, 6 h of reaction time. Only water was exchanged for hydrogen
gas. Initial pressure at room temperature of hydrogen gas was set
by 65 bar (same amount of hydrogen as the optimized condition).
Liquid product conversion was 65 wt.%. Liquid product conversion
at optimized condition is as well as distillate yield with hydrogen
gas.
3.3. Elemental analysis for liquid products
The EA results for liquid products at 0, 10 and 20 g of water
amounts are listed in Table 3. C/H atomic ratio of vacuum residue
was 0.65. However, this ratio for liquid products with 0, 10 and 20 g
of water were reduced to 0.61, 0.53 and 0.51, respectively. C/H ratio
became smaller when larger amount of water was added. Hydro-
genation and saturation were accelerated by water injection, and
sulfur removal was observed. MoNaph catalyst is known as ther-
mally decomposable compound. At high temperature and pressure,
MoNaph transformed to its activated form [32]. Curtis and Pelle-
grino explained that during reaction, sulfur in the gas phase or
feedstock are reacted with thermally decomposed and activated
catalyst [33]. MoS2 active form is made from this procedure. Gen-
erated MoS2 active form acts as catalyst in this experiments. Sulfur
removal is achieved by transformation of MoNaph catalyst into
MoS2 active form with introduction of sulfur in feedstock.
3.4. Nuclear magnetic resonance (NMR) results for liquid
products
The integrated area percentages listed in Table 5 were obtained
based on the assignment of protons in 1 H NMR spectrum in Table 4.

Table 5
NMR results of liquid products with water amount changes at 400 ◦ C (50 g of VR, 0.5 g of MoNaph catalyst, and 6 h of reaction time).

Temp. (◦ C) Water (g) State CT /HT HA H␣ H␤ H␥ fA HAU /CA

VR Solid 0.65 4.93 6.41 62.29 26.37 0.269 0.649

0 0.61 6.88 12.72 60.96 19.44 0.237 0.916
400 10 Liquid 0.53 6.40 12.71 56.30 24.59 0.117 2.057
20 0.51 5.14 11.28 58.19 25.39 0.070 3.019

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Table 7
Liquid product conversions of MoS2 nanosheets catalyst with various water amount and reaction temperatures.
Reaction temperature (◦ C) Catalyst amount (g) Reaction time (h)
400 0.5 6
410
420 0.5 6 10
430
Aromaticity (fA ) and aromaticity condensation (HAU /CA ) were cal-
culated by following formulas same as demonstrated [19,20].
(CT /HT ) − [(H␣ +H␤ +H␥ )/2HT ]
fA =
(CT /HT )
(HA /HT ) + (H␣ /2HT )
HAU /CA =
(CT /HT ) − [(H␣ +H␤ +H␥ )/2HT ]
CT and HT represent the total amount of carbon and hydrogen
present, respectively. HT means HA + H␣ + H␤ + H␥ and CT /HT ratio
was calculated by elemental analysis. Larger value of HAU /CA means
lower aromaticity condensation.
Aromaticity and aromaticity condensation of liquid products
with various water amount changes are listed in Table 5. fA and
HAU /CA values of vacuum residue were 0.269 and 0.649, respec-
tively. fA values of liquid products with 0, 10 and 20 g of water
were 0.237, 0.117 and 0.070, respectively. HAU /CA values of liquid
products with 0, 10 and 20 g of water were 0.916, 2.057 and 3.019,
respectively. Compared to vacuum residue, fA and HAU /CA of liquid
product without water changed from 0.269 to 0.237 and from 0.649
to 0.916, respectively. fA values of liquid products with 10 and 20 g
of water were much smaller than fA value without water. HAU /CA
values of liquid product with water 10 and 20 g were much larger
than HAU /CA value without water.
Chen et al. [23,24] reported that decrease of aromaticity is
attributed to the hydrogenation and saturation of large groups with
decrease of CT /HT ratio. Decrease of aromaticity condensation of
liquid products is caused by the ring-opening, pyrolysis and recon-
struction of the larger aromatic groups. In this study, decreased fA
and increased HAU /CA of liquid products obviously revealed that
liquid product conversions with water are supported by hydro-
genation, saturation, ring opening and pyrolysis. Side chains of large
groups in vacuum residue were abbreviated and shortened.
3.5. Gas chromatography simulated distillation (GC-SIMDIS)
analysis for liquid products
Distillation is the principal process in the petroleum industry.
Gas chromatography simulated distillation (GC-SIMDIS) is used for
powerful analysis of petroleum product [34,35].
Boiling point distributions of liquid products with various
amount of water and vacuum residue were plotted in Fig. 3 ana-
lyzed by GC-SIMDIS. Accumulated mass results classified by boiling
point were given in Table 6. Accumulated mass of liquid prod-
ucts under 500 ◦ C with 0, 10 and 20 g of water were 38.9, 55.0 and
61.2 wt.%, respectively. When larger amount of water was injected,
accumulated mass of liquid products increased; hence, generation
of lighter product is affected by water injection.
Similar tendencies were observed at different boiling point
sections. Between 350 and 500 ◦ C, accumulated mass of liquid prod-
ucts with 0, 10 and 20 g of water were 11.9, 17.5, and 21.2 wt.%,
respectively. Under 350 ◦ C, accumulated mass of liquid products
with 0, 10 and 20 g of water were 27.0, 37.5 and 40.0 wt.%, respec-
tively. Accumulated mass of liquid products increased in amount
of injected water at any boiling point section. Generation of light
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Water amount (g) Maximum pressure (bar) Liquid product conversion (wt.%)
5 50.2 55.9
10 60.1 58.7
20 111.8 48.5
30 160.2 40.8
81.6 53.8
94.2 48.6
118.0 41.5
(2)
(3)
Fig. 3. Boiling point distribution of accumulated mass for liquid products with var-
ious amount of water.
liquid products that have lower boiling point is affected by sub-
critical water. Tendencies between liquid product conversion and
accumulated mass with various amounts of water have good agree-
ment in this study.
3.6. Liquid product conversions with MoS2 nanosheet catalyst
and water
In practice, we prepared a MoS2 nanosheet catalyst to
experiment vacuum residue upgrading reactions. Liquid product
conversions of MoS2 nanosheet catalytic reactions with various
water amounts and reaction temperatures are listed in Table 7. The
maximum liquid product conversion of 58.7 wt.% was observed at
50 g of VR, 0.5 g of MoS2 nanosheet catalyst, 6 h of reaction time,
10 g of water, and 400 ◦ C of reaction temperature. Liquid product
conversion became smaller when reaction temperature increased
over 400 ◦ C.
Similar aspects of liquid product conversion changes for MoN-
aph catalytic reactions were observed. As mentioned before,
MoNaph catalyst transformed into the MoS2 active form [32,33].
Tendencies for liquid product conversions with both catalysts could
be similar. Therefore, cage effect of subcritical water suppresses
liquid product conversion at increased temperature.
4. Conclusions
In this study, vacuum residue upgrading with catalyst in sub-
critical water was investigated. Experiments were carried out with
changing temperature, catalyst amount, reaction time, and water
amount. Maximum conversion of 55.5 wt.% was given at the con-
dition of 400 ◦ C of temperature, 0.5 g of MoNaph catalyst, 6 h of
reaction time, and 20 g of water amount. Liquid product conver-
sion was comparable to that of the hydrogen gas process. Liquid
product conversions were supported by subcritical state water.
Catalyst was dispersed on the vacuum residue and water mixture.
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Hydrogenation and saturation were observed by reduction of C/H
ratio of liquid product. Decrease of fA and increase of HAU /CA for liq-
uid product are related to hydrogenation, saturation, ring opening
and pyrolysis. Large accumulated mass of 61.2 wt.% under 500 ◦ C
for liquid product is accomplished by conversion of light products
which have low boiling point. Similar aspects were observed by
using synthesized MoS2 nanosheet catalyst compared to that of
MoNaph catalyst.
Acknowledgements
Authors appreciate to Jae hyun Koh with the preparation feeds
and assistance for analysis. This research is supported by BK21PLUS
program through the National Research Foundation (NRF).
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