Quinoline Hydrodenitrogenation over NiW/Al-MCM-41 Catalysts with Different Al Contents

Article abstract of DOI:10.1134/S1070427217120242

Al-MCM-41 materials were prepared with different Al contents and used as supports for NiW catalysts. The supports and catalysts were characterized by XRD, N₂ adsorption-desorption, XPS, Raman, H₂-TPR techniques. The XPS result showed that the Al added to MCM-41 promoted the dispersion of W and Ni species. The Raman result showed that the Al added to MCM-41 favored the formation of the suitable W species. The H₂-TPR result showed that the Al added to MCM-41 can reduce the reduction temperature of W species on the catalysts. The hydrodenitrogenation (HDN) results showed that the HDN activity followed the order of NiW/Al-2 > NiW/Al-1 > NiW/Al-4 > NiW. Moreover, this tendency was also valid for the ratio of propylcyclohexane/propylbenzene (PCH/PB). The high HDN activity and PCH/PB ratio of NiW/Al-2 are due to the well dispersion of the W and Ni species, the suitable W species and the low reduction temperature of W species.

Full text of DOI:10.1134/S1070427217120242

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2017, Vol. 90, No. 12, pp. 2055−2063. © Pleiades Publishing, Ltd., 2017.
VARIOUS TECHNOLOGICAL
PROCESSES
Quinoline Hydrodenitrogenation over NiW/Al-MCM-41 Catalysts
with Different Al Contents1
Fang Guoa, Jun Lia, Wanxi Lia, Xiuling Chena, Hongxue Qia, Xiaoxiao
Wangb,*, and Yue Yuc
a Jin Zhong University, College of Chemistry and Chemical Engineering,
Yuci 030619, P. R. China
b Taiyuan University of Science and Technology, School of Chemical and Biological Engineering,
Taiyuan 030024, P. R. China
*e-mail: wang5203264@sina.com
c Lin Yi Academy of Technology Cooperation and Application, Linyi 276000, P. R. China
Received November 12, 2017
Abstract—Al-MCM-41 materials were prepared with differentAl contents and used as supports for NiW catalysts.
The supports and catalysts were characterized by XRD, N2 adsorption-desorption, XPS, Raman, H2-TPR techniques.
The XPS result showed that the Al added to MCM-41 promoted the dispersion of W and Ni species. The Raman
result showed that the Al added to MCM-41 favored the formation of the suitable W species. The H2-TPR result
showed that the Al added to MCM-41 can reduce the reduction temperature of W species on the catalysts. The
hydrodenitrogenation (HDN) results showed that the HDN activity followed the order of NiW/Al-2 > NiW/Al-1 >
NiW/Al-4 > NiW. Moreover, this tendency was also valid for the ratio of propylcyclohexane/propylbenzene
(PCH/PB). The high HDN activity and PCH/PB ratio of NiW/Al-2 are due to the well dispersion of the W and
Ni species, the suitable W species and the low reduction temperature of W species.
DOI: 10.1134/S1070427217120242
INTRODUCTION
supported on MCM-41 materials [5‒9]. Wang et al. [5]
studied the support effect of MCM-41 for Co-Mo catalyst
and found that MCM-41 is a good support for HDS of
DBT. They developed high performance HDS catalysts
by depositing Ni‒Mo and Ni‒W over MCM-41 [10, 11].
Generally, the incorporation of heteroatom and the
amount of heteroatom play important role in the precursor
structure of catalysts and in the activity. Some HDS and
HDN studies have been made using MCM-41 modified
with heteroatom, such as Al, Ti, Zr, and Nb [12‒16]. In
the previous paper [16], we have reported that Al, Zr,
and Ti modified MCM-41, especially Al, can promote
the activity in the HDN of quinoline. The effect of the
amount of heteroatom on the HDS has also been analyzed
in several studies [17, 18]. Souza et al. [17] reported
the effect of Si/Al molar ratio of Al-MCM-41 support
on the CoMo catalysts for thiophene HDS and found
that different Si/Al molar ratios of Al-MCM-41 lead
to different nature and concentration of active phases.
The conventional hydrodesulfurization (HDS) and
hydrodenitrogenation (HDN) catalysts are alumina
supported Mo or W sulfides promoted by Ni or Co.
Generally, HDN is more difficult than HDS. In recent
times, many efforts are aimed to enhance the catalytic
activity of HDS and HDN catalysts. Among the
approaches to achieve this goal, one approach is to
choose proper support for the active components. It was
found that the support can influence catalyst reducibility
or sulfidability, structure and dispersion of the deposited
metal oxides, as well as the morphology of the sulfided
active phases [1–4].
The MCM-41 mesoporous molecular sieves materials,
which have ordered pore structure and high surface area
attracted much interest in the catalytic process. There
are several reports available on HDS and HDN catalysts
1 The text was submitted by the authors in English.
2055

2056
FANG GUO et al.
Table 1. Composition of the catalysts
the way described above. All the catalysts have the same
amounts of WO3 (20 wt %) and NiO (2.5 wt %). Table 1
listed the composition of the catalysts .
Catalyst
NiW
Al, wt %
W, wt %
Ni, wt %
2.5
0
1
2
4
20
20
20
20
NiW/Al-1
NiW/Al-2
NiW/Al-4
2.5
Characterization Techniques
2.5
The structural features of the supports and catalysts
were analyzed by X-ray diffraction patterns (XRD) using
Bruker D8 Advance diffractometer with CuKα radiation.
2.5
N2 adsorption-desorption measurement were
performed on a Tristar-3000 Micromeritics volumetric
apparatus, which reports BET special surface area,
average pore diameter, pore volume, and adsorption
isotherms automatically.
Venezia et al. [18] reported the effect of Al contents of
Al-MCM-41 support on the Pd catalysts for HDS of
thiophene and found that the catalyst with Si/Al = 169
showed the highest HDS activity. However, the effect
of the Al content in the mesoporous Al-MCM-41 on the
HDN activity ofAl-MCM-41supported NiW catalyst has
not been explored.
Surface analyses of the samples were performed by
XPS using Kratos XSAM800 fitted with an AlKα source
(1486.6 eV). Binding energies (BE) were referenced to the
C1s peak (284.8 eV). Quantitative information of surface
composition was obtained from integrated peak areas and
corresponding atomic sensitivity factors. Surface molar
ratio was obtained from the peak area ratios normalized
by the corresponding atomic sensitivity factors.
In the present paper, a series ofAl-MCM-41 supports
with different Al contents were prepared by a simple
and quick incipient wetness impregnation method,
followed by the deposition of Ni and W oxides on these
supports by co-impregnation. The catalytic performance
of HDN for quinoline on the catalysts was investigated.
The systematic study of HDN functionalities of NiW
supported onAl-MCM-41 with variousAl contents were
also explored.
Raman spectra were recorded on a LabRAM
HR800 System equipped with a CCD detector at room
temperature. The samples were excited bythe 514 nmAr+
laser with a power of 1 MW.
EXPERIMENTAL
H2-TPR experiments were carried out in aAutoChem
II 2920 equipment (Micromeritics, USA) using 0.01 g
catalysts for each run. Typically, the catalysts were
pretreated inAr at 550°C for 2 h and then cooled at 30°C.
Subsequently, the Ar flow was switched to 10% H2‒Ar
mixed gas. The H2‒TPR was started from 30 to 900°C at
a heating rate of 10°C/min and simultaneously monitored
by a thermal conductivity detector (TCD).
Catalyst Preparation
The MCM-41 was provided by the Catalyst Plant
of Nankai. The Al-MCM-41 supports with different
Al contents (1, 2, or 4 wt %) were prepared through
an incipient wetness impregnation method by using
appropriate concentration of aluminium isopropoxide
(99%,Aldrich) solution in isopropanol on MCM-41. The
impregnated samples were dried overnight at 80°C and
then calcined at 550°C for 6 h in static air of a furnace.
TheAl-MCM-41 supports withAl content of 1, 2, 4 wt %
were denoted as Al-1, Al-2, Al-4, respectively.
Catalytic Activity
The experiment for the quinoline HDN was performed
in a fixed-bed reactor (i.d. = 6 mm). The catalyst (1 g,
size 20‒40 mesh) was packed in the constant temperature
zone of the reactor and pre-sulfided in situ with a feed
of 5 vol % CS2 in n-hexane at 400°C and 3 MPa for 3 h.
After sulfidation, the feed was switched to the solution
containing quinoline in n-heptane (0.5 wt % N). The HDN
reaction was conducted on the temperature of 350‒390°C,
at pressure of 4 MPa, WHSV of 2 h‒1, H2/feed volumetric
ratio of 1000. The products of reaction were analyzed
using aAgilent-5860 gas chromatograph fitted with a FID
detector, using a commercial DB-5 column.
The NiW/Al-MCM-41 catalysts with different Al
contents were prepared through co-impregnation method.
The nickel nitrate hexahydrate (analytical grade) and
ammonium paratungstate (analytical grade) were used as
Ni and W sources, respectively. The impregnated samples
were dried overnight at room temperature and dried at
80°C for 12 h. Finally, the calcination was performed at
540°C for 3 h to obtain the final catalysts . For comparison,
the NiW/MCM-41 catalyst was also prepared following
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QUINOLINE HYDRODENITROGENATION
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Fig. 1. Small-angle XRD patterns of the supports.
Fig. 2. Wide-angle XRD patterns of supports.
RESULTS AND DISCUSSION
N2 adsorption-desorption. The textural properties
of the MCM-41 and Al-MCM-41 supports are listed in
Table 2. It can be found that the MCM-41 exhibits the
highest specific surface area (SBET), pore volume (Dp) and
pore diameter (Vp) among all the supports. TheAl added to
the MCM-41 gives rise to a decrease in SBET, Dp, and Vp,
but an increase in the wall thickness (Wp). The decrease
in Vp and increase in Wp suggest that some Al species are
deposited inside the pore channels of the MCM-41 [21, 22].
Characterization of Supports
Small-angle XRD. The small-angle XRD patterns
of MCM-41 and Al-MCM-41 of different Al contents
is shown in Fig. 1. The MCM-41 material displayed a
three peak pattern, corresponding to the (100), (110), and
(200) diffraction planes, respectively [19]. These peaks
are related to a ordered hexagonal pore system. From
the Fig. 1, it can be found that the diffraction patterns
corresponding to all Al-MCM-41 samples, except Al-4,
still exhibited the three peaks assigned to the MCM-41,
although with lower peak intensity than bare MCM-41.
It showed that the long-range order of the MCM-41 is
almost preserved for the Al-MCM-41 samples, except
Al-4 [2]. The strong decrease in the peak intensity for
the Al-4 sample indicated the loss of long-range order.
Therefore, the introduction Al into MCM-41 do not
destroy the hexagonal symmetry and only at high Al
content the long-range order of the support decreases
noticeably.
The N2 adsorption‒desorption isotherms of the sup-
ports are shown in Fig. 3. It shows that all the supports
present a type IV isotherm, typical of mesoporous materi-
als. However, as the Al content increases, the height of
sharpness loop decreases Al-MCM-41. As the hysteresis
loop of isotherms is a result of the actual pore structure,
it can be concluded that the structure of Al-MCM-41 is
less uniform than that of the purely MCM-41 material. .
Characterization of Catalysts
Wide-angle XRD. The wide-angle XRD patterns of
the catalysts are reported in Fig. 4. The absence of peaks
Wide-angle XRD. Wide-angle XRD technique was
used to investigate the presence of any crystallite species
in the samples. The wide-angle XRD patterns of the
MCM-41 andAl-MCM-41 with differentAl contents are
shown in Fig. 2. It is demonstrated that theAl species have
been highly dispersed on the MCM-41 surface since no
diffraction peaks of Al crystalline phases can be found
from the XRD patterns ofAl-MCM-41 [20]. Furthermore,
the XRD patterns show that all the supports exhibit a
broad peak caused by the amorphous silica walls.
Table 2. Textural properties of the MCM-41 and Al-MCM-41
supports
SBET
,
Vp,
cm3 g‒1
Wp,
nm
Sample
Dp, nm
m2 g‒1
MCM-41 1071.00
3.83
3.39
3.31
2.94
1.08
0.90
0.91
0.77
0.97
1.36
1.41
1.43
Al-1
Al-2
Al-4
1015.06
980.30
952.68
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FANG GUO et al.
Fig. 3. N2 adsorption–desorption isotherms of the
supports.
Fig. 4. Wide-angle XRD patterns of catalysts.
(a)
(b)
Fig. 5. N2 adsorption-desorption isotherms of (a) supports and (b) catalysts.
due to the Al, Ni, and W crystalline phases in the XRD
patterns of all the catalysts reveals that the particle size
of Al, Ni, and W crystallites is well dispersed into the
support or very small.
is destroyed significantly by impregnation with water
solution of Ni and W, especially the catalysts of NiW and
NiW/Al-4. From the Table 3, it can be found that the SBET
and Vp decrease significantly after the corporation of Ni
and W on the supports. This may be due to the blockage
and occupation of pores by the Ni and W species.
N2 Adsorption-desorption. The textural properties
and N2 adsorption-desorption isotherms of catalysts are
given in Fig. 5 and Table 3, For comparison, the textural
properties and N2 adsorption‒desorption isotherms of
supports are given. From the Fig. 5, it can be found that
the step sharpness of the catalysts is much lower than
that of the supports, which indicates that the structure
Raman spectra. Raman spectroscopy is an important
tool for obtaining detailed information about the metal
oxides phase. In the present work, this technique is used
to study the effect ofAl on the nature of metal oxide phase
of NiW catalysts. The Raman spectra of catalysts are
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QUINOLINE HYDRODENITROGENATION
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Table 3. Textural properties of the catalysts and supports
Table 4. The binding energies of the W4f, Ni2p
Binding energy, eV
SBET
,
Vp,
Wp,
nm
Sample
Al-1
Dp, nm
m2 g‒1
cm3 g‒1
Catalyst
W4f7/2
35.7
W4f5/2
37.8
Ni2p3/2 Ni2p1/2
1015.06
980.30
952.68
601.09
575.39
597.78
593.54
1071.00
3.39
3.31
2.94
3.05
3.35
3.27
2.89
3.83
0.90
0.91
0.77
0.44
0.53
0.49
0.48
1.08
1.36
1.41
1.43
‒
NiW
856.0
862.3
873.9
880.6
Al-2
Al-4
NiW/Al-1
35.8
38.1
855.7
862.1
873.6
880.4
NiW
NiW/Al-1
NiW/Al-2
NiW/Al-4
MCM-41
‒
NiW/Al-2
NiW/Al-4
35.9
35.8
38.0
37.9
855.9
862.3
873.8
880.3
‒
‒
855.6
862.0
873.2
879.6
0.97
presented in Fig. 6. From the literature data, the MCM-41
does not exhibit band, the bands of 804, 710 and 274 cm‒1
is ascribed to the crystalline WO3 presents [23], while
the band of 970 cm‒1 is ascribed to the W=O band in
octahedral polytungstate species. Moreover, the band of
883 cm‒1 is ascribed to the NiWO4, a shoulder at around
811 cm‒1 reflects the Ni‒W‒O stretching vibrations [24].
the BE of W4f7/2 spectrum around 35.8 and 38.0 eV can
be ascribed to WO3 and/or NiWO4 [25]. The doublet
peak of Ni2p3/2 and Ni2p1/2 electrons are exhibited at
BE position of 855.6‒856.0 and 873.2‒873.9 eV, with
the corresponding shake-up satellite at 861.9‒862.3 and
879.6‒880.6 eV. According to the literature, the BE of
Ni2p3/2 spectrum in the range of 855.6‒856.2 eV ascribes
to Ni2O3 and/or NiWO4 [26].
Figure 6 shows that the band assigned to the octahedral
polytungstate species (970 cm‒1) is observed for all the
catalysts and its intensity is higher for the catalysts with
Al than that for the catalyst of NiW. Furthermore, the
bands assigned to crystalline WO3 (804 and 710 cm‒1) and
NiWO4 (883 cm‒1) are observed for the catalyst of NiW.
On the contrary, no bands assigned to them are observed
for the catalysts with Al, whereas a shoulder assigned
to the Ni‒W‒O (811 cm‒1) species is observed. Hence,
the Al added to the MCM-41 facilitates the formation
of octahedral polytungstate species and the Ni‒W‒O
species. This may be as a result of the stronger interaction
between W species with the Al2O3 than that with silica.
The octahedral polytungstate species and Ni‒W‒O
species are precursors of active species for hydrotreating
catalyst. Hence, the Al added to the MCM-41 facilitates
the formation of the suitable W species on the catalysts.
The surface molar ratio by XPS analysis can provide
the important information about the dispersion of metal
species on the catalysts [27]. Table 5 lists the molar ratios
of Ni/Si, W/Si, Si/Al on the catalyst. The surface molar
ratios of W/Si and Ni/Si of all catalysts are higher than in
the bulk. The result indicates that more W and Ni species
were distributed on the surface than they were in the bulk
XPS spectra. The chemical state and surface
composition of catalysts were proved by XPS.
The binding energies (BE) of the Ni, W, the ratios of
Ni/Si, W/Si, Si/Al are compiled in Table 4. It can be seen
that all the catalysts showed similar BE of W4f and Ni2p,
suggesting no significant changes of the chemical state for
W and Ni species. The doublet peak of W4f7/2 and W4f5/2
electrons are exhibited at BE position of 35.7‒35.9 and
37.8‒38.1 eV, respectively. According to the literature,
Fig. 6. Raman spectra of catalysts.
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FANG GUO et al.
Table 5. The ratios of W/Si, Ni/Si and Si/Al on catalysts
Surface compositiona
Catalyst
Bulk compositionb
Ni/Si
W/Si
Ni/Si
Si/Al
W/Si
Si/Al
NiW
0.073
0.084
0.145
0.094
0.037
0.067
0.062
0.064
‒
0.067
0.068
0.069
0.071
0.026
0.026
0.027
0.027
‒
NiW/Al-1
NiW/Al-2
NiW/Al-4
25.585
19.383
6.026
64.912
32.032
15.592
a Determined by XPS. b Calculated number based on the starting material used.
[28]. Moreover, the surface molar ratio of Si/Al on the ratios of Ni/Si and W/Si on the catalysts withAl are higher
catalysts is lower than the expected bulk Si/Al molar ratio, than that on the catalyst of NiW, especially the surface
suggesting that the catalysts withAl reveals an enrichment molar ratio of Ni/Si. Thus, it can be concluded that the
of Al on the surface of the catalysts. The surface molar Al added to MCM-41 can promote the dispersion of W
and Ni species on the catalysts. Furthermore, the surface
molar ratio of W/Si on the catalysts follows the order
of NiW/Al-2 (0.145) > NiW/Al-1 (0.094) > NiW/Al-4
(0.084) > NiW (0.073), indicating that the dispersion of W
species increased and then decreased with increasing the
content of Al in the range studies. However, the surface
molar ratio of Ni/Si on the NiW/Al-MCM-41 catalysts
has not changed significantly.
H2-TPR spectra. The reducibility of the catalysts was
characterized by H2-TPR experiment. Reduction profiles
of the catalysts are presented in Fig. 7. All catalysts
show two principal reduction peaks in the temperature
ranges of 500‒700°C and >800°C, respectively. The low
temperature peak (500‒700°C) can be ascribed to the step
of reduction (from W6+ to W4+) of octahedral tungsten
species with different degrees of polymerization, weakly
bound to the support surface. The broad peak at high
Fig. 7. The H2-TPR spectra of the catalysts.
temperature (>800°C) can be assigned to the second step
of the polymeric octahedral W species (from W4+ to W0)
and to the first step of reduction of isolated tetrahedral
W6+ species, which are in strong interaction with the
support [29, 30]. Moreover, the maximum reduction
temperature of the catalysts in the temperature range of
500‒700°C follows the order of NiW (613°C) > NiW/
Al-4 (568°C) > NiW/Al-1 (558°C) > NiW/Al-2 (543°C),
indicating that theAl added to MCM-41 leads to an easier
reduction of polymeric octahedral tungsten species on the
catalysts. The decrease in reduction temperature favors
for the reduction and sulphidation of the W species
leading to the formation of more active species. Moreover,
in the TPR profiles of supported NiW catalysts one would
expect reduction of NiO species appearing in 150‒400°C
temperature range, but it is not the case of our catalysts.
Fig. 8. Conversion and HDN of quinoline for catalysts.
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QUINOLINE HYDRODENITROGENATION
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NH2
Fig. 9. HDN reaction network of quinoline. (Q) Quinoline, (THQ5) 5,6,7,8-tetrahydroquinoline, (DHQ) decahydroquinoline,
(THQ1)1,2,3,4-tetrahydroquinoline,(OPA)ortho-propylaniline,(PCHA)2-propylcyclohexylamine,(PCHE)propylcyclohexene,
(PCH) propylcyclohexane, (PB) propylbenzene.
The phenomenon is probably due to the presence of well-
dispersed active components and absence of well-defined
bulk species, interacting with the support surface [26].
presents the lowest HDN activity of 17 % at 350°C and
55% at 390°C.
The HDN reaction network of quinoline is presented
in Fig. 9. In general, there are two pathways to remove the
nitrogen atom from quinoline: hydrogenolysis pathway
(pathway I, THQ1 → OPA→ PB) and the hydrogenation
pathway (pathway II, DHQ → PCHA→ PCHE → PCH)
(Fig. 9) [ 31]. Usually, the PCH/PB ratio is supposed to
represent the selectivity of the two pathways [32].
Activity of catalysts. Figure 8 showed the conversion
and HDN of quinoline. It clearly shows that the conversion
of quinoline is about 95‒99 % for all the catalysts,
suggesting that quinoline could be hydrogenated easily.
Figure 8 also shows that the HDN activity for all the
catalysts increases with increasing reaction temperature.
The HDN activity for quinoline follows the order: NiW/
Al-2 > NiW/Al-1 > NiW/Al-4 > NiW. The catalyst of
NiW/Al-2 presents the highest HDN activity of 38% at
350°C and 90% at 390°C, whereas the catalyst of NiW
The product distribution of HDN for quinoline over
the catalysts of NiW/Al-2 and NiW is compared in
Fig. 10. For both catalysts, the main intermediates are
THQ1, THQ5, DHQ. The main final products are PCH
Fig. 10. The distribution of HDN of quinoline for catalysts.
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FANG GUO et al.
supports were clearly revealed by the Raman spectra of
the catalysts. The presence of WO3 peak suggests agglom-
eration of WO3 species on the support surface leading to
the formation of bulk WO3. According to Raman experi-
ments the NiW catalyst shows the crystalline WO3 and
NiWO4 indicates the poor dispersion of W species due
to the inhomogeneous distribution of WO3. TheAl added
to the MCM-41 enhances the formation of octahedral
polytungstate species and the Ni‒W‒O species, moreover,
the NiW/Al-2 catalyst shows the highest intensity of oc-
tahedral polytungstate species and the Ni‒W‒O species,
demonstrating the highest HDN activity. Moreover, the
dispersion of W and Ni were also revealed by the XPS.
TheAl added to the MCM-41 can promote the dispersion
of W and Ni on the catalysts.
A better reducibility of the catalysts will be also an
indication of an increased number of sulfide species
after sulfidation. According to TPR experiments the
NiW catalyst shows the highest reduction temperature,
demonstrating the lowest HDN activity. The Al added to
MCM-41 leads to a decrease in the reduction temperature
of polymeric octahedral tungsten species, moreover the
NiW/Al-2 catalyst shows the lowest reduction tempera-
ture, demonstrating the highest HDN activity.
Fig. 11. The ratio of PCH/PB for catalysts.
and PB, especially PCH. For the catalyst of NiW, THQ1
was the primary product of quinoline HDN at 350°C. The
selectivities of THQ1 and DHQ decrease straightly with
the increase of reaction temperature, accompany with the
THQ5 selectivity increasing, reaching maximum, then
dropping. The selective of OPAremains constant of about
2%, over the temperature range. The selectivities of PCH
and PB increase with the increase in reaction temperature.
For the catalyst of NiW/Al-2, the selectivities of THQ1,
THQ5, and DHQ decrease with the increase in reaction
temperature, accompanying with the increase in the
selectivities of PCH and PB.
CONCLUSIONS
In the present work, a series of Al-MCM-41 molecu-
lar sieves with different Al contents were prepared by a
simple and quick incipient wetness impregnation method.
The NiW catalysts supported on these mesoporous sup-
ports were prepared by co-impregnation method. It was
found that Al content had crucial effect on the physico-
chemical properties ofAl-MCM-41, and then influenced
the catalytic performance of catalysts in the HDN of
quinoline. The experimental results proved that the NiW/
Al-2 catalyst demonstrated the highest HDN activity and
PCH/PB ratio among other three catalysts. This may be
a consequence of the higher dispersion of W and Ni spe-
cies, the lower reduction temperature of W species, and
the suitable W species on the NiW/Al-2 catalyst.
The PCH/PB ratio of HDN for quinoline over
different catalysts is presented in Fig. 11. It follows the
order of NiW/Al-2 > NiW/Al-1 > NiW/Al-4 > NiW. It
is indicated that, the beneficial effect of the Al added
to MCM-41, pathway II is much more preferable than
pathway I. Moreover, the tendency of PCH/PB ratio is
the same as the tendency of HDN activity over different
catalysts. It indicated that the effect of the incorporation
Al into MCM-41 of to PCH/PB ratio and HDN activity
is consistent. Figure 11 also shows that the PCH/PB ratio
for all the catalysts decreases with the increasing the
reaction temperature. The result is in accordance with
those of M. Jian and R. Prins [30] This because the higher
reaction temperature favored the formation of PB [33].
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