Nickel–Tungsten and Nickel–Molybdenum Sulfide Diesel Hydrocarbon Hydrogenation Catalysts Synthesized in Pores of Aromatic Polymer Materials

Article abstract of DOI:10.1134/S0965544119060069

Abstract: Porous aromatic polymer materials based on tetraphenylmethane molecules linked by methylene groups have been synthesized. By impregnating these materials with nickel–tungsten and nickel–molybdenum thiosalts, catalysts for the hydrogenation of bicyclic aromatic hydrocarbons of the diesel fraction have been prepared. Nanoparticles of the active sulfide phase are formed in support pores during the reaction; it is assumed that after the formation of the nanoparticles, the support material will undergo partial degradation to rearrange the mesoporous structure into a macroporous structure providing the best diffusion of substrates to the surface of the sulfide nanoparticles. The synthesized catalysts have been tested in the hydrogenation of naphthalene and naphthalene derivatives at a hydrogen pressure of 5 MPa and a temperature of 380°C.

Full text of DOI:10.1134/S0965544119060069

ISSN 0965-5441, Petroleum Chemistry, 2019, Vol. 59, No. 6, pp. 575–580. © Pleiades Publishing, Ltd., 2019.
Nickel–Tungsten and Nickel–Molybdenum Sulfide Diesel
Hydrocarbon Hydrogenation Catalysts Synthesized in Pores
of Aromatic Polymer Materials
a
a
a
a
R. A. Batryshin , D. A. Makeeva , L. A. Kulikov , Yu. S. Kardasheva ,
a, b
a,
A. L. Maksimov , and E. A. Karakhanov *
Faculty of Chemistry, Moscow State University, Moscow, 119991 Russia
a
b
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
e-mail: kar@petrol.chem.msu.ru
Received November 26, 2018; revised February 3, 2019; accepted February 12, 2019
*
Abstract—Porous aromatic polymer materials based on tetraphenylmethane molecules linked by methylene
groups have been synthesized. By impregnating these materials with nickel–tungsten and nickel–molybde-
num thiosalts, catalysts for the hydrogenation of bicyclic aromatic hydrocarbons of the diesel fraction have
been prepared. Nanoparticles of the active sulfide phase are formed in support pores during the reaction; it is
assumed that after the formation of the nanoparticles, the support material will undergo partial degradation
to rearrange the mesoporous structure into a macroporous structure providing the best diffusion of substrates
to the surface of the sulfide nanoparticles. The synthesized catalysts have been tested in the hydrogenation of
naphthalene and naphthalene derivatives at a hydrogen pressure of 5 MPa and a temperature of 380°C.
Keywords: nanoparticles, catalysis, mesoporous materials, hydrogenation
DOI: 10.1134/S0965544119060069
The ever-tightening environmental standards for the absence of covalent bonding between the active
motor fuels make the problem of decreasing the aro- phase and the support, is the partial incorporation of
matic content in these fuels particularly urgent for the carbon into the sulfide phase particles during their for-
petroleum refining industry. Thus, for diesel fuels, the mation; this process leads to the stabilization of the
limiting content of aromatic compounds and sulfur resulting particles and an increase in the degree of dis-
cannot exceed 8% and 10 mg/kg, respectively. The persion of them [13, 14].
basic method to improve the fuel properties is fuel
hydrotreating, during which the fuel components
undergo hydrodearomatization, hydrodesulfurization,
isomerization, and catalytic cracking [1, 2]. These
processes are most commonly catalyzed by catalysts
based on sulfides of transition metals, such as nickel,
cobalt, molybdenum, and tungsten [3–8]. Unlike cat-
alysts based on platinum group metals, these sulfide
catalysts preserve their high activity in a medium with
a high sulfur and nitrogen content.
It was previously shown that porous aromatic
frameworks (PAFs)—polymer carbon materials con-
sisting of moieties of aromatic molecules linked by
aryl–aryl bonds—can be effectively used for the in situ
synthesis of sulfide catalysts [15–18]. Metal sulfide
particles synthesized in the support pores were active
in the hydroconversion of a broad range of aromatic
substrates and petroleum fractions. However, the cat-
alysts had a number of disadvantages, such as the high
cost of PAFs and the limited diffusion of sterically hin-
dered substrates to the surface of active-phase parti-
cles.
It is known that catalyst properties largely depend
on the properties of the support material and the fea-
tures of the support–active phase interaction [9–11].
This study is focused on the synthesis of catalysts
In most cases, supports for catalysts based on metal based on mesoporous polymer PAFs synthesized by
sulfides are inorganic oxide materials, such as silica, the Friedel–Crafts (FC) reaction between tetra-
alumina, aluminosilicates, and zeolites. However, in phenylmethane and dimethoxymethane (PAF-FC).
this case, covalent bonds between the support material In the synthesized polymer support, the residues of
and the active phase can be formed; this bonding leads tetraphenylmethane molecules are linked by methy-
to a decrease in the catalyst activity [12]. This problem lene bridges; therefore, after the formation of sulfide
can be solved by synthesizing carbon-supported cata- nanoparticles in the support pores, the support struc-
lysts. An advantage of carbon materials, in addition to ture can undergo partial degradation to form macrop-
575

5
76
BATRYSHIN et al.
orous channels for an easier diffusion of substrates to
the surface of the sulfide nanoparticles. The activity of
the synthesized Ni–W and Ni–Mo catalysts was stud-
EXPERIMENTAL
The mesoporous polymer PAF-FC-1 material was
ied in the hydrogenation of bicyclic aromatic com- synthesized by the crosslinking of moieties of tetrap-
pounds—naphthalene, 1-methylnaphthalene, and 2- henylmethane molecules with dimethoxymethane in
methylnaphthalene—at a temperature of 380°C and a accordance with a modified procedure described in
pressure of 5 MPa.
[19, 20] (Scheme 1).
CH3
O
O
FeCl3, DCE
0°C
+
8
CH3
PAF-FC-1
Scheme 1. Synthesis of mesoporous aromatic polymer material PAF-FC-1.
The process was catalyzed by anhydrous ferric num and tungsten in the synthesized PAF-FC-1–
chloride. A suspension of ferric chloride (9.6 g, NiMoS and PAF-FC-1–NiWS materials were 15%.
6
0 mmol) in dichloroethane (DCE, 60 mL) was pre-
pared in a 100-mL single-neck flask equipped with a
magnetic stirrer anchor and a reflux condenser. The
suspension was stirred for 10 min; after that, tetra-
Instruments and Investigation Procedures
Infrared spectroscopy. Infrared spectra were
–1
phenylmethane (6.4 g, 20 mmol) was added to it under recorded in the range of 4000–500 cm on a Nicolet
stirring; next, dimethoxymethane (20 mL, 494 mmol) IR-2000 instrument (Thermo Scientific) by the multi-
was carefully added to the resulting mixture, and the ple attenuated total internal reflection method using a
flask was placed in a water bath. The reaction was run Multi-reflection HATR accessory comprising a 45°
at a temperature of 45°C for 5 h and then at a tempera- ZnSe crystal for different wavelength ranges with a res-
ture of 80°C for 12–19 h. Temperature was controlled olution of 4 nm.
using a thermocouple connected to the magnetic stir-
rer. Upon the completion of the reaction, ethanol was
added into the flask; the PAF-FC-1 precipitate was
filtered off and washed with ethanol, a 2 M ethanol
solution of hydrochloric acid, water, and tetrahydrofu-
ran. After that, the precipitate was dried under a low
pressure at 90°C. The resulting product was a brown-
orange powder with a weight of 13.1 g. The material
was characterized by IR spectroscopy, low-tempera-
ture nitrogen adsorption–desorption, and solid-state
Low-temperature nitrogen adsorption–desorption.
Nitrogen adsorption–desorption isotherms were
recorded at a temperature of 77 K on a Micromeritics
Gemini VII 2390 (V1.02t) instrument. Before mea-
surements, the samples were degassed at a temperature
of 110°C for 6 h. Surface area (S ) was calculated by
BET
the Brunauer–Emmett–Teller (BET) method
using the adsorption data in a relative pressure range of
P/P = 0.05–0.2. Pore volume and pore size distribu-
0
tion were determined from the adsorption branch of
the isotherms in terms of the Barrett–Joyner–Hal-
enda (BJH) model. Total pore volume was determined
from the amount of nitrogen adsorbed at a relative
13
C cross polarization magic angle spinning nuclear
magnetic resonance (CP MAS NMR) spectroscopy.
Nickel–molybdenum and nickel–tungsten thio-
pressure of P/P = 0.995.
0
salts [N(n-Bu) ] [Ni(MeS ) ] (Me = Mo, W) were
4
2
4 2
Solid-state NMR spectroscopy. Analysis by solid-
state MAS NMR spectroscopy was conducted on a
Varian NMR Systems instrument at a rotation fre-
synthesized as described in [17]. The thiosalts were
deposited on the support by impregnating it with a
thiosalt solution in tetrahydrofuran; after that, the sol-
vent was removed under a low pressure. A typical pro-
cedure was as follows: a thiosalt (400 mg) was dis-
solved in tetrahydrofuran (100 mL) in a 250-mL
round-bottomed flask; after that, the PAF-FC-1 pow-
13
quency of 10 kHz. C spectra were recorded by the CP
method in a pulsed mode at an operating frequency of
1
25 MHz.
Gas–liquid chromatography. Reaction products
der (400 mg) was added. The resulting suspension was were analyzed on a Kristallyuks 4000 m chromato-
stirred for 24 h; after that, the solvent was removed on graph equipped with a flame ionization detector and a
a rotary evaporator. The weight fractions of molybde- 100 m × 0.25 mm Petrocol DH low-polarity chro-
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NICKEL–TUNGSTEN AND NICKEL–MOLYBDENUM SULFIDE DIESEL
577
matographic column coated with a polydimethylsilox- vibrations in the benzene ring in the region of 690–
–1
ane phase (deposited layer thickness of 0.50 μm). 715 cm ; and (3) stretching vibrations of C–C bonds
Chromatograms were recorded and analyzed on a
computer using the NetChrom v. 2.1 software for Win-
dows. Helium was used as a carrier gas (pressure,
–1
with the absorption band peak at 1504 and 1602 cm
for phenyl moieties mono- and disubstituted in the
para position, respectively. The spectrum of the PAF-
FC-1 material exhibits, in addition to the above sig-
150 kPa; flow rate, 50 mL/min). The flow rate of
hydrogen and air to maintain the flame of the flame
ionization detector was 60 and 500 mL/min, respec-
tively. The detector and evaporator temperature was
nals, absorption bands with peaks at 1679, 1411, and
–1
1
296 cm and a broad absorption band in the region
–1
of 2800–3000 cm characteristic of CH groups.
2
2
50 and 300°C, respectively. The following tempera-
13
ture programming was used: 100°С (20 min),
The C CP MAS NMR spectrum of the synthe-
sized PAF-FC-1 material is shown in Fig. 1. The spec-
trum exhibits a low-intensity signal with a peak at 66
ppm, which corresponds to carbon atoms in the nodal
positions of the structure, and a number of signals in
20°С/min, 20°С (60 min).
Catalytic Testing Procedure
Fifty milligrams of a catalyst, 50 mg of sulfur, and the region of 110–160 ppm, which are characteristic of
mL of a 0.314 M substrate solution in hexadecane the carbon atoms of aromatic moieties. In addition, a
2
were placed in a steel autoclave equipped with a mag- signal at 42 ppm is observed; the occurrence of this
netic stirrer. The autoclave was sealed, filled with signal confirms the presence of CH groups in the
2
hydrogen to a pressure of 5 MPa, and placed in an structure of the synthesized material. It can be con-
oven. Reaction was run under vigorous stirring at cluded that the spectrum of the PAF-FC-1 material is
3
80°C for 5 h; temperature was controlled using a almost identical to the spectra of PAFs synthesized
thermocouple. After reaction, the autoclave was through the Suzuki reaction, except for the presence of
cooled and then depressurized; the reaction products signals of CH groups [21, 28, 29].
2
were analyzed by gas–liquid chromatography.
The textural characteristics of the synthesized
PAF-FC-1 support were studied by low-temperature
RESULTS AND DISCUSSION
nitrogen adsorption–desorption (Fig. 2). At low pres-
sures (P/P = 0–0.05), an abrupt increase in the
0
A known method for synthesizing tetraphenyl-
methane-based PAFs is based on a Pd-catalyzed reac-
tion of brominated tetraphenylmethane with aromatic
boric acids [21–24]. In this case, the material acquires
a stable rigid ordered structure of moieties of aromatic
molecules directly linked to each other. However, this
method requires the use of expensive reactants, such
absorption of nitrogen is observed; this fact suggests
that the material has a developed surface. The specific
surface area calculated in terms of the BET model was
2
7
68 m /g; it is slightly higher than the standard values
for porous aromatic supports. In addition, in a pres-
sure range of P/P = 0.45–0.50, a hysteresis between
0
as palladium compounds and aromatic boric acids. the adsorption and desorption branches is observed;
The aromatic polymer synthesis method applied in this feature is characteristic of mesoporous materials.
this study is based on the use of much cheaper com- The average pore size in the material is about 4.5 nm,
mercially available reactants, namely, dimethoxy- as determined in terms of the BJH model. However,
methane and ferric chloride. In addition, this method the authors of [19] determined the average pore size
provides the synthesis of PAFs using a significantly using the nonlocal density functional theory
larger range of monomer molecules and their combi- (NLDFT) method and obtained a bimodal pore dis-
nations. To provide the formation of a developed tribution with maxima at 0.8 and 2 nm. The authors of
porous structure of the polymer material, a necessary [27], using tetraphenylsilane as a monomer, also
requirement is imposed on the monomers: they obtained a bimodal pore size distribution with maxima
should have a branched structure with several aro- at 1.69 and 3.8 nm. Thus, the NLDFT method is more
matic rings in different planes and exhibit activity in appropriate for describing the porosity of structures of
the FC reaction; these monomers are tetraphenyl- porous aromatic polymers. However, the results
methane, triphenylamine, triphenylbenzene, triphen- obtained in terms of the different models are not in
ylphosphine, and their derivatives [19, 25–27].
contrast with each other: the BJH model is used to
determine the average pore size and takes into account
the presence of large pores; therefore, the average pore
size increases.
The synthesized PAF-FC-1 material was studied
by IR and NMR spectroscopy (Fig. 1). The IR spec-
trum of the material exhibits absorption bands with
–1
peaks at 500–1700 and 2800–3200 cm , which are
During the deposition of metal thiosalts on the
characteristic of porous aromatic supports. The support material, the color of the synthesized materi-
bands can be conventionally divided into several als changed to dark green and dark orange in the case
groups: (1) absorption bands in the region of 600– of the PAF-FC-1–NiMoS molybdenum catalyst and
–1
7
70 cm attributed to the bending vibrations of C–H the PAF-FC-1–NiWS tungsten catalyst, respectively.
bonds; (2) absorption bands characteristic of bond Similar results were obtained in the case of PAFs syn-
PETROLEUM CHEMISTRY Vol. 59 No. 6 2019

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BATRYSHIN et al.
(a)
PAF-FE.SPA
3800
3400
3000
28
2600
2200
1800
1400
1000
600
−
1
Wave number, cm
1
(b)
139
45
146
6
7
PAF-FC-1
20
0
180
160
140
120
100
80
60
40
Chemical shift, ppm
Fig. 1. (a) Infrared and (b) 13C NMR spectra of the PAF-FC-1 material.
Nitrogen adsorption–desorption isotherm of PAF-FC-1
450
400
350
300
250
200
Adsorption branch
Desorption branch
1
50
00
1
50
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Relative pressure P/P0
Fig. 2. Adsorption–desorption isotherm of the PAF-FC-1 material.
thesized using the Suzuki reaction [16]. The catalytic absence of a substrate was conducted. The reaction
activity of the new materials in the hydroconversion of mixture contained, in addition to the main products of
model substrates—naphthalene, 1-methylnaphtha-
lene, and 2-methylnaphthalene—was compared with
the activity of the previously studied catalysts.
hexadecane cracking, benzene, toluene, a mixture of
xylenes, and an unidentified component with a high
boiling point, presumably, 2-methylbiphenyl. These
hydrocarbons are formed during the degradation of
To provide a more complete understanding of the
processes that occur during the reaction, a blank the carbon skeleton of the polymer support
experiment with a nickel–molybdenum catalyst in the (Scheme 2).
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NICKEL–TUNGSTEN AND NICKEL–MOLYBDENUM SULFIDE DIESEL
579
+
+
+
+
Scheme 2. Possible mechanism of the thermal degradation of the PAF-FC-1 material.
The dominant degradation product was toluene; phenyl, which are degradation products of the frame-
the amounts of produced benzene and xylenes were work material. The reaction product distribution was
smaller. The degradation product of PAFs synthesized calculated with the subtraction of peaks of these com-
ponents of the mixture. The addition of sulfiding
agents to the reaction mixture leads to an increase in
the yield of hydrotreating products owing to an
through the Suzuki reaction—biphenyl—was not
detected in the reaction mixture [30].
The results of naphthalene hydrogenation are increase in the content of the active sulfide phase. The
shown in Fig. 3. In all cases, the reaction products activity of the molybdenum catalysts was higher than
contained benzene, toluene, xylenes, and 2-methylbi- that of the tungsten catalysts. Thus, naphthalene
+
+
+
+
100
9
0
0
0
0
0
0
0
0
8
7
6
5
4
3
2
10
0
NiMoS NiWS
NiMoS NiWS
NiMoS NiWS
Fig. 3. Naphthalene hydrogenation in the presence of the PAF-FC-1–NiMoS and PAF-FC-1–NiWS catalysts (abbreviated as
NiMoS and NiWS, respectively). The dark gray section denotes methyldecalins.
PETROLEUM CHEMISTRY Vol. 59 No. 6 2019

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80
BATRYSHIN et al.
7. B. Yoosuk, J. H. Kim, C. Song, et al., Catal. Today 130,
hydrogenation in the presence of the NiMoS catalyst
occurs almost quantitatively to decalins (22%) and
tetralin (76%), whereas naphthalene conversion to
tetralin in the presence of the NiWS catalyst is 80% at
a tetralin selectivity of more than 95% (Fig. 3). The
two catalysts mediate the hydrogenation of methyl-
14 (2008).
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Thus, a mesoporous polymer aromatic material
based on tetraphenylmethane (PAF-FC-1) has been
synthesized. The selected synthesis method—the FC
reaction—provides a significant decrease in the cost of
the synthesized polymer materials. Compared with
PAFs synthesized using the Suzuki cross-coupling
reaction, the new material has a slightly higher specific
surface area and a bimodal pore size distribution.
The activity of bimetallic sulfide catalysts based on
PAF-FC-1 in the dearomatization reaction is as high
as the activity of catalysts based on conventional PAFs.
In the presence of the synthesized catalysts, the hydro-
genation of naphthalene, 1-methylnaphthalene, and
1
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1
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FUNDING
6. R. Dawson, L. A. Stevens, T. C. Drage, et al., J. Am.
This work was supported by the Russian Science
Foundation, project no. 15-19-00099.
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2019