Journal of Industrial and Engineering Chemistry 43 (2016) 1–12

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Review

A review on the oil-soluble dispersed catalyst for slurry-phase

hydrocracking of heavy oil
Manh Tung Nguyena,b , Ngoc Thuy Nguyena,b , Joungmo Choa,b , Chulwoo Parka ,
Sunyoung Parka , Jinhwan Junga , Chul Wee Leea,b,*
a
Division of Green Chemistry & Engineering Research, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, Republic of Korea
b
School of Science, University of Science and Technology (UST), Daejeon 305-333, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history:
Received 27 May 2016 Nowadays, unconventional-oil becomes a potential candidate for satisfying the world's energy demands
Received in revised form 29 July 2016 due to the scarcity of other energy sources. However, it contains many impurities, such as heavy metal,
Accepted 30 July 2016 sulfur-compounds, and nitrogen-compounds, and leads to quick deactivation of catalyst, high coke
Available online 9 August 2016 formation, and large pressure drop during the operation of a fixed bed or E-bed. Slurry phase
hydrocracking (SHC) with the presence of oil-dispersed catalyst has been proven to be the best solution to
Keywords: overcome those problems. In oil-dispersed, the metal precursor, dispersion ability, and additive strongly
Slurry-phase hydrocracking affect the catalyst performance, and are all reviewed in this paper.
Oil-dispersed catalyst
ã 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Heavy oil process
reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Oil-soluble dispersed catalyst activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Active species in the catalytic environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Reaction kinetic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Catalysts and catalyst development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Metal precursors in oil-soluble dispersed catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Hydrogen donor for catalyst in slurry-phase hydrocracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Optimization oil-soluble dispersed catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Catalyst deactivation and regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Conclusions and future prospective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Introduction predicted to increase by 34% between 2014 and 2035 with an

average growth of 1.6% per year [1]. Moreover, fossil fuels
Nowadays, with the sharp increase in world population and the represented 81% of the primary energy fuel in 2010 and are
rapid development of technology, the global energy demand is predicted to stay at 75% in 2035 (Fig. 1) [2]. Fossil fuel can be simply
becoming a critical issue. The primary energy demand has been classified into the following three types: oil, natural gas and coal.
While coal and natural gas can be used as energy source with
minimal preparation after exploitation, oil often requires many
* Corresponding author at: Division of Green Chemistry & Engineering Research,
other treatments before turning to be valuable products. Generally,
Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, oil can be classified to four types: conventional oil, heavy oil, extra
Republic of Korea. heavy oil and oil sands bitumen. Currently, conventional oil is used
E-mail addresses: chulwee@krict.re.kr, chulwee2304@gmail.com (C.W. Lee).

http://dx.doi.org/10.1016/j.jiec.2016.07.057
1226-086X/ã 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
2 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12
Fig. 1. Primary global energy demand by source: projections for 2035 [2].
as the main source for the petrochemical industry; however
conventional oil’s capacity is just 30% in total [3] and that source
will probably be exhausted in the near future.
Over the last few decades, interest in unconventional oil has
been constantly increased. Processes to convert unconventional oil
especially heavy oil into better quality products such as middle
distillate products are being widely investigated. Heavy oil has low
American Petroleum Institute gravity (API) and low value; it is a
combination of saturate, aromatics, resins, and asphaltenes with
heavy metals, nitrogen, sulfur, oxygen, and other compounds.
Currently, there are three main processes for the hydro-
conversion of heavy oil: fix-bed, ebullated bed and slurry phase.
Among them, the slurry phase process (SHC) is the latest
technology with many advantages such as the following: the
ability to obtain more than 95 wt.% conversion of vacuum residue
and other type of feedstock, including coal. In addition, the low
coke formation benefits in reducing the loss of liquid product in the
sediment. Furthermore, the high quality products can be obtained
through a two-stage design that incorporates a fixed-bed hydro-
treating/hydrocracking reactor; flexibility of feedstock; low-cost,
micron-size deposable catalysts; and a required reactor volume
that is lower than for the E-bed process for a given volume of
residue feed [4].
In the slurry phase hydrocracking process, catalyst can be
divided into two types: heterogeneous solid powder catalysts and
homogeneously dispersed catalysts. As the name, heterogeneous
solid powder catalyst is the powder that contains at least one metal
(cobalt, molybdenum, nickel, iron) in the salt form or sometime,
they are impregnated in a supported material such as alumina,
silica–alumina or carbon nano tube. Heterogeneous solid powder
catalyst involves system in which catalyst and reactants are in
different physical phases. When the reaction occurs, the reactant
having high molecular weight deposits on the active sites of
catalyst and blocks the pores; leads to shortening of the catalyst’s
life [4] and increasing of pressure drop because of the formation of
larger number of solid particle. As the result, operation is
instability and the system is shut-down more frequently.
Unsupported dispersed catalyst has been developed to solve
those problems. It consists of the two catalyst types: water-soluble
dispersed catalyst and oil-soluble dispersed catalyst. Generally, oil-
soluble dispersed catalyst is often more expensive than water-
soluble dispersed catalyst; however, water-soluble dispersed
catalyst has lower catalytic activity due to the fast evaporation
of water and agglomeration of the precursors, finally forming large
particles and causing difficulty to disperse into submicrometer
particle in the feed [5–8]. Meanwhile, oil-soluble dispersed
catalyst can disperse uniformly in the feedstock; favor the rapid
up-take of hydrogen; as the results suppress the coke formation,
increase total conversion and enhance quality of liquid product.
Oil-soluble dispersed catalyst activity
Currently, the research on the mechanism of SHC is still very
limited due to the complexity of feedstock. In slurry-phase
processes, free radicals are created by a thermal cracking reaction
of heavy oil components such as asphaltenes and resins, and then
the hydrogenation occurs on the metal active sites to deactivate
free radicals [9]. The highly dispersed of oil-soluble dispersed
catalyst acts as hydrogen transfer agent and deactivates the
intermediate free radical moieties in the liquid phase, thereby
preventing coke formation and polymerization reactions, and
reducing the yield of gas products [10–12] (Fig. 2).
Active species in the catalytic environment
Metal sulfide has been proved to be the active specie in
hydrocracking processes. It is formed by the reaction between
metal precursors in the catalyst and sulfur compounds in the
feedstock or additional sulfur sources [13]. What Cyr et al. [14]
have done so far is to conduct SHC experiment with oil-soluble
dispersed catalyst and metal-containing compound additives
(such as iron pentacarbonyl or molybdenum 2-ethyl hexanoate).
They realized that metal compounds might react in situ with sulfur
moieties in the feedstock to create the colloids. Then, because of
the wetting property, the colloidal particles would stick on the
surface of precursor spheroids and inhibit the spheroids from
coalescing.
The activities of metal sulfide have been proposed by Daage and
Chianelli [15]. Its activity mostly depends on the disordered edge
planes in the reaction environment. The edge planes often have a
high activity, while the basal planes seem to be inert (Fig. 3). In
Fig. 2. Catalytically controlled thermal cracking [12].
 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12
Fig. 3. Rim–edge theory [15].
their model; the rim site shows the hydrogenation function and
the rupture of the C

S bond while the edge sites are active for only
the rupture of the C

S bond.
During the SHC reaction, the unsupported MoS2 exhibits a
hexagonal coordination, and then the corner and edge ions in MoS2
are removed quickly. As a result, the coordinatively unsaturated
sites (CUS) and sulfur ion vacancies are formed. Due to the Lewis
acid characteristic of sulfur ion vacancies, CUS can easily adsorb
molecules with unpaired electrons.
In a catalytic environment, it is obvious that fewer layers could
enable more benefit in total catalyst activity. However, due to the
anisotropic layered stacked structure and the interaction of the
support with active phases, investigations on catalyst dispersion
have been plagued with many difficulties. Liang et al. [16]
established a procedure for quantitatively determining the size
of MoS2 slabs from the analysis of the diffraction pattern of poorly
crystalline MoS2. As a result, they found that by increasing the
pressure, the catalyst could completely destack and the activity of a
catalyst that consists of a single layer of MoS2 decreased only
slightly. The well dispersion and single layer of MoS2 can be seen in
Fig. 4 [17].
On the other hand, Strausz [7,18] used molybdenum naph-
thenate and nickel di-2-ethylhexanoate as metal precursors for
SHC. Those precursors were chemically reacted with the micellar
dispersed asphaltenes in the bitumen and formed the metal
complexes. During the hydrocracking reaction, micelle–metal
complex breaks down and form metal oxide/sulfide active species.
However, not all of the complexes are broken down; the micelles
that have strong affinity between metal and asphaltenes are very
stable and cannot be decomposed under the reaction condition. As
the results, it will be kept inside the coke.
Fig. 4. High-resolution transmission electron micrographs (HRTEM) of the THF insoluble fraction of the recycle stream of the EST process, showing the dispersion of the
catalyst (left) and a single MoS2 layer with a superimposed atomic model (right) [17].
3
For more detail, a series of studies based on the activity of MoS2
were carried out [19–24]. These studies found that the hexagonal
coordination exhibited by unsupported MoS2 is the main factor to
provide hydrogen uptake function and suppress coke formation.
During the reaction, hydrogen can react easily with sulfur ions in
MoS2 that are located in the corner and edge. As a result, the
unsaturated sites and sulfur ion vacancies are formed and then
become active sites for hydrogenation due to the Lewis acid
characteristic. Hydrogen moves to the surface of active specie and
forms Mo–H and S–H moieties. Those connections are unstable
and can react rapidly with the free hydrocarbon radicals that are
generated by thermal cracking and finally decrease the rate of
condensation and aromatization reactions.
Reaction mechanism
To determine mechanism of reactions in SHC, Du et al. [13]
experimented on Karamay vacuum gas oil (KLVGO), Karamay
vacuum residue (KLVR) and Venezuelan atmospheric residue
(V-AR) with molybdenum naphthenate acting as an oil-soluble
dispersed catalyst precursor. The product was analyzed to
determine the value of two effect parameters RG (the ratio of
i-C4H10 and n-C4H10) and isoparaffin/n-paraffin ratio. The small
value of these effect parameters indicates that the reaction creates
fewer isomerization products; the reaction is followed by a free
radical mechanism. Otherwise, the reaction is followed by
carbonium ion mechanism. The gas product data can be seen in
the Table 1.
It is obvious that the gas product from thermal cracking and
catalytic cracking have the same composition, and paraffin yields
were above 96% volume including a 73–78% volume yield of
methane and ethane. Therefore, the mechanism of slurry phase
hydrocracking is the same as that of thermal hydrocracking,
namely the free radical mechanism.
Normally, the catalyst is activated before hydrocracking
reaction. That procedure is often named the sulfidation; there
are two kind of sulfidation: ex-situ and in-situ sulfidation. Oil-
dispersed catalyst precursors are mixed with carbonaceous
compound; under suitable thermal conditions, it is decomposed
to solid, nano-sized catalyst particles. The sulfur sources are often
in the carbonaceous compound, but sometime, hydrogen sulfide is
used, especially in the case of ex-situ sulfiding. Temperature of
sulfidation is ranged from 300 to 400  C [25], and hydrogen
pressure is about 1000–2500 psig.
As what has been mentioned before, after sulfidation, the
coordinatively unsaturated sites, sulfur ion vacancies are both
formed and distributed uniformly. Then, the mixture of catalyst
4 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12

Table 1
Gaseous product distribution of feedstock oils at thermal hydrocracking and catalytic hydrocracking [13].

Product yield of KLVGO (vol%) Product yield of KLVR (vol%) Product yield of V-AR (vol%)
a b
TH CH TH CH TH CH
CH4 57.10 56.04 58.13 58.19 59.17 58.62
C2H6 18.04 17.78 18.90 16.66 17.99 17.90
C2H4 0.29 0.27 0.26 0.26 0.19 0.19
C3H8 13.37 13.51 13.51 13.35 13.45 13.61
C3H6 0.63 0.98 0.69 0.67 0.82 0.94
i-C4H10 1.86 1.82 2.32 2.25 1.92 1.85
n-C4H10 2.55 2.71 2.75 2.94 2.56 2.77
trans-2-C4H8 0.18 0.23 0.10 0.10 0.14 0.12
1-C4H8 0.20 0.27 0.12 0.12 0.13 0.13
cis-2-C4H8 0.15 0.10 0.15 0.14 0.13 0.11
i-C5H12 2.15 2.49 1.24 1.33 1.29 1.35
n-C5H12 1.82 2.21 0.78 0.85 0.87 0.91
cis-2-C5H10 0.03 0.04 0.20 0.16 0.14 0.18
CO 1.14 1.13 0.56 0.62 0.76 0.91
CO2 0.45 0.37 0.33 0.32 0.41 0.45
C6+ 0.04 0.05 0.06 0.04 0.03 0.06
a
Thermal hydrocracking.
b
Catalytic hydrocracking.

will be transferred to mix again with the feedstock in the case of

ex-situ sulfidation; or reaction will carry out directly by continuing
increase temperature. At higher temperature, the thermal cracking
happens. The poly-aromatic compounds are being broken down in
the weak positions such as C

C, C

S, C

O and etc. and finally
become the smaller free radicals. Meanwhile, H2 molecule moves
to the active sites and forms the intermediate connections Mo–H or
S–H; those connections are not stable and easily to give hydrogen
free radical to other compounds. Consequently, deactivation of free
radical along with the saturation of unsaturated compound is
occurred constantly. Thermal hydrocracking and catalytic hydro-
cracking have been reported to occur in cascade [26]. It means the
vacuum residue is hydrocracked gradually to form the lighter
products following the order: vacuum gas oil, middle distillate,
Fig. 5. Proposed kinetic mode for the hydrocracking of heavy oils [28].
naphtha and so forth. The efficiency of a hydrocracking reaction is
made by the well combination of thermal cracking and hydro-
genation to obtain the desired products. Vaccum gas oil ðVGOÞ : rVGO ¼ k1 y2R
ðk5 þ k6 þ k7 ÞyVGO ð2Þ
In summary, with the presence of oil-dispersed catalyst
precursors, coke and gas yields decrease significantly while the
quality of the liquid product improves. Metal sulfide has been Middle distillate : rMD ¼ k2 y2R þ k5 yVGO
ðk8 þ k9 ÞyMD ð3Þ
formed by the ex-situ or in-situ reaction; and then provides
hydrogenation function. Those active sites saturate aromatics in
the feed, saturate olefins, deactivate the free radicals formed in the Naphtha : rN ¼ k3 y2R þ k6 yVGO þ k8 yMD
k10 yN ð4Þ
cracking, inhibit condensation and polymerization and finally
protect themselves from poisoning by coke [27].
Gases : rG ¼ k4 y2R þ k7 yVGO þ k9 yMD þ k10 yN ð5Þ
Reaction kinetic
The kinetic model was incorporated into an isothermal plug-
Most of kinetic models have been reported in the literature flow reactor model to ignore all the limitations in the mass
propose that the hydrocracking reactions of heavy oil are followed transfers. Then they were solved using Runge–Kutta method.
by the first-order reaction [28]. However, Sanchez and Ancheyta dyi
[29] has presented another point of view when they considered the 1

¼ ri ð6Þ
d LHSV
second-order for the hydrocracking of vacuum residue due to the
first and quick disappear of the most reactive compound in the Finally, all the kinetic parameters were determined using the
residue. optimization of Marquardt [31] and have been shown in the Table 2
The five-lump kinetic model has been used to investigate together with the corresponding activation energies.
kinetic of hydrocracking reaction (Fig. 5) [28]. From those results, some important comments can be pointed
With the assumptions that hydrocracking of vacuum residue out. First, naphtha cracking is extremely difficult to occur and can
follows second order whiles other reactions follow the first order be observe in the investigated conditions. Second, the kinetic
[29,30]. The reaction rates for each reactant have been estimated parameters of residue hydrocracking exhibited the following
by the following equations [29]: order: k1 > k2 > k4 > k3, indicated high selectivity toward VGO,
followed by middle distillates and gases, with naphtha having
Residue : rR ¼
ðk1 þ k2 þ k3 þ k4 Þy2R ð1Þ the lowest selectivity.
 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12 5

Table 2
Kinetic parameters of the proposed model [29].

Pressure = 6.9 MPa Pressure = 8.3 MPa Pressure = 9.8 MPa

a a
Rate constant value Activation energy, EA Rate constant value Activation energy, EA Rate constant valuea Activation energy, EA
(kcal/mol) (kcal/mol) (kcal/mol)
        
380 C 400 C 420 C 380 C 400 C 420 C 380 C 400 C 420 C
Residue
k1 0.0012 0.0035 0.0129 53.3 0.0022 0.0047 0.0197 49.0 0.0025 0.0060 0.0206 47.7
k2 0.0012 0.0029 0.0128 53.1 0.0011 0.0057 0.0215 66.3 0.0011 0.0039 0.0171 62.4
k3 0.0002 0.0008 0.0028 59.0 0.0003 0.0010 0.0029 51.2 0.0004 0.0009 0.0031 45.9
k4 0.0013 0.0019 0.0058 33.4 0.0008 0.0023 0.0054 43.6 0.0005 0.0021 0.0040 31.2

VGO
k5 0.0025 0.0060 0.0135 37.9 0.0048 0.0055 0.0244 36.5 0.0070 0.0150 0.0353 36.3
k6 0.0011 0.0030 0.0081 45.9 0.0016 0.0043 0.0086 37.4 0.0022 0.0055 0.0090 31.8
k7 0.0008 0.0017 0.0036 35.1 0.0009 0.0019 0.0038 33.0 0.0010 0.0021 0.0040 31.2

Middle distillate
k8 0.0027 0.0060 0.0127 34.8 0.0028 0.0065 0.0146 37.5 0.0028 0.0070 0.0166 39.8
k9 0 0 0 0 0 0 0 0 0

Naphtha
k10 0 0 0 0 0 0 0 0 0

1
a
The rate constants for the residue are given in units of wt.% h , whereas the rate constants for the VGO, middle distillates, and naphtha are given in units of h
1.

1

Fig. 6. Comparison between experimental and estimated product compositions at

9.8 MPa: () 380  C, (*) 400  C, and (&) 420  C [28]. Fig. 7. Configurations of SPR: (a) slurry-phase reactor; (b) bubble column reactor;
(c) stirred tank reactor [32].

The comparison between experimental and calculated product
composition obtained by solving Eqs. (1)–(5) is shown in Fig. 6.
The deviations between both the experimental and estimated
values were lower than 5% on average. It indicates that the five-
lump kinetic model is found to represent adequately to the
hydrocracking of heavy oil.
Catalysts and catalyst development
Nowadays, when all of the convenient oil sources are being
exhausted, the inconvenient oil sources are getting dirtier, and
require a high process technique to satisfy the world energy’s
demands. Currently, slurry phase hydrocracking is the latest
upgrade heavy oil technology. It has been investigated and
perfected for decades and gradually affirmed its important
position in the future of petroleum industry.
Slurry phase reactors (SPR) are worked based on the fact that
catalyst is suspended in a liquid in batch mode or it might be move
concurrently or counter-currently with the gas flow. Nowadays,
three main kinds of reactors are used in laboratory and industrial
scale; those are: slurry phase reactors, bubble column reactor and
stirred tank reactor (Fig. 7a) [32].
Generally, slurry phase hydrocracking with oil-soluble
dispersed catalyst are often operated between 420–450  C. Metal
removal can be increased when temperature is increased, however,
it is has side effect when coke formation is also increased.
Hydrogen pressure is often kept from 1000 to 2500 psig. Increasing
hydrogen pressure causes the decrease in coke yield [33,34] but it
seems to be not economical. Catalyst concentration is another
important issue, depends on the activity of metal, catalyst
concentration might be varied between 300–2500 ppm. Resident
time ranges from 20 to 180 min [35]. Some of the typical
advantages and disadvantage of SPR are listed as following Table 3
[10,32].
In the slurry phase hydrocracking technique, catalysts always
attract huge interest from the scientists. Thus far, oil-soluble
dispersed catalyst has proved to be the most excellent catalyst with
almost full conversion, the ability to work in super high impurity
environments and low coke formation. However, the synthesis cost
is the most disadvantage of oil-soluble dispersed catalysts. In this
vein, many papers and patents have been published; as the
scientists have looked for cheaper and better metal precursors, or
tried to improve catalyst activity by combining different metals, or
by adding some additives.
6 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12

Table 3
Typical advantages and disadvantages of slurry phase reactors [10,32].

Advantages Disadvantage
 Operate almost isothermally  Uncertain scale up
 Control temperature easily  Catalyst sedimentation
 Interphase contact well  Catalyst recovery and reuse
 Large liquid hold up
 High conversion rate
 Operational flexibility
 Low pressure drop
 Low construction and operational costs
 Low catalyst consumption compares with other processes.
 Easy addition of catalyst

Metal precursors in oil-soluble dispersed catalysts
Oil-soluble dispersed catalyst precursors are created by the
combination of an oxide, a sulfide or a salt of metal from group IV
through VIII including transition metal-based catalysts derived
from the organic acid salt or metal–organic compounds of Mo, V,
W, Cr, Fe etc. [36].
Table 4 below shows some typical oil-soluble catalysts
precursors that have been used so far.
Among many metal precursors, molybdenum seems to have
attracted the most interest due to its high hydrogenation activity in
sulfide form compared with others. Hooman et al. [47] conducted a
series of SHC experiments with Cold Lake vacuum residue using
Mo-octoate and Mo-micelle precursors. The reactions have been
carried out in 1 h at 415–445  C and 13.8 MPa of hydrogen.
Consequently, coke suppression, residue conversion and hydrogen
uptake were observed. In addition, the optimization catalyst
concentration was also found at 600 ppm with 84 wt.% of residue
conversion and 2.9 wt.% of coke compared with 22 wt.% of coke in
thermal hydrocracking under the same conditions.
Watanabe et al. [48] investigated the activities of
Mo-dithiocarbamate (Mo-DTC) and Mo-dithiophosphate (Mo-
DTP) in vacuum residue. In his research, the Mo complexes and
derived MoS2 were found to be distributed in both asphaltenes and
maltenes. Under hydrotreatment conditions, MoS2 is formed. Mo-
DTC has higher sulfiding efficiency than Mo-DTP and is expected to
be more active. He also found that MoS2 or any type of solid Mo
derived from those catalysts are very fine particles with low
crystallinity and are easily dispersed in feedstock.
Beside the catalysts based on Mo, many scientists have tried
with different metal precursors. Zhang et al. [49] performed slurry
phase residue hydrocracking with nickel oil-soluble dispersed
catalyst and a feedstock of LiaoHe atmospheric residue. Fig. 8
shows the results of thermal hydrocracking and catalytic
hydrocracking with 300 mg nickel/g feedstock.
It is obvious that the presence of nickel oil-soluble dispersed
catalyst significantly improved the product quality and decreased
the coke yield. By experiment, the author also concluded that the
conversion of feedstock to distillate is thermally controlled and
practically independent of both the catalyst concentration and
hydrogen pressure. In addition, the active catalytic species of
dispersed catalyst are the different nickel sulfide crystals:
hexagonal NiS, millerite NiS and cubic Ni3S4.
A series of different catalysts based on different metals was
used in the research of Bearden [50]. Those catalyst precursors
were nickel octoate, cobalt resinate, iron naphthenate, molybde-
num resinate, vanadium resinate and chromium resinate, and they
were mixed separately with heavy oil (Jobo and Cold Lake Crude).

Table 4
Oil-soluble dispersed catalysts precursors for slurry phase hydrocracking.

Licenser Catalyst components Feed Catalyst concentration Main results Ref

no.
Headwaters Technology Ni, Mo etc. oil-soluble PFO 4000 ppm BTX yield 17.0%; gasoline and diesel yield [37]
Innovation, Llc catalysts 72.3%
University of British MoS2 catalyst Vacuum residue 100–1800 ppm Liquid yield achieved 88% [38]
Columbia, Vancouver,
Canada

Exxon Research and Molybdenum alicyclic or Heavy oil with 50–200 ppm 50 wt.% reduction of CCR [39]
Engineering Co. naphthenate CCR > 5% Solid, non-colloidal catalyst
Fe2O3 and Mo naphthenate Cold Lake crude oil 50–200 ppm in-situ 50 wt.% reduction of CCR, coke yield 1% [40]
Iron molybdenum Cold Lake crude oil 0.5–2.0 wt.% Conversion > 50% [41]
Solid particle with low SA and
PV
CrO3tert-butyl alcohol Heavy oil with CCR 5– 0.1–2.0 wt.% Conversion 80–85 wt.% [42]
50 wt.% Solid chromium-containing
catalyst
Alberta Oil Sands Technology Iron pentacarbonyl or Athabasca bitumen 0.1–0.5 wt.% well-dispersed 90% Conversion 0.3 wt.% coke yield [43]
and Research Authority molybdenum 2-ethyl with 50 wt.% diluent colloidal particles
hexanoate
Mo, Ni acetylacetonates or 2- Athabasca bitumen 50–300 ppm mixture of Low coke yield [44]
ethyl hexanoate asphaltene and metal doped
coke
Universal Oil Products Co. Non-stochiometric vanadium Wyoming sour crude Well-dispersed colloidal High Ni, V removal [45]
sulfide oil particles
Headwaters Technology Bimetallic catalyst (CoMo, Heavy oil 100 ppm metal Increase asphaltene conversion (up to [46]
Innovation NiMo, FeMo . . . ) 86%) and reduce coke (down to 1.18%)
 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12
Fig. 8. Effect of nickel oil-soluble dispersed catalyst on slurry-phase hydrocracking
[49].
The active species were formed in-situ. After one hour reaction,
generally, all of the metals were effective in not only suppression of
coke and gas formation but also showing the high levels of
desulfurization, demetallization and Conradson carbon conver-
sion. However, the molybdenum gave the best results in terms of
liquid yield (95.8–97.2 wt.%) and coke (0.5–0.8 wt.%). Oil-soluble
dispersed catalyst based on iron has the greatest advantage in
terms of cost but seems to be not very effective, with the highest
coke formation (5.2 wt.%) and gas yield (2.8 wt.%) (Fig. 9).
Panariti et al. [51] has also worked with various types of oil-
soluble dispersed catalysts. The result is shown in the Table 5. The
catalytic performances of the tested metals follow the order:
Mo > Ni  Ru > Co > V > Fe. The reason for the difference in catalyst
activity might due to the dissimilar in the active form of
molybdenum and the others. Molybdenite disperses into feedstock
in the form of monolayer or crystallites with a limit of two or three
layers; the average dimensions of the layer are only about 20–40 Å,
while the other metals often form a three-dimensional pyrrhotite-
like crystalline structure with a crystal size of 200–300 Å. This
means there is a significantly different surface area, which results
in much lower in catalyst activity.
Fig. 9. Performances of different monometal oil-soluble dispersed catalysts [50].
7
As has been mentioned before, one of the most disadvantages of
oil-soluble dispersed catalyst is high production cost. In order to
overcome that problem, the mixtures of oil-soluble dispersed
catalyst and other cheaper catalysts have been considered. The
mixture of oil-soluble dispersed catalyst and heterogeneous
catalyst has been tested [52]. In that research, Mo oil-soluble
dispersed was used as the homogeneous part, and the heteroge-
neous part was Co–Mo catalyst on g-Al2O3 support. Surprisingly, a
rapid decrease in the conversion of feedstock was observed as the
amount of homogeneous catalyst in the reactor increased. It
appears as though the supported catalyst ties up some of the
dispersed Mo, thereby deactivating the supported catalyst; as a
result the conversions are similar to runs with just-dispersed Mo,
but at a lower concentration.
The ideal of using bimetallic catalyst is attracting considerable
interests. Wang et al. [53] investigated a hydrocracking reaction
with the combination of molybdenum based oil-soluble dispersed
and iron-based water-soluble dispersed catalyst precursors. He
found out that water-soluble dispersed catalyst not only inhibits
coke formation but sacrifices the sites of coke deposition.
Consequently, the active Mo site could be saved from the
deposition of coke and finally improve the quality of the product.
The mixture of two oil-soluble dispersed catalysts has been
tested for SHC of LiaoHe Vacuum Residue [54]. A series of
experiments used Co-naph or Ni-naph or their mixture as the
catalyst. In the experiments, nickel showed better performance
than cobalt, and the presence of Ni–Co combination just produced
a simple mathematical addition effect on the coke inhibition and
conversion of feedstock. However, the combinations of Co or Ni
precursor with Mo precursor have been proven to greatly benefit
both the inhibition of coke and the product quality [46]. Cobalt
precursor was chosen as the second transition metal and was
mixed with molybdenum precursor with a mole ratio varied from
1:98 to 1:10. The inventors found that the active species of metal in
the vacuum residue are CoS and CoMoS; and that their combina-
tion benefited not only economic but also enhanced asphaltene
conversion and reduced sediment. The reason for that phenome-
non has been explained by the synergetic effect of Mo and Co. Due
to the electronic configurations, [Kr] 4d55s1 (cobalt) has a stronger
attraction to sulfur than [Ar] 3d74s2 (molybdenum). Finally, when
the molecular complex of those metals is formed, cobalt becomes a
8 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12

Table 5
Effect of active metals on product yield and quality [51].

Catalyst precusor No catalyst Mo naph Fe naph Ni naph CoRe VRe RuAA

Feedstock conversion (wt.%) 89.6 84.9 87.6 83.2 83.7 85.2 84.1

Product distribution (wt.%)

C1-C4 10.9 7.3 10.0 12.6 11.7 13.2 11.7
C5- 200  C 33.5 38.5 35.3 32.9 35.4 32.0 30.7
200–350  C 16.6 23.8 16.2 21.2 19.2 19.6 21.8
350–500  C 6.7 12.0 6.9 11.5 9.4 8.2 11.8
> 500  C 10.4 15.1 12.4 16.8 16.3 14.8 18.6
Coke 21.9 3.3 19.2 5.0 8.0 12.2 5.4
C5-asphaltenes 8.9 14.3 10.5 13.5 14.1 13.9 15.3

Product quality
HDM (%) >99 82 98 87 89 93 78
S in 200–350  C 3.2 1.9 3.2 2.3 3.0 2.9 2.3
S in 350–500  C 4.9 2.6 4.8 3.3 4.5 4.4 3.3

promoter, attracts the sulfur and then transfers it to the

molybdenum molecular nearby.
Jeon et al. [55], successfully chemically synthesized bimetallic
CoMo oil-soluble dispersed catalyst precursor while in the
previous studies, that kind of precursor was simply prepared by
physical mixing two different monometallic catalysts. Compared
with monometallic and physical mixtures of catalyst, the new
catalyst precursor showed a better performance, enhanced of
liquid yield and reduced of both gas and coke (Table 6).
On the other hand, the multi-metallic liquid catalyst is another
choice for the slurry-phase hydrocracking of heavy oil. Multime-
tallic liquid catalyst can also be classified into two types: water-
dispersed and oil-dispersed. The water-dispersed type often
consists of two metals; one from group VIB and another from
group VIII [56]. During the preparation process, the oxide of a
group VIB metal such as molybdenum or tungsten is dissolved in
ammonia aqueous to form an absolute solution. Then, ex-situ Fig. 10. Product distribution for SHC with multi-metallic liquid catalyst at different
sulfidation steps are carried out to form slurry then the slurry is temperature [57].
promoted with a group VIII metal, for example: nickel, cobalt; and
finally that mixture is introduced with hydrocarbon oil. In the case Consequently, the multimetallic liquid catalyst seems to be a
of oil-dispersed catalyst, the major parts of the metal components promising candidate in slurry-phase hydrocracking due to the
often include nickel, iron, molybdenum, manganese, cobalt and the cheap price and quite high conversion with low coke formation; in
like [57]. Because those metals are obtained from the recovery addition, recycling the catalyst has been proven to provide even
process of industrial waste materials, the cost would greatly better results compared with using fresh catalyst.
reduce. A series of SHC experiment with multi-metallic has been
carried out [57]. 50–200 ppm based on metal of UPC-21 has been Hydrogen donor for catalyst in slurry-phase hydrocracking
used as a catalyst; reaction temperatures were investigated from
430  C to 460  C and initial pressure of hydrogen was about In upgrading heavy oil, hydrogenation is the most important
8–12 MPa. UPC-21 is kind of metal-organic framework that has function of the catalyst. Therefore, theoretically, the presence of a
general formation: [Cu3(L)1.5(H2O)3]3DEF20H2O, where L is the hydrogen donor would be very helpful for the enhancement of
ligand [58]. As a result, conversion rate is quite high at 80–90% with hydrogen uptake, resulting in increased conversion and the
a little coke formation (<1%). Fig. 10 has shown the results of reduction of coke.
experiments that were conducted at different temperatures. Generally, the hydrogen donors in the petroleum industry could
Furthermore, a part of the bottom oil was brought back to the be classified to three types based on the different types of hydrogen
reactor to investigate recycle reactions. Table 7 shows experiment that are provided: anionic hydrogen, radical hydrogen, molecular
conditions and the main results of those experiments. hydrogen. Fisher et al. [59] conducted a series of experiments with
tetralin acting as a hydrogen donor. The results were quite
Table 6 impressive: even with a heterogeneous catalyst of CoMo based on
Performance of monometallic, physical bimetallic and chemical bimetallic oil- alumina, the conversion was about 60%, the desulphurization and
soluble dispersed catalysts [51]. demetallization reached a high level, especially for nickel and
Catalyst No catalyst Co naph Mo octo Co + Mo CoMo
vanadium, and coke formation was just around 1%.
Shi and Que [54] have tested performance of various oil-soluble
Gas yield (wt.%) 21.16 14.77 13.78 13.22 12.38
Liquid yield (wt.%) 76.27 83.77 85.41 86.00 87.08
dispersed catalysts in slurry-phase hydrocracking of LiaoHe
<200  C 19.40 14.33 16.34 16.59 16.65 Vacuum Residue (LHVR) with and without the presence of tetralin
200–350  C 22.42 23.64 22.28 23.44 24.57 (THN) which acted as a hydrogen radical donor. As a result, the
350–500  C 21.37 28.05 26.04 27.53 27.76 performance of the catalyst mixture between an oil-soluble
>500  C 13.08 19.39 19.11 18.44 18.10
dispersed catalyst precursor and hydrogen donor would effectively
Coke yield (wt.%) 2.56 1.46 0.81 0.78 0.55
inhibit coke formation and yield a good upgrade of LHVR. In
 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12 9

Table 7
Recycling experiments with multimetallic liquid catalyst. [57].

Reaction temperature,  C 440 440 445 445

Hydrogen partial pressure, Mpa 10 10 10 10
Hydrogen–oil ratio, Mm3/m3 757/1 800/1 737/1 800/1
Recycling ratio (fresh raw material/bottom oil) 100 66/34 100 70/30
Total volume hourly space velocity, 1/h 1.10 1.14 1.13 1.14
Volume hourly space velocity of fresh raw material, h
1 1.10 0.75 1.13 0.80

Product distribution, wt.%

C1–C4 (gas) 4.76 5.50 4.96 7.40
C5-180  C 9.27 9.60 10.28 13.80
180–350  C 24.08 27.30 27.41 29.60
350–524  C 37.50 53.10 37.62 45.40
<524  C 75.61 96.30 80.27 96.20
>524  C 25.39 4.60 20.90 5.00
Hydrogen loss 1.13 0.92 1.18 1.18
Total yield 101.0 100.92 101.18 101.18

addition, the conversion per coke unit was significantly reduced
with the presence of THN (Table 8).
The only disadvantage of using a hydrogen donor relates to the
energy point of view. Huge amounts of hydrogen donor were used,
from 10% [54] to 100% [58], in mass compared with feedstock; and
this led to the consumption a great deal of energy during the
reaction and in the next distillation stage.
Optimization oil-soluble dispersed catalysts
Catalyst activity is the most important issue in any type of
catalytic reaction. It affects not only the total conversion yield and
the desired products but also on production costs. In the previous
section, active metals were demonstrated to be a critical factor that
affects the activity of catalysts and using molybdenum oil-soluble
dispersed catalyst with the presence of promoters such as cobalt or
nickel could be more beneficial than other cases. However, there
are still many other factors that may affect the performance of oil-
soluble dispersed catalysts such as precursor solubility, degree of
dispersion or the pretreatment of the catalyst.
Panariti et al. [51] has experimented with different oil-soluble
dispersed catalysts based on Mo precursor: molybdophosphonic
compound, dithiocarbamate complex Mo3S7-(DTC)4, MoNaph,
MoAA, PMA and the two Mo-based ultrafine materials: Mo2N
and Mo2C. As a result, the hydrogen consumptions in the case of
Mo2N and Mo2C were found to be lower and the coke formations
were higher than other cases. This suggests that with lower
dispersion, catalyst activity would be lower.
On the other hand, the performance of the dithiocarbamate
complex has not shown a significant difference with the other oil-
soluble dispersed catalysts. This means the addition of a sulfur
source does not affect the sulfidation of Mo precursor; in other
words, the sulfur compounds existing in the feedstock provide a
sufficient amount of sulfur for the activation of the catalyst
precursor. That point of view was also confirmed in Del Bianco
et al’s research [35]. The addition of a phosphorus source increased
the vanadium removal in the upgrading of heavy stock due to the
formation of a P–V oil-insoluble compound [51,60–62]. However, it
does not have much effect on hydrogen consumption, coke
formation or the quality of liquid product [51]. Therefore,
generally, the performance of the catalyst seems to be independent
on the organic group bonded to the active metal.
The ratio of hydrogen sulfide to hydrogen could greatly affect
the number of active sites CUS [24]. As what has been mentioned
before, the SH groups attached to the sulfided Mo and CoMo
moieties seems respond to the acid property of the catalyst. Petit
et al. [63] recently presented evidence for the presence of Brønsted
acid sites not only on the support but also on sulfided Mo, CoMo,
and NiMo phases, using dimethylpyridine as the probemolecule.
Topsøe et al. [64] and Rana et al. [65] conducted research on the
process to form an SH group from anion vacancies with the
presence of hydrogen and hydrogen sulfide (Fig. 11).
During the operation, metal precursors are converted to sulfide
forms; therefore it is expected to save more resident time and limit
the deactivation if the catalyst is presulfided before contacting
with the feed. Presulfiding could be performed either in-situ or ex-
situ. Generally, ex-situ is more beneficial than in-situ for two main
reasons. First of all, in-situ sulfidation requires a complex operation
condition due to the time required to complete the sulfidation
reaction [66–68] (Fig. 12).
In addition, according to research [69] on CoMo catalyst,
increasing the sulfiding temperature from 300  C to 400  C could

Table 8
Slurry-phase hydrocracking of oil-soluble dispersed catalyst with and without a hydrogen donor [54].

Catalyst, mg/g Tetralin wt.% Coke wt.% Conversion wt.% Conversion per unit coke

Co naphthalene Ni naphthalene
0 0 0 9.79 65.20 6.66
10 7.02 63.92 9.11
200 0 0 2.39 56.40 23.60
10 1.39 54.98 39.55
160 40 0 2.51 58.20 23.19
10 1.59 56.00 35.22
100 100 0 2.61 59.00 22.61
10 1.73 57.42 33.19
40 160 0 2.99 59.50 19.90
10 1.93 57.91 30.00
0 200 0 3.34 61.21 18.33
10 2.29 59.35 25.92
10 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12
Fig. 11. Formation of an SH group in a hydrocracking reaction [66].
Fig. 12. Comparison of in-situ and ex-situ (actiCAT) presulfiding [67].
produces a major increase in the degree of sulfiding of molybde-
num species and results in increased activity of the catalyst.
However, on an industrial scale, in-situ presulfiding does not allow
for the optimal temperature control and optimal heat release;
therefore the temperature is always kept lower 320  C to prevent
local overheating.
Catalyst deactivation and regeneration
The most disadvantage of oil-soluble dispersed catalyst
comparing with other types of catalyst is its price. Therefore,
along with the research on developing new catalysts, it is necessary
to do research on catalyst deactivation and the reusability of those
catalysts. In slurry phase hydrocracking, the reaction time is often
very short and the catalyst deactivation is not really significant.
However, on an industrial scale, the long catalyst lifetime has
numerous benefits not only in production cost, but also operation
and maintenance expenses.
Basically, coke can be classified into four types: sponge coke,
shot coke, needle coke, purge coke and catalyst coke [70–73].
Sponge coke has a spongelike appearance with pores and bubbles
stuck inside the solid coke. That type of coke has the ability of
Fig. 13. Sponge coke (a) and shot coke (b) [74].
supporting itself and, therefore, will not fall down to the bottom of
reactor. It has diameter of around 1.83 m when the reactor is open.
Shot coke is a combination of individual particles that often have
spherical or slightly ellipsoidal shape and the diameter is about
1–4 mm. The advantage of that coke is that it is easy to be removed
from the reactor; however it has lower value than sponge coke
(Fig. 13). Needle coke is a premium-grade coke that is made from
special petroleum feedstock. It has a crystalline broken needle
structure and is chemically produced through the cross linking of
condensed aromatic hydrocarbon during the coke formation.
Purge coke is produced by flexi-coking and is used as a fuel in coke-
burning boilers. Catalyst coke is the mixture of coke and catalyst. It
is formed when carbon is deposited on catalysts, is used in various
refining processes, and is burned off and used as a fuel in the
refining process.
Generally, the catalyst will be deactivated when the metal
active site is covered by carbonaceous or heavy metal or other
types of impurities [75]. In general, the formation and deposition
of carbonaceous or coke are the main reasons for catalyst
deactivation; however, until now, not so many researches on that
phenomena has been published. For the fixed-bed catalyst, the
deactivation of the catalyst occurs quickly happened when the
coke blocks catalyst pores [5,76], while with oil-soluble dispersed
catalyst, it is likely different.
In fact, the recycling of catalysts, especially oil-soluble
dispersed catalysts in slurry phase hydrocracking often leads to
many difficulties. The major problem of recycling homogeneous
catalysts is that, in the end of reaction, the catalyst is mixed with
products at the nanometer scale so it is nearly impossible or very
costly to recover.
In the precipitate, the metal precursor changed into the sulfide
form. In the case of the supported catalyst, before recycling, the
solid mixture in the bottom of the reactor will be treated by
burning several times to remove the coke from the catalyst and
then the solid mixture will be directly remixed with the feedstock
[77]. However, with oil-soluble dispersed catalysts, the metal
sulfides created after reactions are very fine crystals. These crystals
are often stuck inside the coke; therefore, when recycling to the
feedstock, the amount of solid loading will be increased.
Rezaei et al. [38,78,79] have done experiments with various
concentrations of Mo octoate precursor and then coke was recycled
back again and again to the feed to investigate the reusability of the
 M.T. Nguyen et al. / Journal of Industrial and Engineering Chemistry 43 (2016) 1–12
Fig. 14. The XRD diffractogram of coke samples recovered after different
hydroconversion experiments [78].
catalyst. They announced some important conclusions. Firstly,
metal precursors were transferred into sulfide form and 90% of
them were well dispersed and were recovered in the solid product
(coke). Even if the solid loading is proportional to the recycling
time, when it is lower than 7.5%, there is no significant effect to
catalyst activity. Rezaei et al. also showed that the recycling
number depends on the initial concentration of the catalyst and
type of catalyst, but then when the initial concentration of a
catalyst is higher than a certain number, the recycling time no
longer depends on that factor anymore. In addition, the coke yield
increased rapidly when the concentration of Mo in the recycled
coke was lower than 1.2%, indicating that the catalyst has been
deactivated quickly. Therefore, both the Mo concentration in the
recycled coke and the age of the coke-catalyst mixture are the
determining factors to the catalyst deactivation and reusability.
Fig. 14 shows an XRD diffractogram of coke samples in a series
of recycling experiment. The peaks at 33 and 59 confirm the
exists of MoS2 crystal planes 11 0 and 1 0 0, respectively. By looking
at the peak intensity ratio between MoS2 crystal planes and
graphite, it is clear that those ratios are decreased following the
recycle times. That trend is due to the increase of coke fraction in
the recycled coke. The broad of peak areas of MoS2 in all
experiments indicates that there is no significant change or
agglomeration of MoS2 during recycling.
Aldridge and Bearden [40] announced a process in which both
oil-soluble dispersed Mo naphthenate and a solid iron compound
were used. After the reaction, a solid comprised of molybdenum
and iron compound was recovered and used as the catalyst for the
next hydrocracking reaction. As a result, a catalyst comprised of
molybdenum and the iron-containing coal ash showed good
activity retention in recycle runs not only for coke and light gas
suppression but also for metal removal and Conradson carbon
conversion.
Conclusions and future prospective
For the past few decades, renewable, nuclear and bio energy
have been developing rapidly, however, these could not satisfy the
ever-increasing energy demands, especially for transportation and
production. That demand requires a huge supply of distillate fuels
that are often produced from the refinery of conventional oil.
However, the capacity of conventional oil has been reducing
quickly since the 1950s. In contrast, unconventional oil is so
abundant and is gaining increasing attention.
11
Significant advantages have been obtained by gaining an
understanding of the role oil-soluble dispersed catalyst in
slurry-phase hydrocracking. Improvement of catalyst performance
is on the top priority to reduce the production cost as well as
undesired product that can harm for environment. Currently,
catalyst design attracts many attentions, the inventions of
bimetallic and multimetallic liquid catalysts are both the impres-
sive steps ahead; however, it is still very potential in the future. In
the other hand, using additive in hydrocracking is not a new ideal,
but it is very efficiency. Hydrogen donor is a great example; it
enhances the hydrogenation and results in better performance of
catalyst during reaction. Coke formation is another critical issue,
until now, the knowledge that relates to it is still very limited.
Investigation of coke and pre-treatment method before recycling
to the reactor is believed to be a crucial part of slurry phase
hydrocracking prospective.
Acknowledgment
This work was supported by the National Research Council of
Science & Technology (NST) grant by the Korea government (MSIP)
(No. CRC-14-1-KRICT).
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