An Effect of a Support Nature and Active Phase Morphology on Catalytic Properties of Ni-Containing Catalysts in Hydrogenation of Biphenyl

Article abstract of DOI:10.1134/S1070427218100191

Ni/Sup catalysts were prepared, where SBA-15, γ-Al₂O₃, SiO₂ were used as supports (Sup). The synthesized catalysts were investigated by the methods of low-temperature nitrogen adsorption, temperatureprogrammed reduction (TPR), and high-resolution transmission electron microscopy. The catalytic properties of the prepared catalysts were tested in liquid phase hydrogenation of biphenyl under conditions of a flow installation at temperatures of 60–100°C, pressure of 4 MPa, volumetric feed rate of 4–10 h^–1 and H₂: feed ratio of 1500 nM. A 1 wt % solution of biphenyl in heptane, as a model mixture, was used. It has been established that the activity of nickel hydrogenation catalysts depends on the nickel content and the type of support. The activity of supported nickel catalysts decreases in the series Ni-12/SBA-15 > Ni-12/SiO₂ >> Ni-12/Al₂O₃. The kinetic characteristics of the biphenyl hydrogenation reaction were determined: the rate constants and activation energy for the hydrogenation of the first and second aromatic rings of the substrate molecule.

Full text of DOI:10.1134/S1070427218100191

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2018, Vol. 91, No. 10, pp. 1701−1710. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © M.M. Chernova, P.P. Minayev, Ye.A. Martynenko, Al.A. Pimerzin, Yu.V. Yeremina, S.P. Verevkin, A.A. Pimerzin, 2018, published in Zhurnal
Prikladnoi Khimii, 2018, Vol. 91, No. 10, pp. 1506−1515.
CATALYSIS
An Effect of a Support Nature and Active Phase
Morphology on Catalytic Properties of Ni-Containing
Catalysts in Hydrogenation of Biphenyl
a
a
a
a
M. M. Chernova , P. P. Minayev , Ye. A. Martynenko , Al. A. Pimerzin ,
a
a
a,
Yu. V. Yeremina , S. P. Verevkin , and A. A. Pimerzin *
a
Samara State Technical University, Samara, 443100 Russia
*
e-mail: pimerzin.aa@samgtu.ru
Received September 21, 2018
Abstract—Ni/Sup catalysts were prepared, where SBA-15, γ-Al O , SiO were used as supports (Sup). The
2
3
2
synthesized catalysts were investigated by the methods of low-temperature nitrogen adsorption, temperature-
programmed reduction (TPR), and high-resolution transmission electron microscopy. The catalytic properties of
the prepared catalysts were tested in liquid phase hydrogenation of biphenyl under conditions of a flow instal-
–
1
lation at temperatures of 60–100°C, pressure of 4 MPa, volumetric feed rate of 4–10 h and H : feed ratio of
2
1
500 nM.. A 1 wt % solution of biphenyl in heptane, , as a model mixture, was used. It has been established that
the activity of nickel hydrogenation catalysts depends on the nickel content and the type of support. The activity
of supported nickel catalysts decreases in the series Ni-12/SBA-15 > Ni-12/SiO >> Ni-12/Al O . The kinetic
2
2
3
characteristics of the biphenyl hydrogenation reaction were determined: the rate constants and activation energy
for the hydrogenation of the first and second aromatic rings of the substrate molecule.
Keywords: biphenyl, hydrogenation, Ni-containing catalysts, SBA-15, Al O , SiO
2
2
3
DOI: 10.1134/S1070427218100191
In recent decades, there has been a trend to tighten
the requirements for energy efficiency and emissions of
pollutants into the environment. In this regard, energy
sources based on alternative fuels, including hydrogen,
are in great demand. The use of such fuel cells is
impossible without the development of efficient hydrogen
storage methods that will ensure its safe storage and
transportation. The use of liquid organic hydrogen carriers
dehydrogenation, availability, low toxicity, and reasonable
price [3]. At the first stage, benzene–cyclohexane and
toluene–methylcyclohexane pairs were considered as the
most promising among hydrogen carriers, the conditions
of hydrogenation and dehydrogenation of which were
well studied [4]. However, a common drawback of these
compounds is the low boiling point, which makes them
highly volatile and causes a loss of the substrate. Recently,
the attention of researchers has increasingly been attracted
to systems based on polycyclic aromatic compounds, and
biphenyl is one of the promising candidates as a hydrogen
carrier because it meets most of the requirements for
LOHC.
(LOHCs) can be one of such methods, which is based on
the use of reversible hydrogenation–dehydrogenation
reactions of organic compounds, for example, aromatic
and polycyclic aromatic hydrocarbons [1, 2].
There are a number of requirements for LOHC
systems: high hydrogen capacity (> 5.0 wt %), thermal
stability, suitable boiling points and melting points,
favorable thermodynamic conditions for hydrogenation–
Considerable attention is also paid to the selection
of catalysts for the processes of hydrogenation and
dehydrogenation. The catalyst, besides the fact that it
1
701

1702
CHERNOVA et al.
must exhibit high activity and selectivity, must be stable
and minimize the possibility of side cracking reactions.
Selective hydrogenation of biphenyl was studied in the
presence of supported catalysts based on Pt [5, 6], Rh, Ru
water, dried at 60, 80, 120°C (5, 2, 5 h, respectively) and
calcined at 240 and 550°C (4 and 6 h, respectively). The
calcined precipitate was tableted under a press (5 tons).
The molded supports were crushed and a fraction of
0.25–0.50 mm was sieved out, which was later used to
prepare catalysts.
[
7], Pt–Pd [8], CoO–MoO [9]. Data on the hydrogenation
3
of biphenyl on Ni-containing catalysts are practically
absent, despite the fact that the hydrogenation of other
aromatic hydrocarbons on nickel catalysts has been
well studied [10, 11]. Data on the reduction of phenol,
naphthalenes, biphenyls, acenaphthenes, and other
compounds are reported to the corresponding hydrocarbon
derivatives on the Raney Ni–Al alloy in a dilute aqueous-
alkaline solution at 90°C and atmospheric pressure.
There is also evidence of the selective hydrogenation of
biphenyl to cyclohexylbenzene on skeletal Ni (Raney
Ni) [13]. According to the literature, nickel catalysts are
less active than platinum, but they are much cheaper,
which makes them attractive for research and potential
use. Changing the type of carrier and the content of the
active phase allows varying the properties of the catalyst
and choosing a system that will ensure efficient operation
of the LOHC system based on biphenyl.
A commercial sample (Sigma-Aldrich), fraction
0
.25–0.50 mm, was used as silicon oxide.
The active component was applied to the prepared
fraction of the support by the method of single
impregnation by capacity with an aqueous solution of
nickel(II) nitrate hexahydrate. The impregnated samples
were kept for 1 day at room temperature, and then dried
(at 60°C for 2 h, at 120°C for 6 h) and calcined at 450°C
in air for 1 h. Recovery of the catalysts was carried out in
an excess of hydrogen at 400°C for 2 h in the reactor, in
which then the catalytic activity of the prepared sample
was studied. The synthesized nickel catalysts had the
abbreviation Ni-x/Sup, where x is the nickel content in
the sample (wt %), Sup is the type of support (γ-Al O ,
2
3
SiO , SBA-15).
2
The textural characteristics of the synthesized carriers
were investigated by the method of low-temperature
nitrogen adsorption on a Quantochrome Autosorb-1
porosimeter. The specific surface area was calculated
using the Brunauer–Emmett–Teller (BET) model.
The total pore volume and pore size distribution were
calculated from the desorption branch of the nitrogen
adsorption isotherm using the Barrett–Joyner–Handenda
model (BJH).
The purpose of this work was the synthesis and
experimental study of the catalytic activity of nickel
catalysts on various supports in the liquid-phase
hydrogenation of biphenyl.
EXPERIMENTAL
Aluminum oxide γ-Al O , mesoporous aluminosilicate
2
3
SBA-15, and silicon oxide SiO (Sigma-Aldrich) with
2
The synthesized catalysts were investigated by the
methods of thermoprogrammed recovery and high
resolution transmission electron microscopy.
textural characteristics (Table 2) were used as supports.
To synthesize a support based on γ-Al6 O , peptization of
2
3
TH-60 pseudoboehmite powder (SASOLfirm) with nitric
acid was carried out, then it was molded by extrusion
Thermoprogrammed recovery of nickel catalysts
was carried out on TPDRO 1100 using a thermal
conductivity detector. Immediately prior to analysis, the
samples were dried under argon at different temperatures.
Thermoprogrammed recovery was carried out in a
(length and diameter of cylinders were 6 and 1.5 mm,
respectively), dried in air at 60, 80, 120°С (for 2 h) and
calcined at 550°С for 2 h (the rate of temperature rise to
–
1
5
50°С was 1 deg min ).
5
vol % hydrogen mixture in nitrogen with the following
SBA-15 was prepared according to the method [14]
–
1
parameters: a volumetric feed rate of 50 mL min , a
temperature range from room temperature to 400°С, a
heating rate of 10 deg min . Recovery was carried out
for 1 h.
using the following reagents: tetraorthosilicate (TEOS)
as a source of silicon, Pluronic 123 as a surfactant, 2 M
HCl solution and distilled water. With stirring, a solution
of Pluronic 123 in distilled water was prepared, then a
solution of HCl was added dropwise to it, and at last
TEOS was added dropwise. The resulting mixture was
kept under static conditions at 80°C for 48 h. The white
precipitate formed was filtered, washed several times with
–
1
The reconstructed samples of the catalysts were
examined by TEM-BP using a Tecnai G2 20 electron
microscope with a LaB6 cathode with a resolution of
0.14 nm and an accelerating voltage of 200 kV in order
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AN EFFECT OF A SUPPORT NATURE AND ACTIVE PHASE MORPHOLOGY
1703
to determine the average sizes of the metal particles
on the surface. High resolution images were analyzed
using the Fourier method. Samples for TEM BP were
placed on a perforated carbon film on a copper grid, then
biphenyl in heptane, was used as a raw material. Samples
were taken at least 1 time per hour and analyzed by gas-
liquid chromatography on a Kristall-2000M instrument
(FID) with a quartz capillary column ZB-35 with a grafted
phenyl (35%)–polydimethylsiloxane phase, helium
carrier gas. Chromatec Analyst software, version 2.6,
was used for recording and processing chromatograms.
Identification of the components of the reaction mixture
was performed by the method of gas chromatography/
mass spectrometry using the device GMS-QP2010 Ultra
1
0–15 micrographs were obtained for each catalyst.
Testing of the synthesized catalysts was carried out
in a laboratory flow-through installation with a plug
3
flow reactor. A 1 cm catalyst (fraction 0.25–0.5 mm)
in a 1 : 1 mixture with silicon carbide (of the same size)
was loaded into the isothermal zone of the reactor. The
hydrogenation of biphenyl was carried out under the
following conditions: temperature in the range of 60–
(Shimadzu).
The hydrogenation of biphenyl (BP) is consistent
1
00°C, pressure of 4 MPa, volumetric feed rate (VFR) of
with the formation of cyclohexylbenzene (TsGB) as an
intermediate product and bicyclohexyl (BCG) as the final
hydrogenation product:
–1
raw materials 4–10 h , and the hydrogen circulation ratio
of 1500 nm m . A model mixture, 1 wt % solution of
3
–3
The activity of the synthesized catalysts was
estimated by the total rate constant for the hydrogenation
of aromatic nuclei in the molecules of biphenyl and
cyclohexylbenzene k, which was calculated in the
approximation of the irreversible pseudo-first order
reaction (a large excess of hydrogen was used in the
experiments, which allowed to neglect the change in its
concentration):
catalyst according to the formula
(
3)
–1
where kNi is the reaction rate constant over nickel (s ),
mNi is the mass of nickel in the catalyst (g).
The conversion of biphenyl was calculated by the
formula
(1)
(4)
where khyd is the rate constant for the reaction of biphenyl
–1
–1
hydrogenation (s ); F , consumption of biphenyl (g s );
wherec , andc aretheinitialandcurrentconcentrations
0 BP BP
BP
m is the mass of the catalyst (g); X is the conversion of
aromatic nuclei to cyclohexane, calculated by the formula
of biphenyl in the reaction mass, respectively (wt.
fraction).
The conversion of cyclohexylbenzene was calculated
by the formula
(2)
(
5)
1
00 is the initial concentration of aromatic nuclei (mol %);
cBP is the concentration of biphenyl in the reaction mixture
mol %); cCHB, the concentration of cyclohexylbenzene
(
where XCHB is the conversion of cyclohexylbenzene (%);
c0,BF, cCHB, the initial concentration of biphenyl and the
current concentration of cyclohexylbenzene (mol %),
respectively.
in the reaction mixture (mol %).
The reaction rate constant, normalized to 1 g of nickel
(kNi), was calculated based on the nickel content in the
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 91 No. 10 2018

1704
CHERNOVA et al.
where k1(2) is the rate constant for the hydrogenation of
–
1
biphenyl (cyclohexylbenzene) (s ); F , consumption
BP
–
1
of biphenyl (g s ); m is the mass of the catalyst (g);
XBP, XCHB, biphenyl and cyclohexylbenzene conversion
calculated by formulas (4) and (5), respectively.
RESULTS AND DISCUSSION
Physicochemical properties of supports and
catalysts. The obtained nitrogen adsorption–desorption
curves for the synthesized supports (Fig. 1) refer to
type IV isotherms. The nitrogen adsorption isotherm
for SBA-15 (Fig. 1, curve 1) is characterized by a
clearly pronounced H1 hysteresis loop according to the
IUPAC classification [15]. This type of hysteresis loop
with symmetric curves of adsorption and desorption
corresponds to capillary condensation and desorption in
open cylindrical pores. The nearly vertical boundaries
of the hysteresis loop (in the region of partial pressures
p/p0
Fig. 1. Adsorption–desorption isotherms of the obtained
supports. (1) SBA-15, (2) SiO , (3) γ-Al O ; the same for
2
2
3
Figs.. 2, 5.
p/p = 0.6–0.75) indicate a narrow pore size distribution
0
(Fig. 2), which is typical of micromesoporous silicates
with an ordered porous structure [16].
The hysteresis loop on the adsorption isotherm SiO2
also belongs to the H1 type, however, it is located in a
much wider range of partial pressures (р/р = 0.6–0.9)
0
and has an elongated S-shape (Fig. 1, curve 2), which
corresponds to spherical pores forms with a wide pore
size distribution (Fig. 2).
Average pores radius, Å
The nitrogen adsorption isotherm obtained for the
Fig. 2. The distribution of pores along the radius.
sample of the γ-Al O support (Fig. 1, curve 3) has an
2
3
asymmetric H3 hysteresis loop, localized in the region of
The rate constants of the first k and second k
reactions were calculated similarly by the formulas
1
2
partial pressures p/p = 0.7–0.9, and indicates the presence
0
of slit-like pores on the support surface formed by the
microcrystalline structure of alumina.
(
6)
7)
At the same relative pressure p/p (Fig. 1), the largest
0
amount of adsorbate corresponds to the SBA-15 support,
which indicates a more developed specific surface area
than the other two carriers. The hysteresis loop of the
(
Table 1. Textural characteristics of the supports
Textural characteristics
Support
2
–1
3
V , cm g
P
–1
SBET, m g
Ref, Å
SBA-15
SiO2
706
360
203
0.84
0.99
0.73
27
45
58
γ-Al O
2
3
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AN EFFECT OF A SUPPORT NATURE AND ACTIVE PHASE MORPHOLOGY
1705
Time, s
Fig. 3. TPV curves of nickel catalysts supported on SiO . (1) Temperature change profile (°C); (2) Ni-24/SiO , (3) Ni-12/SiO ,
2
2
2
(4) Ni-6/SiO2.
nitrogen adsorption isotherm for SBA-15 is shifted to a
region of relatively low partial pressures, which indicates
the predominance of pores with a smaller diameter in this
support compared to SiO and γ-Al O .
Conclusions about the size of the particles of the
reduced metal and the nature of their distribution on the
surface of the catalysts were made on the basis of the
analysis of TEM images (Fig. 4).
2
2
3
As can be seen from Fig. 2 the sample of γ-Al O
2
3
As a result of statistical processing of electronic
images of reduced catalysts, the dependence of the size
distribution of nickel particles on the surface of catalysts
was obtained (Fig. 5).
has the largest pore diameter of 116 Å, SiO has a
2
diameter of 90 Å, and a mesoporous material SBA-15 is
of the smallest diameter (54 Å). Among the synthesized
supports, the mesoporous aluminosilicate SBA-15 has
the highest specific surface area (Table 1).
Nickel deposited on γ-Al O , had a high dispersion,
2
3
the average particle size of 4 nm. The Ni-12/SiO2
catalyst is characterized by a uniform distribution of
particles on the surface; the average size of the metal
clusters is 7.4 nm. The metal active phase of the Ni-
Analysis of the TPR data of Ni-catalysts showed that
the Ni-x/Sup catalysts are completely reduced at 400°C.
It was this temperature that was used when activating
(
reducing) the samples before testing the catalytic activity.
1
2/SBA-15 sample is of two types of particles: nickel
Thermograms (Fig. 3) allow conclusion that the
particles inside the carrier channels and particles located
on the outer surface, whereby the distribution of Ni
particles in the Ni-12/SBA-15 sample is bimodal. About
intensity and temperature of the maximum of the
absorption peak of hydrogen increase with increasing
content of the metal precursor in the sample. Thus, for
6
3% of all visible metal particles are located in the pores
the sample of Ni-6/SiO catalyst, the hydrogen absorption
2
of SBA-15.
maximum occurs at a temperature of 360°С, with an
increase in nickel concentration to 12 wt % (sample
The catalytic activity of Ni-x/SiO in hydrogenation
2
of biphenyl. Samples with a nickel content of 6, 12, and
Ni-12/SiO ) the maximum shifts to 373°С, and with an
2
2
4 wt% were synthesized and tested to determine the
increase in Ni content to 24 wt % maximum occurs at
86°C. The observed facts indicate that with increasing
optimal nickel content in the catalyst. Commercial SiO2
3
was used as a support. The test results for Ni-6/SiO , Ni-
2
precursor concentration (nickel nitrate), the nature of
its distribution on the surface of the support changes.
Probably, at relatively high concentrations, interactions
of the precursor molecules with each other over the
interactions of the precursor with the support surface
begin to prevail (formally, this may correspond to the
transition from monolayer filling the support surface to
the multilayer one).
1
2/SiO , and Ni-24/SiO in the biphenyl hydrogenation
2 2
reaction are shown in Table 2.
From the data presented, it follows that the total rate
constant for the reaction of hydrogenation of biphenyl
increases with increasing nickel content in the sample.
The sample Ni-24/SiO exhibits the highest catalytic
2
activity in the hydrogenation of biphenyl.
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1706
CHERNOVA et al.
(b)
(a)
1
0 nm
20 nm
(d)
(
c)
5
0 nm
2
0 nm
(e)
5
0 nm
Fig. 4. TEM images of synthesized catalysts. (а) Ni-6/SiO , (b) Ni-12/SiO , (c) Ni-24/SiO , (d) Ni-12/Al O , (e) Ni-12/SBA-15.
2
2
2
2
3
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AN EFFECT OF A SUPPORT NATURE AND ACTIVE PHASE MORPHOLOGY
1707
Table 2. Test results of the catalytic activity of Ni-x/SiO catalysts in hydrogenation of biphenyl
2
k × 104
kNi × 104
cBCH
cCHB
cBP
VFR of raw
material, h–1
Conversion,
%
Catalyst
Т, °С
mol g–1 h–1
%
2
Ni-6/SiO2
70
2
3
47
57
77
44
75
56
66
40
75
63
35
67
49
70
69
64
63
51
40
16
55
12
42
7
26
32
46
23
51
30
60
22
61
35
82
38
75
41
59
38
67
0.30
0.39
5.08
6.51
8
9
0
0
2
2
4
2
4
2
4
2
4
2
6
4
8
8
7
0.58
0.73
0.45
0.81
1.40
1.90
2.54
9.70
12.18
3.75
1
13
3
1
00
Ni-12/SiO2
60
27
2
58
2
7
0
0
0
23
3
6.72
34
0
8
9
65
5
11.60
16.00
21.20
28
0
51
7
24
7
1
00
24
6
1
2
30
1
Ni-24/SiO2
60
2
36
0
.65
.05
2.69
4.34
4
4
6
8
8
4
15
3
57
79
63
50
73
57
73
54
53
39
6
32
54
34
27
42
31
49
37
34
7
0
1
34
48
21
41
14
36
39
2
8
0
0
6
1
2
.68
.37
7.03
9.89
1
0
0
2
4
3
1
1
1
13
10
8
9
The dependences of the rate constant for the reaction
of hydrogenation of biphenyl on nickel catalysts on
silicon oxide were constructed based on the experimental
results (Figs. 6, 7). Figure 7 shows that the specific rate
The catalytic activity of Ni-12/Sup in hydrogenation
of biphenyl. Figure 8 shows the results of determining
the rate constant for the reaction of hydrogenation of
biphenyl [Eq. (2)] at various temperatures in the presence
of synthesized Ni-12/Sup catalysts. Under the same
conditions Ni-12/SBA-15 showed the greatest activity.
The activity of the studied catalysts decreased in the
series Ni-12/SBA-15 > Ni-12/SiO >> Ni-12/Al O . The
constants for the Ni-12/SiO catalyst are higher than
2
kNi obtained for the other two samples over the entire
temperature range studied. This suggests a more efficient
operation of the active sites of the catalyst with an active
component content of 12 wt %. Therefore, for further
research, Ni-12/Sup catalysts were synthesized (where
Sup is γ-Al O and SBA-15) with the same concentration
2
2
3
rate constants of the hydrogenation reaction calculated
at 80°С for Ni-12/SBA-15 and Ni-12/SiO turned out
2
–
1
to be 1.68 and 1.39 s , respectively. The Ni-12/Al O
2
3
2
3
of the active component as in the Ni-12/SiO sample.
catalyst showed the least activity, the rate constant of the
2
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1708
CHERNOVA et al.
Temperature, °C
6
‒12
Particle diameter, nm
Fig. 8. The rate constant of the reaction of biphenyl
hydrogenation vs. temperature for nickel catalysts. (1) Ni-12/
SBA-15, (2) Ni-12/SiO2, (3) Ni-12/Al2O3.
Fig. 5. The size distribution of metal particles on the surface
of catalysts.
hydrogenation reaction at 80°С was close to zero. Even
at temperatures above 100°C, the conversion of biphenyl
on this catalyst did not exceed 35%.
Probably, the hydrogenation reaction of biphenyl on
nickel catalysts is structurally sensitive and proceeds
at the highest rate on particles of a certain size. Three
synthesized samples of catalysts with the same nickel
content (12 wt %) had a different size of metal particles
on the surface. The Ni-12/Al O sample was characterized
2
3
by a highly dispersed active phase—an average particle
size of 4 nm. The average particle size of the Ni-12/SiO2
catalyst was 7.4 nm. According to the TEM BP data, in
addition to fine metal particles inside the SBA-15 channels
Temperature, °C
Fig. 6. The observed rate constant of biphenyl hydrogenation
reaction vs. temperature for Ni-x/SiO catalysts. (1) Ni-24/SiO ,
(particle size approximately equal to 6 nm), particles of
2
2
3
0 nm were present on the outer surface on the Ni-12/
(
2) Ni-12/SiO , (3) Ni-6/SiO .
2 2
SBA-15 surface of the sample. From the data obtained
it follows that it is the large Ni particles formed on the
surface of the SBA-15 crystallites that are responsible
for the increase in the catalytic activity of the catalyst
in the hydrogenation of biphenyl. The high dispersion
of the active phase, achieved on the γ-Al O support, on
2
the contrary, led to a loss of the catalytic activity of the
synthesized sample Ni-12/Al O .
2
3
Determination of the activation energy of
hydrogenation reaction of biphenyl on a Ni-12/SiO2
catalyst. For the Ni-12/SiO catalyst sample, which
2
showed a high specific activity, the kinetic characteristics
of the biphenyl hydrogenation reaction were determined
in more detail (Fig. 9). When processing the obtained
data in theArrhenius coordinates (Fig. 10), the activation
energy values were determined for the first and second
Temperature, °C
Fig. 7. The rate constant for the reaction of hydrogenation of
biphenyl normalized to nickel vs. temperature. (1) Ni-6/SiO2,
(
2) Ni-12/SiO , (3) Ni-24/SiO .
2 2
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AN EFFECT OF A SUPPORT NATURE AND ACTIVE PHASE MORPHOLOGY
1709
ln k
Temperature, K
1
03/T, K−1
Fig. 9. The rate constants of the reaction of the first and second
stages of biphenyl hydrogenation vs. temperature. (1) k1,
Fig. 10. ln k vs. the inverse temperature. (1) k , (2) k .
(2) khyd, (3) k2.
i
1
2
–
1
stages of hydrogenation of biphenyl, which were 48
80°С and a bulk flow rate of feed 4 h , the conversion
of aromatic nuclei reaches 90%. This sample can be
recommended as a potential catalyst for the hydrogenation
of aromatic compounds from the LOHC class to create
a technology for preserving free energy into chemically
bound hydrogen.
–1
and 61 kJ mol , respectively. The obtained values are
in good agreement with the literature data, according to
which the activation energy of aromatic hydrocarbons
–
1
on Ni-containing catalysts averages 50–57 kJ mol [4].
CONCLUSIONS
ACKNOWLEDGMENTS
The activity of the synthesized nickel hydrogenation
catalysts increases with increasing nickel content in the
sample, however, the specific catalytic activity of the metal
phase formed on the surface passes through a maximum.
The specific rate constants for the hydrogenation reaction
of biphenyl were significantly higher for a catalyst with
a metal content of 12 wt % as compared with samples
of Ni-6/SiO and Ni-24/SiO over the entire temperature
This work was supported by the Government of
the Russian Federation, resolution no. 220, grant
no. 14.Z50.31.0038 and the RFBR, project no. 16-43-
6
30804.
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2
2
1
2
. Geburtig, D., Preuster, P., Bosmann, A., Muller, K., and
Wasserscheid, P., Int. J. Hydrogen Energy. 2016, no. 41,
pp. 1010–1017.
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