Article
pubs.acs.org/IECR
Cite This: Ind. Eng. Chem. Res. 2019, 58, 2683−2688
Effects of Aging Treatment on the Hydrotreating Performance of the
Unsupported Catalyst
Changlong Yin,* Chengwu Dong, Yan Kong, Kunpeng Li, Haonan Zhang, Dong Liu,
and Chenguang Liu
Downloaded via UNIV OF EDINBURGH on March 3, 2020 at 18:36:02 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
State Key Laboratory of Heavy Oil Processing, Key Laboratory of Catalysis, China National Petroleum Corporation (CNPC), China
University of Petroleum, Qingdao, Shandong 266580, China
ABSTRACT: An unsupported Ni−Mo−W catalyst was synthesized by
the hydrothermal method and treated by an aging treatment to improve its
specific surface area and pore size. The effect of different aging conditions
was studied by BET, XRD, SEM, and HRTEM techniques. The catalytic
activity of the unsupported catalyst was evaluated with a simulated diesel
feed. BET results showed that the catalyst specific surface area and pore
volume increased significantly after aging treatment, and the hydrotreating
results revealed that aging treatment resulted in higher catalytic activity
than untreated catalyst, which is beneficial to the production of Ultra-LowSulfur Diesel (ULSD).
1. INTRODUCTION
Rapidly growing industry has brought people numerous
conveniences. However, a series of environmental problems,
such as industrial waste gas and automobile exhaust, are
considered to be the main cause of air pollution, which is a
result of deteriorating crude oil quality. Low-quality crude oil
contains more sulfur and nitrogen compounds, which can
cause serious air pollution.1−5 To solve this problem, it is
necessary to develop high activity diesel desulfurization and
denitrogenation catalysts. Traditional hydrogenation catalysts
were SiO2 or Al2O3 as support.6−8 Due to their low price and
excellent hydrogenation activity, these catalysts are widely used
in petroleum refining, but the low loading greatly limits further
improvement of catalytic activity, and the stricter diesel
standards cannot be met.9,10
Because of these questions, Albemarle, ExxonMobil, and the
Nippon Ketjen Corporation jointly developed new bulk
catalysts (NEBULA) in 2001,11,12 and achieved industrialization. These overcome the disadvantage of supported hydrotreating catalyst, greatly improving the activity of hydrogenation catalyst.13 The unsupported catalyst consists mainly
of Ni−Mo, Co−Mo, and Ni−W type catalysts. Ni−Mo and
Co−Mo catalysts have better hydrogenolysis,14 while Ni−W
catalyst is stronger in hydrogenation.15 To combine the
advantages of these two kind of catalysts, Soled et al.16
developed a Ni−Mo−W type three-component hydrogenation
catalyst, and the results showed that three-component
hydrogenation catalyst has higher activity in hydrodesulfurization (HDS) than two-component catalysts.
The extrusion technology of the unsupported catalyst is
different from that of traditional supported catalyst. Alumina or
silica is often used as binder for the unsupported catalyst. In
© 2019 American Chemical Society
the wet-mixing-kneading and extrusion processes, some of the
original pores in the precursor will be inevitably destroyed, and
the binder will also cover some of the active components and
the pores, which will thereby reduce the activity of the
extruded unsupported catalyst. So, it is very important to find a
solution for improving the strength and specific surface area of
unsupported catalyst.
As is well-known, aging is a key factor in dough-making in
the food process.17 During the aging process, water will
permeate into the protein colloidal particles and cause them to
expand, then adhere to form a network of dough. Throughout,
the water between the protein and starch can be adjusted
automatically to achieve homogenization, which is beneficial to
the improvement of dough toughness. Based on the views
above, we treated the unsupported catalyst mixture by aging
before extrusion, and the effects of aging temperature and
aging time on the performance of the unsupported catalyst
were evaluated.
2. EXPERIMENTAL SECTION
2.1. Preparation of Unsupported Ni−Mo−W Catalyst
Precursors. The unsupported Ni−Mo−W catalyst precursors
were synthesized by the hydrothermal method. Basic nickel
carbonate, hexaammonium molybdate, and ammonium metatungstate (purchased from Sinopharm Chemical Reagent
Company, PR China) with some deionized water were placed
in a beaker in the molar ratio of Ni:Mo:W = 2:1:1; the mixture
Received:
Revised:
Accepted:
Published:
2683
October 3, 2018
January 29, 2019
February 4, 2019
February 4, 2019
DOI: 10.1021/acs.iecr.8b04849
Ind. Eng. Chem. Res. 2019, 58, 2683−2688
Article
Industrial & Engineering Chemistry Research
m
was stirred with a magnetic stirrer. The mixed solution was
then put into an autoclave (S-2L, China), and reacted for 10 h
at 150 °C to get a Ni−Mo−W catalyst precursor suspension.
The suspension was filtered with a vacuum filter, washed
several times with deionized water, and the filter cake was
dried overnight at 120 °C to get the unsupported Ni−Mo−W
catalyst precursor.
2.2. Preparation of Unsupported Ni−Mo−W Catalyst.
Alumina was used as binder of Ni−Mo−W composite oxide
(precursor/alumina ratio = 80/20). Polyethylene glycol 2000
was used as the pore expanding agent. Acetic acid was used as
glue solvent. The detailed synthesis steps are as follows: First,
the right amounts of alumina and Polyethylene glycol 2000
were mixed in a beaker; the acetic acid and distilled water were
slowly added to get a homogeneous mixture. Then Ni−Mo−W
composite oxides were added, and kneaded uniformly to get a
green solid mixture. The solid mixture was put in a sealed
beaker, and heated in a water bath for 1−4 h at 40−90 °C as
aging. To obtain the fixed-bed catalysts, the aged solid mixtures
were extruded into rods 1.6 mm in diameter with a single
screw extruder; the products were dried at 120 °C and calcined
at 400 °C to get the unsupported oxidic Ni−Mo−W catalyst.
The XRF result shows that the final composition of
unsupported oxidic Ni−Mo−W catalyst is NiO (25.4%),
MoO3 (23.7%), and WO3 (31.2%). The unmodified catalyst
was labeled Cat-0. Catalysts aged at different temperature for 2
h were labeled Cat-40-2, Cat-60-2, Cat-80-2, and Cat-90-2.
The catalysts aged at 80 °C for various times were labeled Cat80-1, Cat-80-2, Cat-80-3, and Cat-80-4.
Theoretically, the aging temperature can be from room
temperature to more than 100 °C. However, considering that
treatment at high temperature may result in reduced strength
of the catalyst, we choose a mild temperature condition, 40−90
°C in this manuscript. Also, temperature that is too low will
make the aging effect very small.
2.3. Characterization. The specific surface area, pore
volume, and pore diameter of the catalysts were measured with
a Micromeritics Tristar 3000 multifunction adsorption instrument (USA). First, the samples were degassed in vacuum for 6
h at 300 °C, and then N2 was adsorbed at −196 °C, the
specific surface area was calculated by the BET (BrunauerEmmett -Teller) method, and the pore volume and pore
diameter distribution curve were calculated by the BJH
(Barrett−Joyner−Halenda) method. The catalyst crystal
phase was analyzed with X-ray diffractometer with Cu Kα
radiation (Panalytical). The morphology of the catalysts was
obtained by using a S-4800 cold field emission scanning
electron microscope (Hitachi company) with a magnification
of 30−800 000. The dispersion of the sulfide active
components was obtained by transmission electron microscopy
(JEM-2100UHR) (Japanese Electronic Company). Then, the
length (L) of the active component and the stacking layers
number (N) were calculated by counting more than 600
layered crystalline grains in at least 15 representative
micrographs. The average layer length (LA) and the average
stacking layer number (NA) were calculated according to
formula 1 and 2.
n
LA =
i=1
m
∑ miNi/∑ mi
i=1
(2)
i=1
The length of the active components was labeled Li, and the
number of stacking layers is labeled Ni. The number of
crystallites with specific length i was represented as ni, and the
number of crystallites with the specific stacking layer number i
was represented as mi.
The MoS2/WS2 dispersion, f Mo/W, was calculated by
dividing the total number of Mo/W atoms at the edge surface
by the total number of Mo/W atoms. By assuming that MoS2/
WS2 slabs are present as perfect hexagons, eq 3 was derived.18
n
fMo/W =
∑i = 1 (6xi − 6)
n
∑i = 1 (3xi2 − 3xi + 1)
(3)
where xi is the number of Mo/W atoms along one edge of a
MoS2/WS2 slab determined from its length (L = 3.2(2xi − 1)
(Å)), and n is the total number of slabs shown in the TEM
micrographs.
2.4. Catalytic Activity Evaluation. The catalyst evaluation was carried out on a 10 mL high pressure microreactor. A
volume of 5 mL catalyst was placed in the middle of the
reaction tube, and the upper and bottom parts of the tube were
filled with quartz sand. The size of the catalysts and quartz
sand particles were 20−40 meshes. The catalysts were
presulfided at 320 °C for 10 h with a cyclohexane solution
containing 3 wt % CS2 at a pressure of 5 MPa and a H2/oil
volume ratio of 300:1. A simulated diesel (1.5 wt % DBT, 5 wt
% naphthalene, and 2 wt % quinoline) in petroleum ether was
used as the feed. The reaction conditions were as follows: total
H2 pressure of 4 MPa, liquid hourly space velocity (LHSV) of
2.0 h−1, H2 /oil volume ratio of 300:1, and reaction
temperature of 280 °C. The samples were collected after 12
h, and analyzed with a GC-214 type chromatograph (Bruker
Corporation). The space time yield of the catalyst was
calculated by eq 4
Y (A ) =
N
× Conv(A)
V
(4)
where Y(A) is the space time yield of A (mol/(mL·h)), N is
the moles of feed per hour (mol/h), Conv(A) represents the
conversion of A, and V is the volume of catalyst (mL).
3. RESULTS AND DISCUSSION
3.1. Effects of Different Aging Conditions. 3.1.1. N2
Adsorption−Desorption. Table 1 shows the N2 adsorption−
desorption results at different aging temperatures. The specific
surface area, pore volume, pore diameter, and mechanical
strength of the catalysts are improved after aging. On the
whole, specific surface area first increases and then decreases
with increasing aging temperature. When the aging temperTable 1. Physical Properties of Unsupported Ni−Mo−W
Oxide Catalyst Treated at Different Aging Temperature
n
∑ niLi /∑ ni
i=1
NA =
(1)
2684
Catalyst
SBET/
(m2·g−1)
VP/
(cm3·g−1)
DP /
nm
Bulk density/
(g·mL−1)
Strength/
(N·cm−1)
Cat-0
Cat-40-2
Cat-60-2
Cat-80-2
Cat-90-2
193
202
238
241
234
0.24
0.30
0.33
0.32
0.32
4.4
5.0
5.6
5.3
5.2
1.3
1.2
1.1
1.1
1.1
90
104
107
113
113
DOI: 10.1021/acs.iecr.8b04849
Ind. Eng. Chem. Res. 2019, 58, 2683−2688
Article
Industrial & Engineering Chemistry Research
ature is 80 °C, the specific surface area reaches a maximum
value of 241 m2·g−1, but at a different aging temperature, the
pore volume, pore diameter, and strength hardly change. On
the whole, after aging, the specific surface area, pore volume,
and pore diameter of the catalysts increased by about 19%,
32%, and 20%, respectively. Table 2 presents the N 2
Table 2. Physical Properties of Unsupported Ni−Mo−W
Oxide Catalyst Treated after Different Aging Time
Catalyst
SBET/
(m2·g−1)
VP/
(cm3·g−1)
DP /
nm
Bulk density/
(g·mL−1)
Strength/
(N·cm−1)
Cat-0
Cat-80-1.0
Cat-80-2.0
Cat-80-3.0
Cat-80-4.0
193
238
241
237
232
0.24
0.31
0.32
0.30
0.31
4.4
5.6
5.3
5.4
5.0
1.3
1.1
1.1
1.1
1.1
90
111
113
111
110
adsorption−desorption results after different aging times.
From Table 2, with the extension of aging time, the catalyst
has the highest specific surface area of 241 m2·g−1 with the
aging time of 2 h. On the whole, after aging, the specific surface
area, pore volume, and pore diameter of the catalysts increased
by about 23%, 29%, and 21%, respectively. It is suggested that
the catalyst needs an optimal aging time; too long or too short
is not conducive to the improvement of specific surface area
and pore structure.
3.2. Effects of Aging on the Physicochemical Properties of Unsupported Ni−Mo−W Catalysts. 3.2.1. XRD.
XRD patterns of the unsupported Ni−Mo−W catalyst
precursors before and after aging treatment are illustrated in
Figure 1. All catalysts have the same diffraction peaks closed to
Figure 2. SEM micrographs of oxide and sulfided catalysts before and
after aging treatment: Oxide catalyst before (A) and after (B) aging;
sulfided catalysts before (C) and after (D) aging treatment.
aging, a more uniform pore structure appears, which is
favorable for hydrotreating catalysts. The sulfided images (C)
and (D) also show that the catalyst treated with aging is
composed of smaller and more dispersed particles, and their
overall structure is more loose and porous, which favors the
dispersion of active components.
3.2.3. HRTEM. It is generally believed that the active
component of sulfided Ni−Mo−W catalyst has a MoS2/WS2
structure, and these structures are usually observed by
HRTEM photographs. Figure 3 presents the HRTEM results
Figure 3. HRTEM photographs of sulfided unsupported Ni−Mo−W
catalysts before (A) and after (B) aging treatment.
of the sulfided Ni−Mo−W catalyst before and after aging. The
photograph shows many striped black lines. These threadlike
fringes exist in a parallel cluster structure with about 0.6 nm
interplanar spacing, which is the typical MoS2/WS2 interplanar
spacing,13,19,20 implying the existence of MoS2/WS2 structures.
In addition, another lamellar structure with about 0.3 nm
interplanar spacing can be seen in Figure 3B, which can be
attributed to the Ni3S2 lamellar structure.21,22 As a whole,
MoS2/WS2 is evenly distributed on the edge of Ni3S2, so that
the two structures can be fully combined, which improves their
synergistic effect.22 Figure 4 shows the XRD pattern of sulfided
unsupported Ni−Mo−W catalysts before and after aging
treatment, XRD results also show the existence of Ni3S2 and
MoS2/WS2 structures, but the diffraction peaks of MoS2/WS2
are overlapping; we cannot tell them apart. In order to further
study the change of MoS2/WS2 structure after aging, the
stacking layer number and laminar length of MoS2/WS2
structures were calculated, and the statistical results are
Figure 1. XRD patterns of the unsupported Ni−Mo−W catalyst
before (A) and after (C) aging treatment and unsupported Ni−Mo−
W catalyst precursor (B).
amorphous structure, which can be attributed to the
unsupported Ni−Mo−W catalyst precursors, indicating that
aging treatment does not affect the crystallization of
unsupported Ni−Mo−W catalysts, but changes its pore
structure.
3.2.2. SEM. The SEM images of oxidized and sulfided
catalysts are shown in Figure 2. Figure 2A,B shows that the
catalyst before aging has a lamellar structure, which is not
conducive to the formation of loose and porous structure,
resulting in a smaller specific surface area. However, after
2685
DOI: 10.1021/acs.iecr.8b04849
Ind. Eng. Chem. Res. 2019, 58, 2683−2688
Article
Industrial & Engineering Chemistry Research
Table 3. Average Slab Length (LA) and Layers (NA) of
MoS2/WS2a
a
Catalyst
LA/ nm
LA/ nm (L ≥ 10)
NA
f Mo/W
Cat-0
Cat-80-2
5.4 ± 2.5
4.9 ± 2.2
11.9
10.8
3.6 ± 1.5
4.0 ± 1.9
0.18
0.20
Values are the means ± standard deviations.
results in lower slab lengths and higher stacking layers of
MoS2/WS2 crystallites, which is mainly concentrated in 3−5
nm and 2−8, respectively. The average slab lengths and
stacking numbers of MoS2/WS2 crystallites are presented in
Table 3. From the data, we can find that the average slab
lengths and the average stacking numbers of the catalysts with
and without aging treatment are almost consistent in
considering the standard deviations. However, the average
length of the larger slabs (≥10 nm) for the aged catalyst
decreased from 11.9 to 10.8 nm, indicating that aging
treatment can mainly disperse the larger catalyst particles
into smaller particles. In addition, the f Mo/W also was shown in
Table 3; the f Mo/W can reflect the dispersion of the active
component: the higher the f Mo/W is, the better the catalyst
dispersion is. From Table 3, the f Mo/W is slightly higher for
Cat-80-2 (0.20) than Cat-0 (0.18), and this is chiefly because
aging treatment can disperse large particles into small ones,
and then improve the dispersion of the catalyst, which is also
beneficial to the improvement of the hydrogenation activity of
the catalyst.23
3.3. Catalytic Performance Evaluation. Catalytic activity
results of sulfided unsupported Ni−Mo−W catalysts are
summarized in Tables 4, 5, and 6. Table 4 show the
Figure 4. XRD pattern of sulfided unsupported Ni−Mo−W catalysts
before and after aging treatment.
summarized in Figures 5 and 6, while the average slab length
and layers of MoS2/WS2 are summarized in Table 3.
Table 4. Product Distribution of the HDS of DBT under
Different Aging Conditions
Figure 5. Relationship between MoS2/WS2 slab lengths and
frequency of occurrence.
Catalyst
BPa
CHBb
BCHc
BCPd
HDS (%)
YeHDS
Cat-0
Cat-40-2
Cat-60-2
Cat-80-2
Cat-80-1
Cat-80-3
Cat-80-4
82.2
82.3
72.8
70.4
81.4
76.4
76.3
13.3
13.2
12.7
14.8
13.5
13.9
13.6
2.3
2.4
9.3
9.2
2.6
6.8
8.9
1.2
1.2
5.0
5.5
1.8
2.7
1.0
89.0
90.1
92.8
99.9
95.3
97.8
98.8
9.4
9.9
10.2
11.0
10.4
10.7
10.8
a
Biphenyl. bCyclohexylbenzene. cBicyclohexane. dBenzyl cyclopentane. eSpace time yield (mol/mL (cat.)·h/10−5).
hydrogenation product distribution of the HDS of DBT
under different aging conditions for unsupported Ni−Mo−W
catalysts. Aging treatment leads to higher DBT conversion
Table 5. Product Distribution of Quinoline under Different
Aging Conditions
Figure 6. Relationship between MoS2/WS2 stacking layer number and
frequency of occurrence.
Figures 5 and 6 show the distribution of the lengths and
stacking layers of MoS2/WS2 crystallites, respectively. The slab
lengths of MoS2/WS2 are within the range of 1−15 nm, and
the stacking numbers are between 2 and 12. Specifically, aging
a
Catalyst
THQa
DHQb
Quinoline
HDN (%)
YcHDN
Cat-0
Cat-40-2
Cat-60-2
Cat-80-2
Cat-80-1
Cat-80-3
Cat-80-4
34.3
38.7
26.3
23.1
34.2
24.3
19.9
0.2
0.9
1.1
1.8
1.2
1.7
1.8
2.1
1.8
0.9
0.5
1.2
1.6
3.2
60.3
60.4
72.6
73.5
63.4
72.4
75.1
12.1
12.1
14.6
14.8
12.7
14.6
15.1
Tetrahydroquinoline. bDecahydroquinoline.
((mol/mL (cat.)·h/10−5).
2686
c
Space time yield
DOI: 10.1021/acs.iecr.8b04849
Ind. Eng. Chem. Res. 2019, 58, 2683−2688
Article
Industrial & Engineering Chemistry Research
After aging, the binder can fully extend to the surrounding
by absorbing water, so as to form a larger space for the catalyst
particles dispersion, which leads to a more loose and porous
structure (Figure 7). On the other hand, aging can also
promote the fully absorbing water of catalyst particles.
Therefore, the initially aggregated catalyst particles are
dispersed into smaller particles uniformly dispersed on the
binder, which improves the specific surface area and pore
structure of the catalysts, so that the active components are
exposed more fully, and increase the probability of contacting
with the impurities in the diesel; then, the hydrogenation effect
is improved.
The HRTEM results of sulfided unsupported Ni−Mo−W
catalyst revealed that aging is also conducive to the uniform
dispersion of the active phase, promoting the synergistic effect
of Ni3S2 and MoS2/WS2, which is the key factor to improve the
hydrogenation activity of the catalyst.27
Table 6. Product Distribution of Naphthalene under
Different Aging Conditions
Catalyst
Tetralin
Cis-Decalin
Trans-Decalin
HDAr (%)
YaHDAr
Cat-0
Cat-40-2
Cat-60-2
Cat-80-2
Cat-80-1
Cat-80-3
Cat-80-4
25.8
26.8
27.4
30.4
16.6
23.8
23.1
1.3
0.9
1.1
2.3
1.5
1.7
1.4
2.4
1.8
2.1
5.6
3.1
2.9
3.0
29.5
29.9
30.6
38.3
31.6
32.2
31.7
15.0
15.2
15.5
19.4
16.0
16.3
16.1
Space time yield ((mol/mL (cat.)·h/10−5).
a
than untreated Ni−Mo−W catalyst. The catalyst matured at 80
°C for 2 h has the highest DBT conversion of 99.9%. Table 5
gives the hydrogenation result of quinoline. Before aging, the
hydrodenitrogenation rate of quinoline is 60.3%; aging at 80
°C for 2 h results in a higher hydrodenitrogenation rate of
73.5%, which is very considerable due to the low hydrodenitrogenation (HDN) rate of diesel.24 It illustrated that the
catalyst matured at 80 °C for 2 h has the highest
hydrogenation activity. Table 6 shows the product distribution
of naphthalene. The hydrogenation products of naphthalene
are mainly tetralin and decalin. On the whole, the conversion
rate of naphthalene is relatively low. The reason is that there is
a competition of different substances in the process of
hydrogenation,25,26 but it can be enhanced to 38.3% from
29.5% by aging, which further illustrates that the hydrogenation activity of the catalyst can be improved with aging.
3.4. Mechanism of Aging on Improving the Hydrogenation Activity of Catalyst. According to the SEM results
of catalyst precursors, the mixture of binder, glue solvent, and
unsupported Ni−Mo−W catalyst precursor powder was
kneaded into catalyst mixture. At the beginning, the binder,
glue solvent, and unsupported Ni−Mo−W catalyst precursor
powder aggregate together without fully absorbing water,
which is detrimental to the formation of the porous structure
and the particles dispersion. The catalyst particles aggregate
together without being uniformly dispersed on the binder,
causing low specific surface area, which restricts the full
exploitation of active components, reducing the hydrogenation
activity of the unsupported Ni−Mo−W catalyst.
4. CONCLUSION
The solid mixture kneaded with binder, glue solvent, and
unsupported Ni−Mo−W catalyst precursor powder was
treated by aging. The results show that aging can not only
reduce the particle size of the catalyst and thus improve the
specific surface area, but also significantly enhance the strength
of the catalyst, which is conducive to industrial application.
The HRTEM results reveal that aging also promotes the
synergistic effect of Ni3S2 and MoS2/WS2, which favors the
improvement of the catalyst hydrogenation activity. The aging
condition of the catalyst was investigated, and we found that
the catalyst aged at 80 °C for 2 h had the higher specific
surface area. The hydrogenation performance of the catalyst
before and after aging was evaluated with a simulated diesel
feed. The results suggest that aging can give a higher
hydrogenation activity.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: yincl@upc.edu.cn. Tel: +86-532-86984629.
ORCID
Changlong Yin: 0000-0001-6750-6274
Notes
The authors declare no competing financial interest.
Figure 7. Sketch for aging of unsupported Ni−Mo−W catalyst.
2687
DOI: 10.1021/acs.iecr.8b04849
Ind. Eng. Chem. Res. 2019, 58, 2683−2688
Article
Industrial & Engineering Chemistry Research
■
(17) Cao, S. Y.; Lin, Y.; Yin, X. H.; Hong-Sheng, L. I.; Ming-Yi, Q.;
Tang, R.; Luo, Z. The effect of making process about rice flour on
springiness of fresh rice noodle. Food Science & Technology, 2017.
(18) Kasztelan, S.; Toulhoat, H.; Grimblot, J.; Bonnelle, J. P. A
geometrical model of the active phase of hydrotreating catalysts. Appl.
Catal. 1984, 13 (1), 127−159.
(19) Yin, C.; Zhao, L.; Bai, Z.; Liu, H.; Liu, Y.; Liu, C. A novel
porous ammonium nickel molybdate as the catalyst precursor towards
deep hydrodesulfurization of gas oil. Fuel 2013, 107 (9), 873−878.
(20) Payen, E.; Hubaut, R.; Kasztelan, S.; Poulet, O.; Grimblot, J.
Morphology Study of MoS2- and WS2-Based Hydrotreating Catalysts
by High-Resolution Electron Microscopy. J. Catal. 1994, 147 (1),
123−132.
(21) Ghezelbash, A.; Korgel, B. A. Nickel sulfide and copper sulfide
nanocrystal synthesis and polymorphism. Langmuir 2005, 21 (21),
9451.
(22) Yin, C.; Wang, Y.; Xue, S.; Liu, H.; Li, H.; Liu, C. Influence of
sulfidation conditions on morphology and hydrotreating performance
of unsupported Ni−Mo−W catalysts. Fuel 2016, 175, 13−19.
(23) Hensen, E. J. M.; Kooyman, P. J.; van der Meer, Y.; van der
Kraan, A. M.; de Beer, V. H. J.; van Veen, J. A. R.; van Santen, R. A.
The Relation between Morphology and Hydrotreating Activity for
Supported MoS2 Particles. J. Catal. 2001, 199 (2), 224−235.
(24) Angelici, R. J. An overview of modeling studies in HDS, HDN
and HDO catalysis. Polyhedron 1997, 16 (18), 3073−3088.
(25) Schulz, H.; Böhringer, W.; Waller, P.; Ousmanov, F. Gas oil
deep hydrodesulfurization: refractory compounds and retarded
kinetics. Catal. Today 1999, 49 (1−3), 87−97.
(26) Girgis, M. J.; Gates, B. C. Reactivities, reaction networks, and
kinetics in high-pressure catalytic hydroprocessing. Ind. Eng. Chem.
Res. 1991, 30 (9), 2021−2058.
(27) Pedraza, F.; Fuentes, S. Ni−Mo and Ni−W sulfide catalysts
prepared by decomposition of binary thiometallates. Catal. Lett. 2000,
65 (1−3), 107−113.
ACKNOWLEDGMENTS
This work was financially supported by the National Key R &
D program of China (2017YFB0602500), the National Natural
Science Fund of China (Grant No. 21676301), and Shandong
Province Natural Science Foundation (Grant No.
ZR2016BM19). Financial support from PetroChina Corporation Limited was also greatly appreciated.
■
REFERENCES
(1) Amaya, S. L.; Alonso-Núñez, G.; Zepeda, T. A.; Fuentes, S.;
Echavarría, A. Effect of the divalent metal and the activation
temperature of NiMoW and CoMoW on the dibenzothiophene
hydrodesulfurization reaction. Appl. Catal., B 2014, 148−149, 221−
230.
(2) Song, C. An overview of new approaches to deep desulfurization
for ultra-clean gasoline, diesel fuel and jet fuel. Catal. Today 2003, 86
(1), 211−263.
(3) Souza, M. J. B.; Pedrosa, A. M. G.; Cecilia, J. A.; Gil-Mora, A.
M.; Rodríguez-Castellón, E. Hydrodesulfurization of dibenzothiophene over PtMo/MCM-48 catalysts. Catal. Commun. 2015, 69,
217−222.
(4) Stanislaus, A.; Marafi, A.; Rana, M. S. Recent advances in the
science and technology of ultra low sulfur diesel (ULSD) production.
Catal. Today 2010, 153 (1), 1−68.
(5) Liu, H.; Yin, C.; Li, X.; Chai, Y.; Li, Y.; Liu, C. Effect of NiMo
phases on the hydrodesulfurization activities of dibenzothiophene.
Catal. Today 2017, 282, 222−229.
(6) Egorova, M.; Prins, R. Hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene over sulfided NiMo/γAl2O3, CoMo/γ-Al2O3, and Mo/γ-Al2O3 catalysts. J. Catal. 2004, 225
(2), 417−427.
(7) Li, X.; Wang, A.; Egorova, M.; Prins, R. Kinetics of the HDS of
4,6-dimethyldibenzothiophene and its hydrogenated intermediates
over sulfided Mo and NiMo on γ-Al2O3. J. Catal. 2007, 250 (2), 283−
293.
(8) Zhao, Y.; Prins, R. Mechanisms of hydrodenitrogenation of
alkylamines and hydrodesulfurization of alkanethiols on NiMo/Al2O3,
CoMo/Al2O3, and Mo/Al2O3. J. Catal. 2005, 229 (1), 213−226.
(9) Guzmán, M. A.; Huirache-Acuña, R.; Loricera, C. V.; Hernández,
J. R.; Diaz de León, J. N.; de los Reyes, J. A.; Pawelec, B. Removal of
refractory S-containing compounds from liquid fuels over P-loaded
NiMoW/SBA-16 sulfide catalysts. Fuel 2013, 103 (1), 321−333.
(10) Zhang, M. H.; Fan, J. Y.; Chi, K.; Duan, A. J.; Zhao, Z.; Meng,
X. L.; Zhang, H. L. Synthesis, characterization, and catalytic
performance of NiMo catalysts supported on different crystal alumina
materials in the hydrodesulfurization of diesel. Fuel Process. Technol.
2017, 156, 446−453.
(11) Plantenga, F. L.; Cerfontain, R.; Eijsbouts, S.; van Houtert, F.;
Anderson, G. H.; Miseo, S.; Soled, S.; Riley, K.; Fujita, K.; Inoue, Y.
89 “Nebula”: A hydroprocessing catalyst with breakthrough activity.
Stud. Surf. Sci. Catal. 2003, 145 (03), 407−410.
(12) Eijsbouts, S.; Mayo, S. W.; Fujita, K. Unsupported transition
metal sulfide catalysts: From fundamentals to industrial application.
Appl. Catal., A 2007, 322 (6), 58−66.
(13) Gochi, Y.; Ornelas, C.; Paraguay, F.; Fuentes, S.; Alvarez, L.;
Rico, J. L.; Alonso-Núñez, G. Effect of sulfidation on Mo-W-Ni
trimetallic catalysts in the HDS of DBT. Catal. Today 2005, 107−108
(44), 531−536.
(14) Grange, P.; Vanhaeren, X. Hydrotreating catalysts, an old story
with new challenges. Catal. Today 1997, 36 (4), 375−391.
(15) Vradman, L.; Landau, M. V. Structure−Function Relations in
Supported Ni−W Sulfide Hydrogenation Catalysts. Catal. Lett. 2001,
77 (1−3), 47−54.
(16) Soled, S. L.; Miseo, S.; Krycak, R.; Vroman, H.; Ho, T. C.;
Riley, K. L., Nickel molybodtungstate hydrotreating catalysts; U.S.
Patent 6,299,760 B1, 2001.
2688
DOI: 10.1021/acs.iecr.8b04849
Ind. Eng. Chem. Res. 2019, 58, 2683−2688