China Petroleum Processing and Petrochemical Technology

Novel Technology 2015, Vol. 17, No. 4, pp 30-36 December 31, 2014

Development of Light Cycle Oil (LCO) Hydrocracking

Technology over a Commercial W-Ni Based Catalyst
Peng Chong1, 2; Yang Xuejing1; Fang Xiangchen1, 2; Huang Xinlu2; Cheng Zhenmin1;
Zeng Ronghui2; Guo Rong2
(1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology
(ECUST), Shanghai 200237; 2. Fushun Research Institute of Petroleum and Petrochemicals
(FRIPP), Sinopec, Fushun 113001)

Abstract: Because of its high density and low cetane number, the light cycle oil (LCO) containing heavy aromatics
(60%80%) can hardly be transformed through the conventional hydro-upgrading technology. In this report, a novel LCO
hydrocracking technology (FD2G) was proposed for the utilization of LCO to manufacture high value-added products.
Through the ingenious combination of hydroprocessing catalyst and the hydrocracking process, the high octane gasoline
and the ultra-low sulfur diesel (ULSD) blendstocks were produced simultaneously. The influence of catalyst type, reaction
temperature, pressure, respectively, on the research octane number (RON) of produced gasoline was studied in a fixed bed
hydrogenation reactor. It indicated that high reaction temperature and medium pressure would favor the production of high-
octane gasoline through the conversion of bi-aromatic and tri-aromatic hydrocarbons. The typical results of FD2G tech-
nology on commercial units showed that it could produce clean diesel with a sulfur content of less than 10 g/g and
clean gasoline with a research octane number (RON) of up to 92. It would be contributed to the achievement of the
maximum profit of a refinery, the FD2G technology could provide a higher economic efficiency than the other diesel
quality upgrading technology under the current gasoline and diesel price system.
Key words: LCO; hydrocracking; high octane gasoline; ULSD; aromatics

1Introduction fore besides desulfurization, the dearomatization process is

also needed to transform this stream into a feasible blending
Generally, LCO is a secondary stream obtained from
the catalytic cracking unit (FCC), having a boiling point component of refinery automotive diesel pool[4]. The disposal
similar to that of diesel. Its production is increasing in
step with the predicted role of the FCC unit for meeting
the increasing demand for light olefins and the increasing
trend of feeding heavy feedstocks into the FCC unit[1].
However, due to its high content of aromatics, high spe-
cific gravity, high sulfur and nitrogen contents as well as
low cetane rating[2], LCO is a poor diesel fuel blending
component. For instance, the aromatics content of LCO
delivered from FCC units varies between 75% and 90%.
The relatively high sulfur and nitrogen contents can go
up to 1.5 wt% and 750 g/g, respectively. Typically, its Figure 1Typical LCO properties and disposition
cetane index of LCO ranges from 15 to 25, whereas it can
be 4060 for the straight run distillates produced from
Received date: 2015-06-08; Accepted date: 2015-09-02.
the same crude[3] as summarized in Figure 1. In China, Corresponding Author: Prof. Fang Xiangchen, E-mail: fxc@
LCO amounts to over 33% of the distillate pool and there- ecust.edu.cn.

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 Peng Chong, et al. China Petroleum Processing and Petrochemical Technology, 2015, 17(4): 30-36

of LCO is one of the major concerns to the refiners.
LCO was reported to be treated either by catalytic crack-
ing[5-6] or hydrogenation[7-21]. The hydrocracking of LCO
is obviously of great interest in a bid to maximize the
economic profit of a refinery and upgrade the utiliza-
tion efficiency of the crude oil resource. In recent years,
LCO hydrocracking has been studied using model com-
pounds[22], light fractions of LCO[23] and the LCO blended
with other refinery streams[24]. Noble metals, such as Pt,
Pd and Pt-Pd alloy are reported to be more active for this
process. It is revealed that the acidity of the support is of
curial importance as well. Zeolite materials with medium
acidity showed high conversion, including H, HY and
HZSM-5[25]. The effects of pressure, temperature, space
velocity on LCO hydrocracking[26-30] were also studied.
Nevertheless, these noble metal catalysts are of low sta-
bility and are liable to fast deactivation during the hydro-
cracking of feeds with heteroatomic aromatics containing
S and N. Accordingly, these feeds require pretreatment
steps (hydrodesulfurization, hydrodenitrogenation, and
hydrodemetallization) prior to hydrocracking. Hydrotreat-
ing, aromatics saturation, and mild hydrocracking as well
as selective ring opening are primary elemental processes
for treating LCO. However, aiming to reduce the exces-
sive sulfur compounds, the harsh operating conditions
have to be applied. Meanwhile, the aromatic ring is usual-
ly over-saturated, which leads to the undesirable decrease
of the cetane number as well as the waste of hydrogen
resource. The UOP Company has developed a new LCO
UnicrackingTM technology, which can process LCO to
produce gasoline blendstocks with high octane number,
and then the LCO-X technology based on the LCO Uni-
crackingTM technology and selective alkyl transfer tech-
nology can produce benzene and xylene. However, it has
not yet been in practical use in commercial scale. In this
paper, we will introduce the LCO hydrocracking technology
(FD2G) for the production of a high octane gasoline based
on a commercial hydrogenation system based on non-noble
metal (W-Ni based) catalysts. This technology was developed
in 2002 and then was applied in commercial scale in 2013.
2Development of the Technology
Figure 2 demonstrates the hydrocarbon distribution of
a typical LCO produced using a Middle East vacuum
gas oil and residue. Numerous aromatic hydrocarbons
are found in LCO, including the majority of polycyclic
aromatic hydrocarbons, the di-aromatic content of which
reaches >50%. The proportion of polycyclic aromatic
hydrocarbons increases when the LCO narrow fractions
gradually become heavier, while mono-aromatics
content is reduced. The tri-aromatic hydrocarbons are
mainly concentrated in the fraction boiling at >290 .
The high aromatic content of LCO is undesirable in the
diesel fraction because aromatics in LCO can cause high
density and poor burning behavior of diesel fuel. Mean-
while, researchers also realize the potential value of poly-
aromatics in LCO, which can be hydrocracked selectively
into mono-aromatics to obtain high-octane gasoline.
Figure 2Distribution of aromatics in the LCO
tri-aromatic; di-aromatic; mono-aromatic
Hydrocracking technology is an excellent choice for
transforming the molecular structure of hydrocarbons and
upgrading oil quality. One of the characteristics of hydro-
cracking technology is the ability to control the occur-
rence of a reaction and the reaction extent by combining
catalysts with process technology. The FD2G technology
provides a full initiative effect on these characteristics, in-
cluding preventing mono-aromatics from being hydroge-
nated into naphthenes by controlling the hydroconversion
process, and ultimately transforming heavy aromatics into
light aromatics. For example, the ideal reaction pathway
of the FD2G technology in the di-aromatics hydrocrack-
ing reaction is demonstrated in Figure 3.
The key factors of this technology are the selection of a
suitable catalyst and operating conditions. The desired
reaction pathway is the transformation of di-aromatic and
triaromatic hydrocarbons contained in LCO to mono-
aromatics with high octane number in the gasoline distil-

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 Peng Chong, et al. China Petroleum Processing and Petrochemical Technology, 2015, 17(4): 30-36

Certain differences occur in selecting process parameters

between the FD2G and the conventional hydrocracking
process in order to maintain the content of light aromatic
hydrocarbons in the gasoline product as much as possible.
A series of experiments are performed in pilot units to de-
termine the optimized catalysts and operating conditions.

3.1The flow diagram

Figure 3The ideal reaction path of LCO hydrocracking
late, rather than further hydrogenation saturation into low
octane naphthenes. To maintain a proper operating run
length of the catalyst while obtaining high-octane gaso-
line is still an issue.
3Pilot Verification
Reaction conditions are the main factors that influence the
reaction rate. For example, both the reaction temperature
and space velocity can affect the conversion and product
distribution, while the hydrogen/oil volume ratio can af-
fect the hydrogen partial pressure in the system. The key
issue of the FD2G technology is controlling the degree
of aromatic hydrogenation saturation using appropriate
catalysts combined with the optimal process condition.
A fixed-bed hydrogenation unit is utilized, as shown in
Figure 4. All technical parameters are precisely controlled
using a distributed control system. Both top and bottom
of the reactor are filled with inert particles to maintain
the uniform distribution of fluids and to prevent catalyst
particles from entering the pipelines. The catalysts are
loaded into the hydrofining and cracking reactors with
dimensions of D/dp>18, and L/dp>350. (D, L, dp are the
inner diameter of the reactor, bed height, and catalyst
size, respectively.) Electrolytic hydrogen with a purity of
over 99.9 vol% is used in this experiment, and the content
of oxygen in hydrogen stream, which is subject to high-
pressure deoxygenation followed by dehydration using silica
gel, is less than 5 L/L. The tail oil can be recycled back to
the feed tank of this unit. Thus, the influence of different pro-
cess schemes on the reaction can be examined.
3.2Effects of the catalyst
Selecting a hydrocracking catalyst is an important step in

Figure 4Schematic flow diagram for a single-pass hydrocracking reactor system

1Feed tank; 2Oil pump; 3Hydrofining reactor; 4Hydrocracker; 5Gas-liquid separator; 6Fresh hydrogen; 7Recycle hydrogen;
8Compressor; 9Water scrubber

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 Peng Chong, et al. China Petroleum Processing and Petrochemical Technology, 2015, 17(4): 30-36
developing the FD2G technology; and the selected cata-
lyst used in the experiments is a multi-functional catalyst
with its active centers capable of performing hydrogena-
tion, cracking and isomerization reactions. A hydrocrack-
ing catalyst is usually designed according to the differ-
ences in raw materials and the requirements for targeted
products. Three different types of hydrocracking catalysts
are generally widely applied in industry. For instance, the
hydrocracking catalysts with strong acidity and relatively
weak hydrogenation activity are used to produce light
oil. The hydrocracking catalysts with medium acidity and
strong hydrogenation activity are used to produce middle
distillates. Single-stage hydrocracking catalysts have ap-
propriate hydrocracking activity, good quality mid-barrel
distillates, strong heterogeneous properties, and high se-
lectivity for diesel fuel with good cold flow property.
Theoretical analysis showed that the hydrocracking
catalysts for producing light oil were more suitable for
the hydrocracking process of light cycle oil. To produce
more gasoline with high octane number, light aromatic
hydrocarbons should be retained in the gasoline distillate
as much as possible. The effects of three different com-
mercial catalysts on LCO hydrogenation process under
the same conditions have been studied. The properties of
the three commercial catalysts are summarized in Table
1. The LCO is a stream with high sulfur content (1.05%)
and low cetane number (about 17) because of its high
aromatic content.
Figure 5 shows the results of LCO hydrocracking over
Table 1Properties of the catalyst used
Catalyst A Catalyst B
Catalyst C
Items (used in single- (for middle
(for light oil)
pass stage) distillate)
Active metal content, %
MoO3
WO3 22.0 24.0
NiO 5.8 6.8
Physical properties
Shape Cylindrical Cylindrical Cylindrical
Pore volume, mL/g 0.34 0.28
Specific surface area,
160 210
m2/g
Particle diameter, mm 1.41.7 1.41.6 1.41.6
Figure 5The effects of catalyst on LCO hydrocracking
RON; Aromatics content
different commercial catalysts under the same operating
conditions. It shows that a stream of excellent quality gas-
oline with a high research octane number of 84.4 and an
aromatic content of 57.8% could be obtained with catalyst
C. By contrast, the research octane number obtained using
catalysts A and B only reached 74.5 and 71.6, respective-
ly. Therefore, catalyst C is suitable for LCO hydrocrack-
ing because the strong acidic nature and relatively weak
hydrogenation activity of this catalyst could retain more
light aromatic hydrocarbons in gasoline.
3.3Effects of pressure
Studies have shown that the reaction pressure greatly affects
hydroprocessing reaction and aromatic content. The product
slate is directly related to the reaction pressure and hydroge-
nation saturation of aromatic components, which are more
advantageous under a higher pressure[31-35]. Pressure great-
ly influences the LCO hydrocracking, while 60%80%
of aromatics are found in the feed. Greater differences oc-
cur between LCO hydrocracking and conventional hydro-
cracking processes. Experiments under different reaction
pressure are conducted based on experiments 13 using
catalyst C. The RON of the gasoline distillates along with
15.0 the change of pressure are shown in Figure 6. It shows
that the research octane number of the gasoline distillate
increases significantly as the reaction pressure decreases
5.0
from 13.7 MPa to 6.0 MPa. The reduction in reaction
pressure is favorable to LCO hydrocracking for produc-
ing excellent high-octane gasoline. However, a decrease
0.29 in reaction pressure also hampers the overall productivity.
According to the general experience of industrial appli-
380
cations of conventional hydrocracking, a low operating
pressure affects the service life of catalyst, accelerates
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 Peng Chong, et al. China Petroleum Processing and Petrochemical Technology, 2015, 17(4): 30-36
coking, and hinders quality improvement of diesel prod-
ucts. Such hydrocracking requires a comprehensive con-
sideration to determine the proper pressure used in the
LCO hydrocracking technology.
Figure 6The effects of total pressure on the RON of
produced gasoline
Hydrogen /oil volume ratio= 1 200:1; LHSV= 0.8
3.4Effects of temperature
The reaction of aromatic hydrogenation is a reversible
exothermic reaction with the amount of substance re-
duced (hydrogen consumption). It means that the activa-
tion energy of the positive reaction (hydrogenation) is
lower than that of the reverse reaction (dehydrogenation).
Thus, the acceleration of the dehydrogenation reaction
will be more significant than that of hydrogenation reac-
tion, when the reaction temperature increases, which will
lead to the reduction of the equilibrium constant as well.
In consequence, the conversion rate of aromatics will
reach the maximum. The corresponding temperature to
the maximum conversion rate is the optimal temperature
for hydrogenation reaction. Below this temperature, the
hydrogenation of aromatic hydrocarbon is kinetic con-
trolled. Then, the conversion of aromatic hydrocarbon
will be greatly thermodynamically hampered, when the
temperature is higher than the optimal one. The balance
between thermodynamic limitation and the hydrogenation
degree of the aromatic hydrocarbons should be carefully
evaluated.
Another challenge on the technology development is to
control the hydrogenation of aromatics to avoid the ex-
cess hydrogenation of aromatic hydrocarbons. Higher re-
action temperature is favorable to this technology which
34
is verified by the experiments. As shown in Figure 7, the
cracking depth can be significantly improved and the
yield of gasoline distillate can increase by increasing the
reaction temperature. In consequence, the octane number
of gasoline fractions was increased with the increase of
the cracking depth.
Figure 7The effects of temperature on LCO hydrocracking
4Commercial Application
The LCO hydrocracking technology had been applied
in the hydrocracking unit I at the Jinling Petrochemical
Company in 2013 and Maoming Petrochemical Company
to successfully produce high research octane gasoline
and excellent quality diesel. Only the catalyst system was
changed, and process conditions were optimized with-
out large equipment modifications. The results showed
that this technology could produce gasoline blendstock
at a yield of 35%50% coupled with a high research
octane number of 9194 and a sulfur content of less
than 10 g/g. In addition, the sulfur content of clean die-
sel blendstock was also less than 10 g/g, and its cetane
number was increased by 1014 units as compared with
the feedstock.
At present, deep desulfurization and aromatic hydroge-
nation of diesel refining technology (HF), the maximum
diesel cetane number technology (MCI) have both been
applied in the commercial units. The systematic compari-
son between the HF technology, MCI technology and the
present FD2G technology are summarized in Table 2. The
main operating conditions, chemical hydrogen consump-
tion, the production yield and the properties of obtained
products were compared under the same quality of the
 Peng Chong, et al. China Petroleum Processing and Petrochemical Technology, 2015, 17(4): 30-36

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The FD2G technology can effectively convert heavy
aromatics in LCO to light aromatics through selective hy-
drocracking of aromatics, thereby producing high-octane
gasoline blendstocks and clean low-sulfur diesel blend-
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Typical results of FD2G technology on commercial units
show that it could produce clean diesel with a sulfur
content of less than 10 g/g and clean gasoline with a re-
search octane number (RON) of up to 92.
FD2G technology was deemed to be a good choice for
refineries abundant in FCC diesel with high aromatics
content and are seeking to improve cetane numbers and
produce more gasoline and aromatics.
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