Design and synthesis of metal sulfide catalysts supported on zeolite nanofiber bundles with unprecedented hydrodesulfurization activities

Article abstract of DOI:10.1021/ja4043388

Developing highly active hydrodesulfurization (HDS) catalysts is of great importance for producing ultraclean fuel. Herein we report on crystalline mordenite nanofibers (NB-MOR) with a bundle structure containing parallel mesopore channels. After the introduction of cobalt and molybdenum (CoMo) species into the mesopores and micropores of NB-MOR, the NB-MOR-supported CoMo catalyst (CoMo/NB-MOR) exhibited an unprecedented high activity (99.1%) as well as very good catalyst life in the HDS of 4,6-dimethyldibenzothiophene compared with a conventional γ-alumina-supported CoMo catalyst (61.5%). The spillover hydrogen formed in the micropores migrates onto nearby active CoMo sites in the mesopores, which could be responsible for the great enhancement of the HDS activity.

Full text of DOI:10.1021/ja4043388

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Communication
Design and Synthesis of Metal Sulfide Catalysts Supported on Zeolite
Nanofiber Bundles with Unprecedented Hydrodesulfurization Activities
Tiandi Tang, Lei Zhang, Wenqian Fu, Yuli Ma, Jin Xu, Jun Jiang, Guoyong Fang, and Feng-Shou Xiao
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 19 Jul 2013
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Design and Synthesis of Metal Sulfide Catalysts Supported
on Zeolite Nanofiber Bundles with Unprecedented Hy-
drodesulfurization Activities
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Tiandi Tang,*,† Lei Zhang,† Wenqian Fu,† Yuli Ma,† Jin Xu,† Jun Jiang,† Guoyong Fang,† and Feng-
Shou Xiao*,‡
† College of Chemical and Materials Engineering Wenzhou Unveristy, Wenzhou 325035, P. R. China
‡ Department of Chemistry, Zhejiang University Hangzhou 310028, P. R. China
Supporting Information Placeholder
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ABSTRACT: Developing highly active hydrodesulfurization
(HDS) catalysts is of great importance for producing ultra-clean
fuel. Herein, we show crystalline mordenite nanofibers (NB-MOR)
with bundle structure containing parallel-mesopore channels.
After introducing cobalt and molybdenum (CoMo) species in the
mesopores and micropores of NB-MOR, the NB-MOR supported
CoMo catalyst (CoMo/NB-MOR) exhibits an unprecedented high
activity (99.1%) as well as very good catalyst life in the HDS of
4,6-DMDBT, compared with a conventional γ-alumina-supported
CoMo catalyst (61.5%). The spillover hydrogen formed in the
micropores migrates onto nearby active CoMo sites in the meso-
pores, which could be responsible for the great enhancement of
HDS activities.
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Increasingly stringent environmental legislation is pressuring
manufacturers to reduce the sulfur content in gasoline and diesel
fuel to a level of 10 ppm and lower.1 To reach this low sulfur
level, even highly refractory sulfur compounds in the fuel, such as
4,6-dimethyldibenzothiophene (4,6-DMDBT), must be almost
completely removed.2 Generally, conventional hydrodesulfuriza-
tion (HDS) catalysts, γ-alumina-supported metal sulfides (Co-
Mo/γ-Al2O3 or NiMo/γ-Al2O3), have difficulty to fully remove
4,6-DMDBT due to steric hindrance by the methyl groups adja-
cent to the sulfur atom.3 One of the solutions for this problem is to
increase the hydrogenating ability by replacing the metal sulfides
by noble metals.4 However, the relatively short catalyst life and
high cost of these noble metals strongly limit their applications.5
e
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It has been reported that hydrogen spillover can greatly en-
hance the hydrogenating ability;6 thus, an improvement of the
hydrogen spillover ability for conventional HDS catalysts would
facilitate very high HDS activities.7 Thanks to recent successful
syntheses on mesoporous zeolites,8 it should be possible to design
catalytic active sites in micropores and mesopores of mesoporous
zeolites that have hydrogen spillover ability and hydrogenating
ability, respectively.
Figure 1. (a) XRD patterns, (b) N2 adsorption isotherm, (c) low
resolution SEM image, (d) high resolution SEM image, (e) low
resolution TEM image and (f) high resolution TEM image (Fast
Fourier Transform (FFT) inset.) of NB-MOR sample.
Herein, we first report a facile method to synthesize nanofiber
bundles of zeolite MOR (NB-MOR). The resulting material has
parallel-mesopore channels in the nanofiber bundles of the mi-
croporous MOR zeolite. In addition, after introducing cobalt and
molybdenum species in the mesopores and micropores,
followed by sulfidation, the NB-MOR supported CoMo catalyst
(CoMo/NB-MOR) exhibits an unprecedented high activity in the
HDS of 4,6-DMDBT, compared with conventional Co-
Mo(NiMo)/γ-Al2O3 catalysts. This feature may be attributed to
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Figure 2. (a) Low resolution TEM image of the sulfided CoMo/NB-MOR catalyst. (b) High resolution TEM image in the selected area in
Figure 2a marked by white square. (c) High resolution TEM image of the sulfided CoMo/γ-Al2O3 catalyst.
the migration of spillover hydrogen formed in the micropores
onto nearby active CoMo sites in the mesopores, which signifi-
cantly enhances the hydrogenating ability of the catalyst. This
catalyst design concept provides a new strategy for the rational
preparation of multi-functional highly active catalysts.
consist of parallel zeolite nanofibers (Figure 1d-f). The zeolite
nanofibers have diameters ranging from 10-30 nm and these
nanofibers aggregate into bundles. In this manner, parallel-
mesoporous channels are formed in the aggregated bundles (Fig-
ure S2). Furthermore, fast fourier transfrom (FFT) of the NB-
MOR TEM image (insert in Figure 1f) shows that the b-axis of
MOR (010 face, pore size at 3.4 × 4.8 Å) is perpendicular to the
mesopore direction. This micro-mesopore structure feature could
be beneficial for the mass transfer of small molecules such as
hydrogen from micropores to mesopores.
Despite the recent successful synthesis of nano-sized zeolite
materials, such as nanosheets and nanoparticles by using
mesoscale organic templates,9 it is difficult to obtain zeolite nano-
fibers by the similar route. In this work, we synthesized a random
cationic copolymer containing quaternary ammonium groups and
used it as a template for the synthesis of mordenite zeolite nano-
fibers, which can be assembled to a bundle structure (see section
S1 in the Supporting Information).
In catalyst preparation, the aim is to disperse the active metal
species not only in the mesoporous channels but also in the mi-
cropores of the NB-MOR. To introduce the active metal species
into the support micropores, the pH of the impregnation solution
Figure 1 shows the X-ray diffraction (XRD) pattern, nitrogen
isotherm, scanning electron microscopy (SEM) images, and
transmission electron microscopy (TEM) images of NB-MOR.
The XRD pattern shows well-resolved peaks in the range 4-40°,
which correspond to the MOR zeolite structure (Figure 1a). The
nitrogen sorption isotherm of NB-MOR exhibits a hysteresis loop
at a relative pressure of 0.45-0.96, which is typically assigned to
the presence of mesostructure (Figure 1b). Correspondingly, the
mesopore-size distribution of the NB-MOR is mainly centered at
13 nm (insert, Figure 1b). Sample textural parameters are present-
ed in Table S2. The SEM images (Figure 1c,d) reveal that NB-
MOR has a particle size of 3×5 ꢀm. The NB-MOR particles
6-
was adjusted to about 10.0. In this case, most of the Mo7O24 is
converted to small MoO4 species,10 which easily penetrate into
2-
the micropores of NB-MOR. After sulfidation by a mixture of H2
and H2S (400 °C, 10 vol% H2S), the CoMoS2 phases (marked by
white arrows) are uniformly located in the parallel mesopore
channels of the NB-MOR (Figure 2a and 2b). Moreover, very
small metal sulfide clusters may be formed in the micropores of
zeolite. This suggestion is confirmed by additional TEM images
and X-ray energy dispersive spectroscopy (EDS) analysis of a
thin-sectioned sulfided microporous Mo/MOR catalyst sample, as
shown in Figures S3-S6. The TEM images
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Figure 3. The catalysts activities. (a) 4,6-DMDBT conversion and (b) the remaining sulfur content in the reaction products at different
temperatures over (■) CoMo/NB-MOR and (●) CoMo/γ-Al2O3 catalysts. (c) Dependence of the 4,6-DMDBT conversion on reaction time
over (■) CoMo/NB-MOR and (●) CoMo/γ-Al2O3 catalysts. (Reaction conditions: total pressure, 5.0 MPa; temperature, 290 ºC; feed stock,
0.5 wt.% 4,6-DMDBT in decalin; WHSV of feed solution is 14.6 h-1; H2/oil = 700 Nm3/Nm3. The two catalysts have the same metal load-
ing, the molar ratio of Co/Mo was 1:2, and the Mo loading was 10.7 wt.%).
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Figure 4. Dependences of the 4,6-DMDBT conversion on the reaction time over series catalysts on the hydrogen spillover experiments. (a)
(■) 0.2 g CoMo/MOR (2.7 wt.% Mo), (●) 0.3 g CoMo/NB-MOR (12.5 wt.% Mo) and (▲) 0.3 g CoMo/NB-MOR (10.7 wt.% Mo) mixed
with 0.2 g CoMo/MOR (2.7 wt.% Mo). (b) (●) 0.3 g CoMo/NB-MOR (12.5 wt.% Mo) and (ꢀ) 0.3 g CoMo/NB-MOR (12.5 wt.% Mo)
mixed with 0.2 g MOR. (c) (◄) 0.3 g CoMo/γ-Al2O3 (12.5 wt.% Mo) and (ꢁ) 0.3 g CoMo/γ-Al2O3 (10.7 wt.% Mo) mixed with 0.2 g
CoMo/MOR (2.7 wt.% Mo). For all catalysts the molar ratio of Co/Mo was 1:2.
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(Figures S3 and S4) of a selected zone of the microporous
Mo/MOR catalyst sample show that the catalyst only contains
micropores and that no larger MoS2 nanoparticles can be ob-
served. However, the EDS element mapping of the selected zone
confirms the presence of Mo and S (Figure S5); the atomic Mo/S
ratio is about 0.88 (Table S3). Therefore, it is suggested that only
very small metal sulfide clusters (MoSx, 1<x<2) are highly dis-
persed in the micropores of zeolite MOR. Interestingly, after de-
struction of the ordered micropores by the strong electron beam,
larger nanoparticles (1-2 nm) were observed (Figure S6). The
large nanoparticles are attributed to the aggregation of the very
small metal sulfide clusters. These results also support that the
micropores of the Mo/MOR catalyst sample contain very small
metal sulfide clusters. It is worth noting that results published
previously show that very small metal sulfide clusters such as Ni-
Mo-S and MoSx could be dispersed inside the micropores of zeo-
lite Y and ZSM-5.11 The authors also suggested that the MoSx or
Ni-Mo-S clusters inside the zeolite micropores are more active in
the toluene hydrogenation and the HDS of the dibenzothiophene
than MoS2 slabs.11c,d In addition, the argon sorption results show
that the micropore-size distribution and micropore volume de-
crease with increased metal loadings in NB-MOR (Figure S7).
This phenomenon might be related to the existence of the very
small metal sulfide clusters in the micropores of NB-MOR.
(Figure S9). Moreover, we also tested the HDS activity of Co-
Mo/NB-MOR for treating industrial diesel with a sulfur content of
5240 ppm. After reacting for 10 h, the remaining sulfur content in
the product was below 20 ppm over the CoMo/NB-MOR catalyst,
which is much lower than the value of about 500 ppm obtained
over the CoMo/γ-Al2O3 catalyst (Figure S10). These results show
the potential importance of industrial applications of the Co-
Mo/NB-MOR catalyst in the future.
Because of the large size of the 4,6-DMDBT molecule, HDS
mainly occurs in the mesopores rather than in the micropores over
the CoMo/NB-MOR catalyst. Notably, although γ-Al2O3 has a
larger mesopore surface area (288 m2/g) than NB-MOR (182
m2/g), the CoMo/NB-MOR catalyst exhibits much higher activity
than the CoMo/γ-Al2O3 catalyst (the two catalysts have the same
metal loading). This phenomenon is attributed to the difference in
microporosity between the NB-MOR and γ-Al2O3 supports. The
NB-MOR has a mesopore volume of 0.37 cm3/g as well as a mi-
cropore volume of 0.13 cm3/g, while the γ-Al2O3 only has a mes-
opore volume of 0.45 cm3/g (Table S2). Possibly, the small mo-
lybdenum sulfide clusters in the micropores of the NB-MOR sup-
port create a large amount of spillover hydrogen, which then mi-
grates onto nearby active CoMo sites in the mesopores; this can
enhance the hydrogenating ability of the CoMo/NB-MOR catalyst.
This suggestion is strongly supported by catalytic tests over the
mesopore-free MOR-supported CoMo catalyst (CoMo/MOR) and
the mechanical mixture of CoMo/NB-MOR or CoMo/γ-Al2O3
with CoMo/MOR (Figure 4). When mesopore-free MOR support
is used, the CoMo/MOR catalyst shows very low conversion
(1.7%) because the HDS of the bulky 4,6-DMDBT molecule only
occurs on the external surface of the CoMo/MOR catalyst (Figure
4a). However, when the CoMo/NB-MOR catalyst is mechanically
mixed with CoMo/MOR, the conversion reaches 82.1%. In con-
trast, CoMo/NB-MOR itself shows a conversion at 70.6% (Figure
4a). Interestingly, when pure MOR zeolite is added to CoMo/NB-
MOR, the catalyst activity is close to CoMo/NB-MOR itself (Fig-
ure 4b). These results indicate that the very small metal sulfide
clusters in the micropores play an important role in enhancing the
HDS activities of the CoMo/NB-MOR catalyst. As expected, the
4,6-DMDBT conversion is also improved after mixing CoMo/γ-
Al2O3 with the CoMo/MOR catalyst, increasing from 36.8% to
44.6% (Figure 4c). Furthermore, the selectivities for the hydro-
genation products confirm that the hydrogenating ability of both
CoMo/NB-MOR and CoMo/γ-Al2O3 catalysts is remarkably in-
creased by mixing with CoMo/MOR (Table S5). Moreover, tem-
perature-programmed desorption of ammonia (NH3-TPD) curves
Figure 3 shows catalytic data in the HDS of 4,6-DMDBT over
activated CoMo/NB-MOR and CoMo/γ-Al2O3 catalysts. The reac-
tion network of the HDS of the 4,6-DMDBT is shown in Figure
S8. Compared with CoMo/γ-Al2O3 (61.5%), the CoMo/NB-MOR
catalyst exhibits very high 4,6-DMDBT conversion (99.1%) (Fig-
ure 3a). Correspondingly, the lowest remaining sulfur content in
the reaction products over CoMo/NB-MOR is 12 ppm, while that
over the CoMo/γ-Al2O3 catalyst is 331 ppm (Figure 3b). These
results indicate that the CoMo/NB-MOR catalyst shows an un-
precedented high HDS activity. Very importantly, the CoMo/NB-
MOR catalyst shows a long catalyst life. There is no activity loss
for the CoMo/NB-MOR catalyst in the HDS of 4,6-DMDBT
(Figure 3c). The good catalyst life of the CoMo/NB-MOR catalyst
is one of the key features in applications of industrial catalysts.
Additionally, the yield of the hydrocracking products (C5-C9) over
the CoMo/NB-MOR catalyst (0.10%) is very low (Table S4),
which is also an important factor for industrial applications of
HDS catalysts.
It is worth mentioning that not only the CoMo/NB-MOR but
also the NiMo/NB-MOR catalyst has excellent HDS activity
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In summary, we demonstrate a facile method for synthesizing
novel zeolite nanofiber bundles containing parallel-mesopore
channels. More importantly, CoMo and NiMo catalysts supported
on these nanofiber bundles showed an unprecedented high activi-
ty and excellent catalyst life in the HDS of the 4,6-DMDBT and
industrial diesel, compared with a conventional γ-alumina-
supported CoMo catalyst. These features should be important in
the future for design and preparation of multi-functional high
activity catalysts for HDS, selective cracking, and hydrocracking.
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ASSOCIATED CONTENT
Supporting Information
Experimental details, catalyst test, characterization, and the prod-
uct selectivity of the HDS. This material is available free of
charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
tangtiandi@wzu.edu.cn; fsxiao@zju.edu.cn
ACKNOWLEDGMENT
This work was supported by the National Natural Science Foun-
dation of China (U1162115 and 21076163), the Natural Science
Foundation of Zhejiang Province of China (Y4090084).
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CoMo/NB-MOR
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CoMo/γ−Αl O
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NB-MOR
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Temperature (oC)
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