Nickel-tungsten sulfide polyaromatic hydrocarbon hydrogenation nanocatalysts prepared in an ionic liquid

Article abstract of DOI:10.1134/S0965544115010120

Nickel-tungsten sulfide nanocatalysts for the hydrogenation of aromatic hydrocarbons (HCs) have been prepared by the in situ decomposition of nickel thiotungstate precursors in an ionic liquid (IL) using the [BMPip]₂Ni(WS₄)₂ nickel thiotungstate complex as a precursor and the thermally stable IL 1-butyl-1-methylpiperidinium trifluoromethanesulfonate BMPipCF₃SO₃ as a solvent for the precursor. The Ni-W-S particles in situ synthesized in the IL have been characterized by X-ray photoelectron spectroscopy and TEM. It has been shown that the particles are 0.5-nm-wide nanoplates associated in agglomerates with a diameter of 100-150 nm. Catalytic activity has been studied using the example of naphthalene hydrogenation in various solvents in a batch reactor at a temperature of 350°C and a pressure of 5.0 MPa. It has been shown that the IL can be used for the selective hydrogenation of aromatic HCs in a mixture with olefins.

Full text of DOI:10.1134/S0965544115010120

ISSN 0965ꢀ5441, Petroleum Chemistry, 2015, Vol. 55, No. 1, pp. 38–44. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © I.A. Sizova, S.I. Serdyukov, A.L. Maksimov, N.A. Sinikova, 2015, published in Neftekhimiya, 2015, Vol. 55, No. 1, pp. 41–47.
Nickel–Tungsten Sulfide Polyaromatic Hydrocarbon Hydrogenation
Nanocatalysts Prepared in an Ionic Liquid
I. A. Sizovaa, S. I. Serdyukova, b, A. L. Maksimova, b, and N. A. Sinikovab
aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
bFaculty of Chemistry, Moscow State University, Moscow, Russia
eꢀmail: isizova@ips.ac.ru
Received June 5, 2014
Abstract—Nickel–tungsten sulfide nanocatalysts for the hydrogenation of aromatic hydrocarbons (HCs)
have been prepared by the in situ decomposition of nickel thiotungstate precursors in an ionic liquid (IL)
using the [BMPip]2Ni(WS4)2 nickel thiotungstate complex as a precursor and the thermally stable IL 1ꢀbutylꢀ
1ꢀmethylpiperidinium trifluoromethanesulfonate BMPipCF3SO3 as a solvent for the precursor. The Ni–W–S
particles in situ synthesized in the IL have been characterized by Xꢀray photoelectron spectroscopy and TEM.
It has been shown that the particles are 0.5ꢀnmꢀwide nanoplates associated in agglomerates with a diameter
of 100–150 nm. Catalytic activity has been studied using the example of naphthalene hydrogenation in variꢀ
ous solvents in a batch reactor at a temperature of 350°C and a pressure of 5.0 MPa. It has been shown that
the IL can be used for the selective hydrogenation of aromatic HCs in a mixture with olefins.
Keywords: nickel–tungsten sulfide catalysts, ionic liquid, twoꢀphase catalysis, hydrogenation of aromatic
hydrocarbons
DOI: 10.1134/S0965544115010120
The depletion of light oil resources and the involveꢀ ity of the catalysts [5]. This has given rise to the develꢀ
ment of increasingly heavier petroleum fractions with opment of a new approach to the synthesis of catalysts:
a high content of sulfur and aromatic hydrocarbons the use of supports is waived and catalyst nanoparticles
(HCs) in the processing have stimulated increased are formed directly in the HC feedstock (in situ).
interest in research into new sulfurꢀresistant catalysts Thiosalts are typically used as precursors for the prepꢀ
for the hydrogenation of aromatic compounds [1]. aration of sulfide nanocatalysts [6–10]. The in situ
Owing to the exceptional resistance to catalyst poiꢀ decomposition of thiosalts in the reaction medium
sons, supported transition metal sulfides [2]—mostly provides a high sulfur content in the final sulfide cataꢀ
molybdenum and tungsten sulfides promoted with lyst and contributes to the production of stable fine
cobalt or nickel—are widely used to remove heteroatꢀ particles [6, 11].
oms, such as sulfur and nitrogen. However, data on the
It is known that the efficiency of sulfide catalysts
use of these systems for the hydrogenation of aromatic
depends on their particle size and the higher the
HCs are quite scarce [3].
degree of dispersion, the higher the efficiency of cataꢀ
The main problem in the selection of the composiꢀ lytic action. However, the use of nanocatalysts is
tion and preparation method for Moꢀ and Wꢀbased fraught with a number of significant problems, such as
catalysts for the hydrogenation of aromatic HCs difficulties in the separation of nanoparticles from the
(hydrodearomatization) of petroleum feedstocks is the reaction products and recycling the catalysts. A possiꢀ
necessity to increase the hydrogenation activity of ble solution to these problems is the use of twoꢀphase
Mo(W)Co(Ni) catalyst systems with respect to aroꢀ catalysis involving alternative solvents, such as water
matic HCs, while maintaining their efficiency in [12], ionic liquids (ILs) [13], perfluorinated HCs [14],
hydrotreating reactions. It is known that the substituꢀ and supercritical carbon dioxide [15].
tion of Ni for Co and W for Mo makes it possible to
The basic concept of twoꢀphase catalysis is that
improve the hydrogenation activity of the catalysts.
after the reaction, the catalyst remains in one phase
With respect to hydrogenation activity in the presence
while the reaction products and the precursors in the
of sulfur compounds, the catalysts are arranged in the
other. Separation into two phases facilitates the sepaꢀ
following order: Ni–W > Ni–Mo > Co–Mo [4].
ration of the catalyst from the reaction products and
In recent years, interest in the study of nanocataꢀ simplifies recycling the catalyst. It is convenient to use
lysts has significantly increased, which is attributed to ILs as a solvent because these media are favorable for
the possibility of improving the efficiency and selectivꢀ synthesizing particles [16–19].
38

NICKEL–TUNGSTEN SULFIDE POLYAROMATIC HYDROCARBON HYDROGENATION
39
The aim of this study is to prepare nickel–tungsten CH2CH2CH2CH2NCH2CH2); 3,1 (s, 3H, NCH3);
sulfide nanocatalysts by the in situ decomposition of 3.5 (m, 6H, N(CH2)3).
thiosalts in an IL and test the resulting catalysts in the
replaced by the CF3SO–3 triflate anion. To a solution of
hydrogenation of polyaromatic HCs.
At the second stage, the anion in [BMPip]Br was
1ꢀbutylꢀ1ꢀmethylpiperidinium bromide (16.9 g of
[BMPip]Br in 50 mL of water), 13.5 g of potassium triꢀ
fluoromethanesulfonate salt KCF3SO3 was added and
EXPERIMENTAL
the resulting mixture was stirred at 80°C for 1 h. After
that, the reaction mixture was cooled to room temperꢀ
ature, 25 mL of distilled water was added, and the
resulting mixture was extracted with dichloromethane
Synthesis Procedures
Ammonium thiotungstate (NH4)2WS4 was prepared
as described in [20]. To this end, 0.03 mol of sodium
tungstate Na2WO4 2 H2O was dissolved in 40 mL of
⋅
(3
×
25 mL). The separated organic phase was washed
20 mL) and dried over
H2O; the solution was admixed with 15 mL of hydroꢀ
chloric acid; and the mixture was stirred for 10 min
until the formation of a yellow precipitate of tungstic
acid H2WO4. The mixture was centrifuged at a rate of
3000 rpm for 5 min and then twice washed with water.
The resulting H2WO4 acid was placed in a furnace and
evaporated by one third of its mass at 95°C. Sixty milꢀ
liliters of concentrated aqueous ammonia was added
to H2WO4. Hydrogen sulfide was passed through the
resulting solution at 60°C for 30 min; after that, the
formed green precipitate was filtered off. Hydrogen
sulfide was then passed through the resulting bright
yellow solution at 60°C for 8 h. Next, the mixture was
cooled; the resulting orange precipitate of (NH4)2WS4
was filtered off and washed with isopropanol and
diethyl ether.
with freshly distilled water (2
×
MgSO4. The resulting [BMPip]CF3SO3 IL was dried
in a vacuum at a temperature of 90°C. The purity and
1
structure of the product were confirmed by H NMR
1
data. H NMR (CDCl3):
δ
, ppm: 0.89 (t, 3H,
CH2CH3); 1.3 (m, 2H, CH2CH3); 1.8 (m, 8H,
CH2CH2CH2CH2NCH2CH2); 2.9 (s, 3H, NCH3);
3.3 (m, 6H, N(CH2)3).
Catalyst Investigation Methods
Analyses for carbon, hydrogen, nitrogen, and sulꢀ
fur were performed with a CarboErba CHNSꢀ
OEA1108 elemental analyzer. The metal content was
determined by atomic absorption spectroscopy using
an AAnalyst 400 instrument.
Elemental analysis: found (%): C, 0; H, 2.3; N, 8.4;
S, 38.0; W, 51.3; calcd. (%): C, 0; H, 2.3; N, 8.0;
S, 36.8; W, 52.8.
The in situ prepared catalyst samples were examꢀ
ined using a Carl Zeiss LEO912 AB OMEGA transꢀ
mission electron microscope. Xꢀray photoelectron
spectroscopy (XPS) studies of the samples were conꢀ
ducted using a LASꢀ3000 electronic instrument
equipped with an OPXꢀ150 retardingꢀpotential phoꢀ
toelectron analyzer. Photoelectrons were excited using
1ꢀButylꢀ1ꢀmethylpiperidinium nickel thiotungstate
complex [BMPip]2Ni[WS4]2 was prepared using an
ingenious technique described in [21]. A nickel chloꢀ
ride solution containing 0.238 g of NiCl2 6H2O and
⋅
10 mL of a H2O–CH3CN mixture (a H2O : CH3CN
volume ratio of 1 : 1) acidified with a few drops of aceꢀ
tic acid was added to a solution containing 0.7 g of
ammonium thiotungstate (NH4)2WS4 and 10 mL of a
H2O–CH3CN mixture (a H2O : CH3CN volume ratio
of 1 : 3). The resulting mixture was admixed with a
solution containing 2.1 g of [BMPip]Br and 15 mL of
the Xꢀray emission of an aluminum anode (AlK =
α
1486.6 eV) with a tube voltage of 12 kV and an emisꢀ
sion current of 20 mA. Photoelectron peaks were caliꢀ
brated against the carbon C 1s line with a binding
energy of 285 eV.
CH3CN
.
The formed brown precipitate of
Catalytic Testing Procedure
[BMPip]2Ni(WS4)2 was filtered off, washed with water
and isopropanol, and then dried in the air. Elemental
analysis: found (%): C, 24.35; H, 4.3; N, 3.2; S, 27.1;
Ni, 5.69; and W, 35.36; calcd. (%): C, 24.13; H, 4.45;
N, 2.81; S, 25.76; Ni, 5.89; W, 36.93.
Catalytic hydrogenation tests were conducted in a
steel autoclave in a hydrogen atmosphere under a high
pressure and vigorous stirring of the reaction mixture.
The [BMPip]2Ni[WS4]2 precursor dissolved in 1 mL of
1ꢀButylꢀ1ꢀmethylpiperidinium trifluoromethaneꢀ the [BMPip]CF3SO3 IL was placed into the glass carꢀ
sulfonate ([BMPip]CF3SO3) IL was according to a tridge of the autoclave; after that, 1 mL of the substrate
standard procedure [22]. At the first stage, 1ꢀmethꢀ was added. The autoclave was filled with hydrogen to a
ylpiperidine C6H13N and 1ꢀbromobutane C4H9Br in pressure of 50 atm and held at a temperature of 350°C
methyl ethyl ketone were used to prepare 1ꢀbutylꢀ1ꢀ for 1–10 h. The hydrogenation products were anaꢀ
methylpiperidinium bromide [BMPip]Br. The resultꢀ lyzed on a 4000 M Kristallyuks chromatograph
ing product was purified by recrystallization. The equipped with a FID and a SPBꢀ1 capillary column
purity and structure of the product were confirmed by coated with the polydimethylsiloxane stationary phase
1H NMR data. 1H NMR (CDCl3):
CH2CH3); 1.2 (m, 2H, CH2CH3); 1.6 (m, 8H, split ratio, 1 : 90).
δ
, ppm: 0.8 (t, 3H, (dimensions, 30 m
×
0.25 mm; carrier gas, helium;
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40
SIZOVA et al.
WО3
WS2
WO Sy
x
W 4
f
50 nm
45 44 42 40 38 36 34 32 30 28 26
Binding energy, eV
Fig. 1. Micrograph of the Ni–W–S catalyst prepared by in
situ decomposition in an IL.
Fig. 2. Deconvolution of the W 4f level.
RESULTS AND DISCUSSION
XPS analysis of the samples has shown that all the
catalysts exhibit peaks characteristic of tungsten, sulꢀ
fur, carbon, and nickel.
Characterization of Ni–W–S Catalysts Prepared
in Situ in IL
Figure 2 shows the deconvolution of the W 4
The studied samples contain tungsten in three forms:
sulfide (W 4 7/2, 32.5 eV; W 4 5/2, 34.2 eV), oxysulfide
(W 4 7/2, 33.4 eV; W 4 5/2, 35.2 eV), and oxide (W 4 7/2
35.8 eV; W 4 5/2, 37.8 eV). The specified binding enerꢀ
f level.
All of the nickel–tungsten catalysts were nanoꢀ
f
f
plates associated in agglomerates, as evidenced by
TEM. A typical micrograph of these catalysts is shown
in Fig. 1. The width of the plates is ~5 Å; the length of
each plate is about 100–150 nm. The plates are assoꢀ
ciated in agglomerates with a size of 100–150 nm.
f
f
f ,
f
gies are consistent with the literature data [23]. The
weight ratios of the resulting phases are listed in Table 1.
It is evident from the data that only 26.4% W is in the
sulfide form, while the remaining 73.6% is in the
oxysulfide and oxide forms, and the latter is dominant.
Table 1. XPS data for the W 4f and Ni 2p levels
Figure 3 shows the deconvolution of the Ni 2
The studied samples contain nickel in the form of sulꢀ
fide NiS (Ni 2 3/2, 852.6 eV; Ni 2 1/2, 869.8 eV), in the
form of NiWS (Ni 2p3/2, 853.8 eV; Ni 2 1/2, 870.6 eV),
and in the form of oxide NiO (Ni 2 3/2, 856.2 eV;
Ni 2 1/2, 873.7 eV). The specified binding energies are
consistent with the literature data [23]. The peaks that
are not marked in color correspond to satellites. The
weight ratios of the resulting phases for nickel are listed
in Table 1. It has been found that more than 70% of
nickel is in the oxide form.
p level.
Weight
fraction, %
Element Binding energy, eV
State
WS2
p
p
p
p
W 4
f
4 7/2
4 5/2
4 7/2
4 5/2
4 7/2
4 5/2
f
32.5
34.2
33.4
35.2
35.8
37.8
26.4
30.1
43.5
p
f
f
WOxSy
WO3
f
f
The deconvolution of the S 2p level (Fig. 4) has
shown that the sulfur is in two states: S2– (161.4 eV) and
in the form of oxysulfide (163.9 eV). The weight ratios
of the resulting phases for sulfur are listed in Table 2. It
should be noted that the data suggest that there is no
sulfur in the +6 oxidation state, which must correspond
to a peak at a binding energy of 169 eV [24].
f
Ni 2p
2p3/2
2p1/2
2p3/2
2p1/2
2p3/2
2p1/2
852.6
869.8
853.8
870.6
856.2
873.7
7.6
20.5
71.9
NiS
NiWS
NiO
The data on the typical composition of the sample
surface are indicative of an excess carbide phase (the
atomic concentration of carbon on the sample surface
is 69.2%) and a deficiency of nickel; the atomic conꢀ
centration of nickel on the surface is as low as 2.2%,
PETROLEUM CHEMISTRY Vol. 55
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NICKEL–TUNGSTEN SULFIDE POLYAROMATIC HYDROCARBON HYDROGENATION
41
NiS
NiWS
Ni 2p
NiO
888
878
868
Binding energy, eV
858
848
Fig. 3. Deconvolution of the Ni 2p level.
6–
(O2S)
S2–
S 2p
179 177 175 173 171 169 167 165 163 161 159 157 155 153
Binding energy, eV
Fig. 4. Deconvolution of the S 2p level.
while that of tungsten is 8.6%. These findings are conꢀ solution of naphthalene in
nꢀhexadecane was used as a
sistent with the literature data [20]. The atomic conꢀ
centration of sulfur on the surface of the prepared catꢀ
alysts is about 20%.
model feedstock. The tungsten to nickel molar ratio in
the precursor was 2 : 1. Table 3 shows the dependence
of the conversion of naphthalene on the W : Ni ratio;
nickel nitrate Ni(NO3)2 6H2O was used as an addiꢀ
⋅
tional source of nickel; it is evident that nickel nitrate
without the salt precursor and the salt precursor in the
absence of nickel nitrate exhibit low catalytic activity
(the conversion of naphthalene is 3–9%). The optiꢀ
Catalytic Properties
The catalytic properties of the prepared catalyst
were studied in a batch reactor at a temperature of
350°C and a hydrogen pressure of 5.0 MPa. A 10% mum W : Ni ratio is 1 : 1; in this case, the conversion
PETROLEUM CHEMISTRY Vol. 55
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42
SIZOVA et al.
Table 2. XPS data for the S 2p level
reaction time, the main product of the reaction is tetraꢀ
lin, while decalins are hardly formed at all.
Binding
energy, eV fraction, %
Weight
Figure 6 shows the dependence of the conversion of
naphthalene on the precursor concentration in the IL
at a tungsten to nickel molar ratio of 1 : 1 and a reacꢀ
tion time of 10 h. It is evident that as the naphthalene
to tungsten ratio decreases from 73 : 1 to 7.3 : 1, which
corresponds to a change in the precursor concentraꢀ
tion in the IL from 4.3 to 43 g/mL, the conversion of
naphthalene increases from 6.0 to 92%. The main
product of the reaction is tetralin; however, the selecꢀ
State
S 2p
161.4
163.9
36.6
63.4
Sulfide S2–
Oxysulfide (O2S)6–
Table 3. Dependence of the conversion of naphthalene on
the W : Ni molar ratio ( = 350 C, PH = 5.0 MPa,
naphthalene : tungsten = 7.3 mol/mol)
T
°
t
= 10 h, tivity for decalins increases to reach 20% at a naphthaꢀ
lene to tungsten ratio of 73 : 1 with a decrease in the
precursor concentration in the IL.
2
Naphthalene
conversion, %
The catalyst systems prepared can be repeatedly
used without loss of activity. Thus, in the case of using
the catalyst system with a naphthalene to tungsten
molar ratio of 7.3 : 1 and a tungsten to nickel atomic
ratio of 1 : 1, the conversion of naphthalene does not
decrease during four catalytic runs.
Precursor
W : Ni
Ni(NO3)2
[BMPip]2Ni(WS4)2
–
3
9
2 : 1
[BMPip]2Ni(WS4)2 + Ni(NO3)2 1 : 1
[BMPip]2Ni(WS4)2 + Ni(NO3)2 2 : 1
92
4
Examination of the conversions of octeneꢀ1 over a
Ni–W–S catalyst dissolved in the IL has shown that
this sample exhibits high catalytic activity. The degree
of conversion of octeneꢀ1 was 95%; however, the nꢀ
octane content did not exceed 3%. In general, the
doubleꢀbond migration occurred; in addition, among
the octeneꢀ1 isomers, the octeneꢀ4 content was ~60%.
Next, a set of experiments on the hydrogenation of
of naphthalene achieves 92%. The main product of
hydrogenation is tetralin; the selectivity for decalins
does not exceed 4%.
Figure 5 shows the dependence of the naphthalene a mixture of aromatic HCs with olefins was conducted
conversion on the reaction time for a catalyst exhibitꢀ using the example of a 10% solution of naphthalene in
ing an optimum catalytic activity (the tungsten to octeneꢀ1. The conversion of naphthalene was 77% (a
nickel ratio is 1 : 1). As the reaction time increases from naphthalene to tungsten ratio of 6.7 : 1), while the
3 to 10 h, the conversion of naphthalene increases from conversion of octeneꢀ1 to nꢀoctane did not exceed 5%.
14 to 92%. If the reaction time is 3 h, the selectivity for In a similar experiment without using an IL, i.e., in the
decalins does not exceed 30%. In the case of a longer case of preparing a Ni–W–S catalyst by the in situ
100
80
60
40
20
0
100
80
60
40
20
0
10
20
30
40
50
2
4
6
8
10
12
Precursor concentration in IL, g/mL
Reaction time, h
Fig. 5. Dependence of the conversion of naphthalene on
reaction time. Experimental conditions: = 350°C, PH
Fig. 6. Dependence of the conversion of naphthalene on
the precursor concentration in the IL. Experimental conꢀ
T
=
2
ditions:
T = 350°C, PH = 5.0 MPa, t = 10 h, and W :
2
5.0 MPa, naphthalene : tungsten = 7.3 mol/mol, and W :
Ni = 1 : 1.
Ni = 1 : 1.
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NICKEL–TUNGSTEN SULFIDE POLYAROMATIC HYDROCARBON HYDROGENATION
43
Table 4. Distribution coefficients of the substrates between
ꢀhexadecane and the [BMPip]CF3SO3 IL
exceed ~3%. The solubility of 2ꢀmethylnaphthalene in
ILs is poorer; under similar reaction conditions, the
conversion of this material was 40%. The main prodꢀ
uct of hydrogenation was 6ꢀmethyltetralin; the selecꢀ
tivity for this product was 70%. The methyldecalin
content in the hydrogenation products did not exceed
2%. There results on the hydrogenation of methylꢀ
naphthalenes are consistent with the data on the soluꢀ
bility of these materials in ILs. The higher solubility of
1ꢀmethylnaphthalene leads to a higher degree of
hydrogenation of this substance.
n
Distribution coeffiꢀ Converꢀ
Substrate
cient (Corg.ph./CIL)
sion, %
Naphthalene
Octeneꢀ1
1.75
27.5
6.2
92
3
Tetralin
5
These findings suggest that the determining factor
of hydrogenation is the solubility of substrates in the
IL. The degree of conversion of the substrates exhibitꢀ
ing poor solubility did not exceed 10%. The converꢀ
sion of the substrates that are highly soluble in the IL
achieved 90%. Thus, the use of Ni–W–S catalysts
prepared in an IL makes it possible to selectively
hydrogenate polyaromatic HCs.
Toluene
6.4
0
Ethylbenzene
1ꢀMethylnaphthalene
2ꢀMethylnaphthalene
9.6
0
1.35
1.82
80
40
In this study, 1ꢀbutylꢀ1ꢀmethylpiperidinium nickel
thiotungstate [BMPip]2Ni(WS4)2 has been first preꢀ
pared. This complex has been in situ decomposed in
an IL to prepare nickel–tungsten sulfide nanocatalysts
for the hydrogenation of polyaromatic HCs.
TEM studies have shown that the catalyst particles are
0.5ꢀnmꢀwide nanoplates associated in agglomerates
with a size of 100–150 nm.
The properties of the prepared catalysts in the
hydrogenation of aromatic HCs and octeneꢀ1 have
been studied. It has been shown that nickel–tungsten
catalysts prepared in ILs can be used for the selective
hydrogenation of polyaromatic HCs in a mixture with
olefins. The activity of the studied catalysts is deterꢀ
mined by the solubility of the used substrates in the IL.
decomposition in a HC feedstock, the conversion of
octeneꢀ1 to ꢀoctane and naphthalene to tetralin was
100%. It is of interest to note that, in this case, the
product of the hydrogenation of naphthalene was not
only tetralin, but also decalins, and the decalin conꢀ
tent in the reaction products was ~50%.
n
The high conversion of naphthalene compared that
of octeneꢀ1 is apparently attributed to the different
solubility of the used substrates in the IL. Table 4
shows the distribution coefficients of the used subꢀ
strates between [BMPip]CF3SO3 and nꢀhexadecane.
It is evident from Table 4 that the solubility of naphꢀ
thalene in the IL is significantly higher than that of
octeneꢀ1. It is significant that tetralin is also poorly
soluble in ILs. It is this phenomenon that can explain
the fact that the main product of naphthalene hydroꢀ
ACKNOWLEDGMENTS
genation is tetralin, which passes from the IL into nꢀ
hexadecane and does not undergo further hydrogenaꢀ
tion to decalin.
This work was supported by the federal target proꢀ
gram “Research and Development in Priority Fields
of Science and Engineering in Russia for 2007–2013,”
state contract no. 14.516.11.0093.
The work was performed using the equipment of
the Center for collective use “New Petrochemical
Processes, Polymer Composites, and Adhesives.”
To confirm this result, a set of experiments on the
hydrogenation of toluene and ethylbenzene, which
exhibit low solubility in ILs, was conducted (Table 4).
At a substrate to tungsten ratio of 7.3 : 1 and W : Ni =
1 : 1, the conversion of both toluene and ethylbenzene
did not exceed 5%. In a similar experiment on the in
situ decomposition of the precursor in an HC feedꢀ
stock without using an IL, the conversion of toluene
and ethylbenzene was 50 and 30%, respectively (a subꢀ
strate to tungsten ratio of 105.3 : 1).
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1 : 1, the conversion of 1ꢀmethylnaphthalene was 80%.
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PETROLEUM CHEMISTRY Vol. 55
No. 1
2015