Catalytic activity of in situ synthesized MoWNi sulfides in hydrogenation of aromatic hydrocarbons

Article abstract of DOI:10.1134/S0036024417020327

MoWNi–sulfide catalysts were obtained in situ by thermal decomposition of metal–polymer precursors based on the copolymers of polymaleic anhydride in a hydrocarbon raw material. The activity of the synthesized catalysts in hydrogenation of bicyclic aromatic hydrocarbons was studied, and the composition and structure of active phase nanoparticles were determined.

Full text of DOI:10.1134/S0036024417020327

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2017, Vol. 91, No. 2, pp. 205–212. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © Yu.A. Topolyuk, A.L. Maksimov, Yu.G. Kolyagin, 2017, published in Zhurnal Fizicheskoi Khimii, 2017, Vol. 91, No. 2, pp. 205–212.
NANOMATERIALS
AND ENVIRONMENT
Catalytic Activity of In Situ Synthesized MoWNi Sulfides
in Hydrogenation of Aromatic Hydrocarbons
Yu. A. Topolyuka,b*, A. L. Maksimova,c, and Yu. G. Kolyaginc
a Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
b Gubkin Russian State University of Oil and Gas (National Research University), Moscow, 119991 Russia
c Department of Chemistry, Moscow State University, Moscow, 119991 Russia
*e-mail: topolyuk@ips.ac.ru
Received June 16, 2016
Abstract—MoWNi–sulfide catalysts were obtained in situ by thermal decomposition of metal–polymer pre-
cursors based on the copolymers of polymaleic anhydride in a hydrocarbon raw material. The activity of the
synthesized catalysts in hydrogenation of bicyclic aromatic hydrocarbons was studied, and the composition
and structure of active phase nanoparticles were determined.
Keywords: metal–polymer composites, hydrogenation catalysts, transition metal sulfide, hydrodearomatiza-
tion
DOI: 10.1134/S0036024417020327
Hybrid organo-inorganic composites have recently polyoxometal precursors of variable composition and
found increasing use as sensors, photo- and electro- of heteropoly compounds in the presence of different
catalytic devices, pharmaceutical preparations, and sulfurating agents [16]. The use of bi- and trimetallic
catalytically active materials [1–6]. The main advan- precursors, which include metals such as Mo, W, Ni,
tage of these systems is the possibility of tuning the and Со, allows synthesis of catalysts that are highly
physicochemical characteristics of the composite by active in hydroskimming of the hydrocarbon raw
varying the structure and composition of the organic materials [15–17]. The presence of an organic poly-
polymer unit and the nature of the metal.
mer, in particular, a polymer with chelating properties
not only improves the metal binding and changes the
relative rate of metal sulfidation, but also leads to a
removal of water from the coordination environment,
resulting in catalyst deactivation [18].
This paper presents the results of our study of the
activity of MoWNi–sulfide catalysts, prepared in situ
by thermal decomposition of metal–polymer precur-
sors, in hydrogenations of bicyclic aromatic hydrocar-
bons.
The structure of the complexes formed during the
interaction of the polymer molecule with metal ions
depends on many factors such as the nature of the
polymer (determined by the type and concentration of
the available functional groups and the presence of
asymmetric centers in the polymer chain) and metal
(s, p, d element), and the conditions of complexation
(рН, concentration, temperature, etc.) [5]. By varying
the synthesis conditions, one can obtain various cata-
lysts with a definite structure and dispersity of the
active component [7, 8]. Particle aggregation, leading
to catalyst deactivation, can be prevented due to the
presence of the polymer component having a large
number of donor functional groups [9].
In the last decade, unsupported sulfide catalysts
used in hydroskimming of oil stock have attracted par-
ticular attention [10–12]. The structure and catalytic
properties of these systems directly depend on the syn-
thesis conditions. The nanostructured sulfide catalysts
are obtained in industry by the hydrothermal method
[13], mechanoactivation (STARS technology) [14],
and codeposition (Nebula technology) [15]. One of
EXPERIMENTAL
The metal–polymer composites were obtained by
mixing the aqueous solutions of hydrolyzed polymers
and metal salts followed by their ultrasonic dispersion
in a hydrocarbon raw material. Ammonium heptamo-
lybdate (NH4)6Mo7O24 · 4H2O, ammonium dodeca-
tungstate (NH4)10W12O41 · nH2O, and nickel nitrate
hexahydrate Ni(NO3)2 · 6H2O (all of “ch.d.a.” (ana-
lytical) grade) were used as the starting materials. As
the polymer components, we chose the copolymers of
maleic anhydride with octadecene (С18–PMA) and
the most effective methods for the synthesis of sulfide methylvinyl ether (MVE–PMA) (Mn 30000–80000,
catalysts is selective synthesis of the active phase from Aldrich Chemical). The concentrations of the com-
205

206
TOPOLYUK et al.
plexes were chosen such that the metal ratio obtained a CrystalLux 4000 М chromatograph equipped with
in the synthesized precursor was equal to the ratio a flame ionization detector and an SPB-1 column
chosen for the given experiment. The sample is (30 m × 0.25 mm) with a polydimethylsiloxane sta-
denoted by МoxWNi–Р, where х is the Mo : W mole tionary liquid phase (helium carrier gas).
ratio, and P is the polymer component. The Me : P
ratio was chosen based on the molar mass of the poly-
mer and the number of functional groups per polymer
unit such that there were two or three polymer units (1
mol) per 1 mol of the metal ((Mo + W + Ni)/3).
RESULTS AND DISCUSSION
Synthesis and Characteristics
of Sulfide Polymer Catalysts
To form the catalytically active Mo(W)Ni-sulfide
phase in situ, we used elementary sulfur as the sulfi-
dating agent in such a way that its content in the
hydrocarbon raw material was 2.5 wt %. When the
synthesis was performed outside the reaction medium
(ex situ), aqueous solutions of metal salts were added
in sequence to the polymer solution while vigorously
stirring the mixture. The reaction was conducted for 6
h, after which the mixture was evaporated on a rotary
evaporator and dried to a constant mass. The symbol
for the sample is MoxWNi–P-ex.
Earlier, the synthesis of hybrid materials from the
copolymers of polymaleic anhydride and transition
metals [19, 20] and an effective method for the prepa-
ration of metal nanoparticles using copolymers of this
series [21] were reported. To prepare the metal–poly-
mer precursors of the sulfide catalysts, as the polymer
components we chose the polymaleic anhydride
copolymers with methylvinyl ether (MVE–PMA) (1)
and octadecene (С18–PMA) (2). Polymer 1 in hydro-
lyzed form is well soluble in water; polymer 2 is amphi-
philic. The optimum Ni content in the precursors was
chosen such that Ni/(ΣMe) = 0.27 based on the data
of [22, 23].
The obtained precursors were introduced in the
hydrocarbon raw material containing 2.5 wt % ele-
mentary sulfur in the form of a powder or aqueous
solution.
The synthesized polymer composites were studied
by UV and NMR spectroscopy, transmission electron
microscopy (TEM), and X-ray photoelectron spec-
Methods of Investigation of the Obtained Catalysts
The structure and morphology of the in situ troscopy (XPS). The UV spectra of the aqueous solu-
obtained catalysts were studied on a JEM 2100 (JEOL) tions of the precursors (pH 6–7) showed a shift of the
analytical electron microscope. The composition and absorption maxima toward long waves and a simulta-
valence states of elements on the sample surface (the neous decrease in their intensity compared with that of
layer thickness was 5–40 Å) were studied by X-ray the aqueous polymer solutions containing no metal
photoelectron spectroscopy (XPS) on a PHOIBOS ions (λmax = 209 nm). The only weak diffuse maxi-
150MCD (SPECS) instrument. The spectrum decon-
volution was performed by the nonlinear least squares
method using the mixed Gauss–Lorentz function.
The elemental analysis of the samples (mass content of
carbon, hydrogen, nitrogen, and sulfur) was per-
formed on a CHNS–OEA1108 Elemental Analyzer
(Сarlo Erba). The metal content was determined by
atomic absorption spectroscopy on an Analyst 400
instrument.
mum was detected in the region of 230 20 nm. One
possible explanation of this evolution of bands in the
absorption spectra is the formation of new molecular
structures with an ordered spatial position [24, 25].
Thus, as is known, the composition and structure
of transition metal complexes (Мо, Со, W, V, etc.)
with di- and polycarboxylic acids strongly depend on
pH of solution, the number of donor groups of the
ligand, and its concentration in solution [26–32]. For
molybdenum and tungsten complexes with maleic
acid (Kd = 6.8 × 10–9), the structure was determined at
a metal to ligand mole ratio of 1 : 2 and pH 6–8
(Fig. 1).
Catalytic Experimental Procedure
The catalytic experiments were performed in
20-mL steel autoclaves in the temperature range 350–
380°С (heating at 15 K/min) at an initial hydrogen
pressure of 5 MPa while vigorously stirring the mixture
(700 rpm). The model raw materials were 10% solu-
tions of bicyclic aromatic hydrocarbons in n-hexadec-
ane. The substrate : metal mole ratio was 60–100 : 1
(the metal was Mo, W, or Ni). The hydrogen : sub-
strate mole ratio was 50 : 1. The solution of the catalyst
precursor in 2 mL of the model mixture was subjected
to ultrasonic dispersion and then transferred in a glass
liner of an autoclave. The autoclave was heated to the
temperature of experiment at a rate of 15 K/min. The
products of the catalytic experiments were analyzed on
2−
O
C
O
C
HC
HC
O
O
O
O
CH
CH
MoO2
C
O
C
O
Fig. 1. Structure of the Mo(W) complex with maleic acid
[26].
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CATALYTIC ACTIVITY OF IN SITU SYNTHESIZED MoWNi SULFIDES
207
C18−PMA
30.4
Mo−C18−PMA
(a)
(b)
173
180
32.5
34.8
28.2
23.3
41.8
49.1
14.6
200
180
160 [ppm]
80
60
40
20
0 [ppm]
13
Fig. 2. C NMR CP-MAS spectra of the С –PMA and Mo–C –PMA samples. For notation, see the text.
18
18
275
600
30
0
−20
−40
570
0
−20
−40
−60
−80
20
20
371
10
369
429
10
465
0
−60
−80
0
205
−10
−20
−10
−20
726
668
−100
185
C18−PMA
Mo1.7WNi−C18−PMA
100
300
500
700
900
100
300
500
700
900
T, °C
T, °C
Fig. 3. TG–DTA profiles of the samples of the (a) С –PMA polymer аnd (b) Mo WNi–C –PMA complex.
18
1.7
18
At рН > 6, the mononuclear anion complexes that also with the oxygen atoms of the surrounding coordi-
2−
2−
nation polyhedra [7].
form around
or
were found to be dom-
WO4
MoO4
In the 13С NMR spectrum of the Mo–C18–PMA-
ex precursor sample, the signal of carboxyl groups
shifted relative to that of the starting С18–PMA poly-
mer (173 ppm → 180 ppm) (Fig. 2а). This may be
related to molybdenum and tungsten coordination at
the carboxyl groups of the polymer and hence the shift
of electron density to the metal or to the change in the
spatial structure of the polymer. The aliphatic region
of the spectrum is the same for both materials
(Fig. 2b).
inant [27]. The complex forms according to the fol-
lowing scheme:
MoO42− + LHn → MoO OH Ln−2
.
(
)
3
In acid media, however, the polynuclear complexes
are dominant. The coordination sphere can include
both metals of the active phase, as demonstrated on
the Ni–Mo complex obtained in a citric acid solution
[33]. The polynuclear complexes obtained in the pres-
ence of polydentate ligands were just shown to have
the highest catalytic activity [34]. These complexes are
The elemental analysis data for the Mo1.7WNi–C18–
stabilized due to the bonds of the donor groups of the PMA-ex sample (at. (wt) %) are as follows: С 53.90, H
polymer not only with the atoms of the d metals, but 8.54, N 0.52, O 29.52, Ni 1.53, Mo 4.53, W 1.46.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 91 No. 2 2017

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TOPOLYUK et al.
30
28
26
24
22
20
18
16
14
12
10
8
6
4
2
0
5
6
7
8
9
10 11 12 13 14 15 16 18 19
Particle length, nm
50
45
40
35
30
25
20
15
10
5
0
4
6
7
8
9
Average number of layers in a packing
20 nm
10 nm
Fig. 4. Micrographs of the Mo NiW–С –PMA catalyst isolated after the reaction.
1.7
18
MoS2 (Mo 3d5/2
)
MoS2 (Mo 3d3/2
)
MoOxSy (Mo 3d4+)
S2p
Mo 3d6+
MoOxSy (Mo 3d4+)
Mo 3d6+
220
222
224
226
228
230
232
234
236
238
E, eV
Fig. 5. XPS spectrum of the Mo NiW–C –PMA sample after the reaction, the Mo 3d line.
1.7
18
According to the thermogravimetric analysis data mass loss for it is up to 2%. The thermal destruction of
(Fig. 3), mass loss for the Mo1.7WNi–С18–PMA pre-
cursor below 200°C is ~10% probably because of the
removal of water from the molecular complexes. The
the polymer starts above 190°C and is accompanied by
a more than 95% loss of the total mass of the sample.
The precursor loses ~35% of its mass on heating to
polymer is relatively stable under these conditions; 350°C. The exothermal peak at 360°C on the DTA
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CATALYTIC ACTIVITY OF IN SITU SYNTHESIZED MoWNi SULFIDES
209
NiW(Mo)S
Ni2+
NiS
840 844 848 852 856 860 864 868 872 876 880 884
E, eV
Fig. 6. XRS spectrum of the Mo NiW–C –PMA sample after the reaction, the Ni 2p line.
1.7
18
%
100
80
60
40
20
0
Mo(0)
0.6
1
1.7
W(0)
Mo/W, mol.
α, % → MoxNiW−C18−PМА
S, %
S, %
α, % → MoxNiW−МVE−PМА
Fig. 7. Effect of the precursor composition on the conversion of naphthalene (α) and decalin selectivity (S). Reaction conditions:
1% H O, 2.5% S, 380°C, 5 h, 5 MPa H
2
2.
curve can be assigned to the formation of the poly- under the reaction conditions [39]. Nickel is mainly pres-
metal oxide phase. The active decomposition of the ent as mixed NiW(Mo)S (65.2%); sulfur is in the sulfide
(S2–, 48.1%) and oxysulfide ((O2S)6–, 49.4%) form.
The element composition (at. %) of the sample
surface is as follows: C 66.52, O 17.63, S 9.91, Ni 0.26,
Mo 2.94, W 2.74.
The exaggerated carbon content (66%) may be
explained by the presence of hydrocarbons adsorbed
on the catalyst surface after the reaction. Similarly, the
high oxygen content (18%) may be due to the oxida-
tion of the sample during the analysis.
sample on heating (Т > 480°C) is accompanied by a
~80% loss of the mass of the metal–polymer complex.
The micrographs of the Ni–Мо(W)–S sample
obtained in situ show spheroid particles with a diame-
ter of 20–30 nm, in which one can isolate Мо(W)S2
nanoplatelets with a layered structure (Fig. 4). Each of
these platelets contains approximately six layers on
average with a mean layer length of 7 nm.
According to the XPS data (Figs. 5 and 6, Table 1),
the major part of the metal on the surface of the sample
synthesized in situ is in the form of the corresponding
sulfides (64.8% Mo and 50.8% W). The obtained binding
energies agree with the literature data [35–38]. The rela-
tively high content of the oxysulfide phase for tungsten
(41.2%) is explained by the low rate of its sulfidation
Hydrogenation of Bicyclic Aromatic Hydrocarbons
in the Presence of the Prepared Hybride Catalysts
The activity of the catalysts obtained by decompo-
sition of the MoxWNi–P precursors was studied in
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TOPOLYUK et al.
Table 1. Distribution of the valence states of Mo, W, Ni, and
S in the XPS spectrum of the Mo1.7NiW–C18–PMA cata-
lyst after the reaction
reaction temperature and water content in precursors
on the yield and distribution of hydrogenation prod-
ucts showed that the catalysts were inactive below
360°C. The results correlate with the TG–DTA data
of the precursors. According to [23, 39], the presence
of water in the catalyst formation zone favors the for-
mation of the mainly inactive oxysulfide phase. As a
consequence, the activity of the in situ obtained cata-
lysts decreases as the water content in the precursors
increases.
Element
Е, eV
m, %
State
Мо 3d
3d5/2 228.9 64.83
3d3/2 232.1
MoS2
3d5/2 229.4 22.65
3d3/2 233.3
MoSxOy
Mo6+
WS2
The Mo1.7WNi–C18–PMA sample obtained from
the С18–PMA polymer at a mole ratio of Mo : W = 1.7
was most active in hydrogenation of naphthalene at
380°C and 1 wt % water in the precursors. The conver-
sion of naphthalene in the presence of this catalyst
reached 98%, and the total decalin selectivity was
55%. Similar results were obtained for the Mo1.7WNi–
C18–PMA-ех catalyst synthesized ex situ (96% con-
version, decalin selectivity 53%).
Figure 7 shows the results of hydrogenation of the
model mixture (10 wt % naphthalene in n-hexadec-
ane) using the MoхWNi–C18–PMA and MoхWNi–
MVE–PMA precursors. It was found that the metal
ratio in the precursor is much more critical to the cat-
alyst activity than the nature of the complexating poly-
mer.
Based on the data of kinetic experiments (Fig. 8) it
was assumed that the rate of precursor decomposition
limits the hydrogenation: the conversion of naphtha-
lene reaches 90% only in 3 h after the start of the reac-
tion. For Mo1.7WNi–MVE–PMA, there is an induc-
tion period of ~2 h probably due to the change in the
structure of the catalyst and its transition to the active
phase.
3d5/2 232.2 12.52
3d3/2 235.8
W 4f
Ni 2p
S 2p
4f7/2 32.3
4f5/2 34.5
4f7/2 33.1
4f5/2 35.5
4f7/2 36.6
4f5/2 38.3
50.98
41.20
7.82
WSxOy
WO3
2p3/2 852.9 12.26
2p1/2 869.6
NiS
2p3/2 854.1
2p1/2 870.6
65.19
NiW(Mo)S
NiO
2p3/2 855.8 22.55
2p1/2 873.6
Sulfide S2–
Oxysulfide (O2S)6–
2p3/2 161.8
2p3/2 163.3 49.44
2p3/2 169.1 2.44
48.12
Sulfate SO24−
Е is the binding energy, and m is the mass fraction.
According to [40], sulfidation of nickel under the
given conditions starts when Mo(W)S2 crystallites
have already formed. The formation of nickel sulfide
particles on the edges of the structure obtained form
Mo and W sulfides leads to selective synthesis of the
Ni–Mo(W)–S phase of types II and III [23, 40].
Decalins started to form in appreciable amounts
only after 4 h of the reaction. The highest activity was
shown by the Mo1.7WNi–C18–PMA catalyst. This
may be explained by better dispersion of the precursor
in the hydrocarbon medium. The reaction conducted
for prolonged time (10–12 h) leads to very high (90%
and higher) selectivity with respect to decalins in the
presence of Mo1.7WNi–C18–PMA (Fig. 8).
Table 2. Results of hydrogenation of mono- and dimethyl-
naphthalenes in the presence of the Mo1,7WNi–C18–PMA
catalyst
α, %
Decalins/tetralins
Model raw material
5 h
8 h
5 h
8 h
1-Methylnaphthalene
2-Methylnaphthalene
2,3-Dimethylnaphtha- 65
lene
66
75
85
98
76
0.13
0.16
0.07
0.33
0.23
0.14
2,6-Dimethylnaphtha- 78
lene
85
0.16
0.25
A replacement of naphthalene by sterically more
hindered mono- and dimethylnaphthalenes led to a
pronounced decrease of both the total conversion and
the decalin selectivity (Table 2).
Reaction conditions: 1% H O, 2.5% S, 380°C, 5 MPa H ; model
2
2
raw material (10% solution of hydrocarbon in hexadiene); reac-
tion time 5 and 8 h; α is the conversion into the products of
hydrogenation.
According to the presented data, the rate of hydro-
genation of substituted naphthalenes depends on the
number and position of substituents in the aromatic
ring. Naphthalene with a methyl group is adsorbed
hydrogenation of model compounds such as naphtha-
lene, methylnaphthalenes, and dimethylnaphtha-
lenes. The preliminary experiments on the effect of the much more slowly, but, when adsorbed, is hydroge-
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CATALYTIC ACTIVITY OF IN SITU SYNTHESIZED MoWNi SULFIDES
211
%
100
80
60
40
20
0
1
2
3
4
5
6
7
8
9
10
τ, h
α, % → MoxNiW–C18–PMA
Sdec, %
S, %
α, % → Mo1.7NiW–MVE–PMA
Fig. 8. Hydrogenation of naphthalene in the presence of the Mo WNi–C –PMA and Mo WNi–MVE–PMA catalysts; reac-
1.7
18
1.7
tion conditions: 1% H O, 2.5% S, 380°C, 5 MPa H .
2
2
9. E. A. Karakhanov, A. L. Maksimov, A. V. Zolotukhina,
and Yu. S. Kardasheva, Russ. Chem. Bull. 62, 1456
(2016).
nated faster than its unsubstituted analog [40, 41]. Also
note that adsorption is more strongly hindered by the
methyl groups lying in the vicinal position (as in 2,3-
dimethylnaphthalene) or near the main carbon atoms
(as in 1-methylnaphthalene).
Thus, MoWNi–sulfide catalysts were synthesized
by thermal decomposition of metal–polymer precur-
sors in a sulfur-containing hydrocarbon raw material.
The thus obtained catalysts showed high activity in
hydrogenation of bicyclic aromatic hydrocarbons. The
optimum ratio of metals in the precursor was found at
which the maximum conversion of naphthalene and
decalin selectivity can be reached.
10. S. N. Khadzhiev, Kh. M. Kadiev, and M. Kh. Kadieva,
Pet. Chem. 54, 323 (2014).
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RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 91
No. 2
2017