Hexadecane Conversion on an Alumina–Nickel Catalyst

Article abstract of DOI:10.1134/S0023158419040025

Abstract: The conversion of hexadecane on a 4% Ni/Al₂O₃ catalyst in a temperature range of 20–300°C was studied using IR spectroscopy and catalytic methods. It was found that the dehydrogenation of hexadecane occurred at 20–100°C with the subsequent formation of aromatic products, but the rates of these processes were very low. As the reaction temperature was increased to 200°C, the 4% Ni/Al₂O₃ catalyst exhibited a maximum activity and high selectivity for the formation of 1-hexadecene, and aromatic compounds and cracking products were present in the reaction products. As the reaction temperature was further increased, the catalytic activity significantly decreased. This was due to the fact that polyaromatic deposits gradually accumulated on the catalyst surface in a temperature range of 200–300°C.

Full text of DOI:10.1134/S0023158419040025

ISSN 0023-1584, Kinetics and Catalysis, 2019, Vol. 60, No. 4, pp. 439–445. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Kinetika i Kataliz, 2019, Vol. 60, No. 4, pp. 471–478.
Hexadecane Conversion on an Alumina–Nickel Catalyst
a,
a,
a
a
a
V. V. Chesnokov *, A. S. Chichkan **, E. A. Paukshtis , Yu. A. Chesalov , and A. V. Krasnov
a
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
*
e-mail: chesn@catalysis.ru
**e-mail: AlexCsh@yandex.ru
Received December 17, 2018; revised February 7, 2019; accepted February 19, 2019
Abstract—The conversion of hexadecane on a 4% Ni/Al O catalyst in a temperature range of 20–300°C was
2
3
studied using IR spectroscopy and catalytic methods. It was found that the dehydrogenation of hexadecane
occurred at 20–100°C with the subsequent formation of aromatic products, but the rates of these processes
were very low. As the reaction temperature was increased to 200°C, the 4% Ni/Al O catalyst exhibited a max-
2
3
imum activity and high selectivity for the formation of 1-hexadecene, and aromatic compounds and cracking
products were present in the reaction products. As the reaction temperature was further increased, the cata-
lytic activity significantly decreased. This was due to the fact that polyaromatic deposits gradually accumu-
lated on the catalyst surface in a temperature range of 200–300°C.
Keywords: hexadecane, nickel, aluminum oxide, coking
DOI: 10.1134/S0023158419040025
INTRODUCTION
Although the introduction of nickel intensified the
coking process, the exact mechanism of this effect has
not been studied. It is well known [7] that paraffin
hydrocarbons, which are the main components of oil,
are prone to thermal cracking reactions by a radical
chain mechanism.
Currently, the consecutive reaction scheme of
hydrocarbon condensation is considered as a conven-
tional mechanism of the coking of oil residues; this is
a series of sequential reactions of the formation of
compaction monomers and intermediate products
based on condensation, polymerization, dehydrocy-
clization, binding of aromatic rings, and hydrogen
depletion up to a graphite structure [8–12].
Present-day oil production is hampered by a
decrease in the amount of recoverable so-called light
oil. Valuable products such as gasoline, kerosene, and
diesel fuel are obtained from oil based on currently
available technologies. The utilization of heavy distil-
lation residues creates more and more problems for oil
refineries because the fraction of heavy oil in the raw
materials increases and the market of heavy residual
oil fuels decreases. Therefore, the improvement of
available and the development of new technologies
oriented to increasing the degree of conversion of
heavy oils and oil residues are of considerable current
interest [1, 2].
The conversion of hydrocarbon mixtures is very
difficult to study; therefore, tests are carried out with
the use of an individual hydrocarbon. Hexadecane is
most often used as a model hydrocarbon, which
undergoes both radical-chain and catalytic transfor-
mations under the reaction conditions.
Coking is one of the most economically feasible
methods for the conversion of heavy oil residues,
which makes it possible to obtain valuable petroleum
products at minimum cost and hence to increase the
depth of oil refining [3, 4]. Delayed coking is the most
common method of coking. In the consideration of
the intensification of coking process, the attention of
The thermal reactions of hexadecane have been
researchers focused on technological aspects: the res- described in detail in the literature [13–19]. It was
idence time of raw materials and temperature fields in shown that its transformation proceeds according to
the reactor volume, the composition of raw materials, the Rice–Kossyakov radical chain mechanism under
etc. [5]. Recently, methods involving the use of cata- the action of temperature. The thermal cracking of
lytic additives in the thermolysis of heavy oil fractions n-hexadecane at moderate temperatures (330–375°C)
have also been developed. Kelemen et al. [6] estab- was studied in liquid and gas phases. Wu et al. [13]
lished that the introduction of nickel-containing trace established that the distribution of products strongly
additives in amounts up to 2000 ppm into raw materi- depends on the phase state of the reagent. At low con-
als for delayed coking led not only to an increase in the versions, an equimolar distribution of n-alkanes and
yield of light distillate fractions but also to a significant 1-alkenes was observed for C
improvement in the properties of petroleum coke. ucts in the process of liquid phase cracking, and the
–C13 hydrocarbon prod-
3
439

4
40
CHESNOKOV et al.
amount of alkanes was greater than that of alkenes as pump was turned on and hexadecane was supplied.
the conversion was increased. On the contrary, The catalytic experiment was carried out at 200°C for
alkenes were always predominant in the products of 30 min, and the compositions of the gas and liquid
gas-phase cracking.
phases were analyzed; next, the reaction temperature
was raised to 250°C and then to 300°C. The hexadec-
In the 1980–1990s, a previously unknown carbide
–1
cycle mechanism of the formation of carbon on iron ane space velocity was 1 h . Gas was analyzed using a
subgroup metals was discovered and studied [20, 21]; Kristall 2000 gas chromatograph (IEMZ KUPOL,
this mechanism opens up new possibilities in improv- Russia) with a column packed with activated charcoal,
ing the delayed coking process [22]. Nickel metal and a liquid phase was analyzed on an Agilent 7000B
exhibits the highest activity in the formation of carbon gas chromatograph–mass spectrometer (Agilent, the
nanomaterials. The carbide cycle mechanism of car- United States) with a DB-5ms column (30 m ×
bon formation from C –C hydrocarbons on nickel 0.25 mm × 0.25 μm).
1
4
metal includes the following two steps:
(
1) Chemical step at which the catalytic decompo-
X-Ray Diffraction Analysis of Samples
sition of hydrocarbons on the surface of a metal parti-
cle, the formation of carbon atoms, and an increase in
their concentration to limiting values occur.
The phase composition of the samples was investi-
gated by X-ray diffraction analysis. Diffraction pat-
terns were obtained on a Thermo ARL X’TRA diffrac-
tometer (Thermo Fisher Scientific, Switzerland) using
CuKα radiation with a wavelength of 1.54184 Å and
point scanning. The scan range of 2θ angles was 5°–
(
2) Physical step at which the formation of crystal-
lization centers (nuclei) of a graphite phase on certain
parts of the surface of a metal particle, the migration
(
diffusion through the bulk of a metal particle) of car-
9
0°, the scanning step was 0.05°, and the accumula-
bon atoms from their formation sites to the crystalliza-
tion centers of the graphite phase, and its growth with
the formation of carbon nanofibers occur. From the
carbide cycle mechanism, it follows that the diffusion
of carbon atoms occurs under the action of a concen-
tration gradient of carbon atoms in the metal.
tion at a point was 5 s. To identify the phases, we used
diffraction (PC-PDF) and structural (ICSD) data
bases. The sizes of coherent scattering regions (CSRs)
were determined from the Selyakov–Scherrer formula
using the integral widths of peaks.
Catalytic transformations on metallic nickel in the
case of high-molecular-weight hydrocarbons are still
not clearly understood.
This paper is devoted to a study of the adsorption
and transformations of hexadecane on an alumina–
nickel catalyst.
IR-Spectroscopic Characterization of the Samples
In static IR experiments, the sample was pressed as
a thin plate without a binder with a surface density of
2
15 mg/cm , loaded in an IR cell, and calcined in a vac-
uum for 1 h at 500°C. Next, the sample was cooled to
room temperature (T ) and the background spec-
room
EXPERIMENTAL
trum was recorded. After that, 4 μL of liquid hexadec-
ane (equivalent to 5 mmol/g of catalyst) was injected
into the cell. Hexadecane has a low saturated vapor
Synthesis of the Ni/Al O Catalyst
2
3
Nickel was supported onto grade A-1 γ-Al O from
2
3
pressure of <1 Torr at T ; therefore, it was supplied
room
an aqueous solution of Ni(NO ) using an incipient
3
2
to the cell wall at a distance of ~ 20 cm from the pellet
with the use of a microsyringe, and changes in the
spectra were observed for 1.5 h. First, the spectra were
recorded at room temperature 5, 15, 30, and 70 min
after the injection of hexadecane. Then, the sample
was sequentially heated to 200, 300, 400, 450, and
wetness impregnation method. Water was evaporated
to dryness, and the dry residue was transferred to a
porcelain dish and calcined in a muffle furnace at
5
00°C for 30 min. The nickel content of the synthe-
sized catalyst was 4 wt %. After calcination, the
nickel–alumina catalyst was reduced in a reactor with
a quartz spring balance in a flow of hydrogen at a tem-
perature of 700°C for 1 h.
5
00°C with keeping at each temperature for 10 min.
The spectra were recorded on a Shimadzu FTIR 8300
–1
spectrometer (Japan) in a range of 4000–600 cm
–1
with a resolution of 4 cm and an accumulation of
Catalytic Experiments
2
00 scans. In flow experiments, the IR spectra were
recorded on a Cary 660 FTIR spectrometer (Agilent
Technologies, the United States) in a range of 4000–
The catalytic activity and selectivity of hexadecane
conversion were studied in a flow-through setup at
–1
–1
temperatures of 200–300°C. Hexadecane from Kom- 600 cm with a resolution of 4 cm and an accumu-
ponent-reaktiv (Russia), GOST [State Standard] lation of 40 scans. For IR studies, the catalyst was
1
2525-85, was used in this work. The purity of hexade- sprayed onto a BaF window using a spray column.
2
cane was 98 wt % or higher. A 2-g portion of the alu- The procedure was repeated many times to achieve an
mina–nickel catalyst was loaded in a flow reactor. optimum thickness of the catalyst layer, which was
After heating in argon to a specified temperature, a monitored by the transmission of IR radiation. The
KINETICS AND CATALYSIS
Vol. 60
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2019

HEXADECANE CONVERSION ON AN ALUMINA–NICKEL
.25
.00
0.75
.50
441
1
0
.12
1
5
4
0.08
3
2
×5
0
0.04
4
3
2
1
1
0.25
0
0
1200 1400 1600 1800 2800 3000 3200 3400
–
0.04
Wavenumber, cm–1
1
200 1400 1600 1800 2800 3000 3200 3400
Wavenumber, cm–1
Fig. 2. IR spectra of hexadecane adsorbed on the 4 wt %
Fig. 1. IR spectra of hexadecane adsorbed on the 4 wt %
Ni/Al O catalyst measured in a static cell at room tem-
perature after injecting 4 μL of liquid hexadecane after (1)
, (2) 15, (3) 30, and (4) 70 min.
Ni/Al O catalyst measured in a static cell after heating at
2
3
2
3
temperatures of (1) 200, (2) 300, (3) 400, (4) 450, and (5)
5
00°C. Conditions: 4 μL of liquid hexadecane was
5
injected, and the exposure time was 10 min.
window with the sprayed catalyst was placed in a
quartz IR reactor cell. Before the start of an experi-
ment, the sample was activated for 1 h in a flow of
helium at a temperature of 300°C directly in the IR
reactor cell. Then, the cell with the catalyst sample was
cooled to a specified temperature in an atmosphere of
helium. Hexadecane was supplied by saturating a flow
of helium by bubbling through an evaporator with
hexadecane at room temperature. The reaction gas
mixture entered the IR reactor cell at a flow rate of
terminal olefin fragments in the composition of
hydrocarbon deposits. The intensity of the band at
–1
1
660 cm gradually increased with the reaction tem-
–1
perature (Fig. 2). At 300°C, the band at 1590 cm due
to coke or aromatic products reached its maximum
intensity and, on the contrary, the bands of hexadec-
–1
ane in a range of 2800–2970 cm completely disap-
peared from the spectrum. Thus, hexadecane was
gradually converted into coke deposits on the sample
surface.
120 mL/min.
All of the spectra given in this paper are difference
The adsorption and conversion of hexadecane on
spectra; that is, they were obtained by subtracting a the surface of the 4 wt % Ni/Al O catalyst was also
2
3
background spectrum, which was measured after acti-
vating the sample and cooling it to a specified adsorp-
tion temperature, from the recorded spectra.
studied by in situ IR spectroscopy under flow condi-
tions. When the reactant was supplied to the closed cell
volume at room temperature, we observed a slow pro-
cess of the conversion of adsorbed hexadecane with-
out the interaction of surface products with new por-
tions of hexadecane. In the flow experiment on the
RESULTS AND DISCUSSION
The phase composition of the alumina–nickel cat-
alyst was examined by X-ray diffraction analysis.
Based on the diffraction data, it was established that
the catalyst contained a phase of γ-Al O with a unit
4
wt % Ni/Al O catalyst, reactions proceeded in the
2 3
same way as in a real catalytic reactor.
Figure 3 shows the spectra of the surface com-
2
3
cell parameter of 7.923 Å and an CSR size of 55 Å and pounds of hexadecane on the Ni/Al O catalyst
a metallic nickel phase with an CSR size of 80 Å.
2
3
recorded upon passing a reaction mixture (C H in
16 34
Figure 1 shows the IR spectra recorded at room He) through the IR reactor cell with a catalyst sample
temperature after injecting hexadecane onto the at 100°C for 1 (curve 1), 3 (curve 2), 10 (curve 3), 15
Ni/Al O catalyst.
(curve 4), and 30 min (curve 5). The spectra contained
2
3
–1
absorption bands at 2965, 2923, and 2856 cm are
assigned to the stretching vibrations of the CH and
Hexadecane has a low saturated vapor pressure;
therefore, it adsorbs slowly. Absorption bands at 1371,
3
–1
CH groups of adsorbed hexadecane. An absorption
1
463, 2852, 2923, and 2967 cm are assigned to the
2
–1
bending and stretching vibrations of the CH and CH
band at 3057 cm due to the stretching vibration of
2
3
groups of hexadecane. In addition, two new bands at the CH group at the double bond appeared in the
–1
1
590 and 1660 cm appeared in the spectra. The for- spectra after passing the mixture for 30 min. It is likely
–1
mer can be attributed to the vibrations of compounds that a band at 1660 cm in the spectra shown in
containing aromatic rings or coke and the latter, to the Figs. 1 and 2 also characterized the above fragment.
KINETICS AND CATALYSIS Vol. 60 No. 4 2019

4
42
CHESNOKOV et al.
0.016
(а)
0.01
5
4
5
4
0.008
3
3
2
0
2
1
1
3200
3000
2800
2600
Wavenumber, cm–1
0
3200
3000
(b)
2800
2600
Fig. 3. IR spectra of the surface compounds of hexadecane
on the 4 wt % Ni/Al O catalyst measured upon passing the
2
3
reaction mixture through the reactor cell with a catalyst sam-
ple at 100°C for (1) 1, (2) 3, (3) 10, (4) 15, and (5) 30 min.
0.01
Thus, the dehydrogenation reaction of hexadecane at
00°C proceeded with the formation of alkenes.
1
1
2
At temperatures of 160–200°C, a gradual decrease
in the concentration of surface compounds was
observed (Figs. 4a and 4b). In this case, new bands did
not appear in the spectra; that is, a further conversion
of hexadecane and olefins did not occur. Therefore, a
decrease in the concentration of surface compounds
with increasing temperature was associated with a
faster increase in the rate of desorption of the surface
compounds, as compared with the rate of their forma-
tion.
3
4
At 300°C (Fig. 5), the IR spectra exhibited wide
bands related to aromatic compounds and coke depos-
–1
its in a range of 1600–1100 cm . Therefore, olefins
underwent further transformations into aromatics and
coke at 300°C.
The study of the catalytic activity and selectivity of
the 4 wt % Ni/Al O catalyst in the conversion of
hexadecane in a flow reactor was carried out at tem-
peratures of 200, 250, and 300°C. As an example,
Fig. 6 shows the chromatogram of the reaction prod-
ucts including 44 hydrocarbons at 200°C, and Table 1
summarizes their composition.
0
3200
3000
2800
2600
2
3
Wavenumber, cm–1
Fig. 4. IR spectra of the surface compounds of hexadecane
on the 4 wt % Ni/Al O catalyst measured upon passing
2
3
Table 2 summarizes the results of studying the
effect of reaction temperature on the conversion of
hexadecane and the group composition of conversion
products in the presence of 4 wt % Ni/Al O .
the reaction mixture through the reactor cell with a catalyst
sample: (a) under the conditions of temperature-pro-
grammed heating from 100 to 200°C at a rate of 5 K/min
at (1) 100, (2) 140, (3) 160, (4) 180, and (5) 200°C; (b) at
2
3
1
00°C for (1) 1, (2) 3, (3) 10, and (4) 30 min.
KINETICS AND CATALYSIS Vol. 60 No. 4
2019

HEXADECANE CONVERSION ON AN ALUMINA–NICKEL
443
0.01
decreased in the following order: hexane > undecane >
hexadecane.
It should also be noted that, at Т < 350°C, С –С
1
4
paraffins adsorbed on the surface of nickel underwent
the rupture of C–H bonds and carbon atoms formed a
nickel carbide phase; then, the carbonization of the
catalyst surface occurred very slowly [24]. At T >
4
3
2
3
50°C, carbon deposits were formed from the C –C
1
1 4
hydrocarbons on the nickel catalyst at a high rate by
the carbide cycle mechanism. It is almost impossible
to observe the dehydrogenation reaction of light
hydrocarbons because olefins are rapidly converted
into carbon nanofibers. A different situation is typical
for hexadecane. At temperatures of 200–300°C, the
dehydrogenation of hexadecane to 1-hexadecene pro-
ceeds with high selectivity. Hydrogen atoms are
detached from terminal carbon atoms in a hydrocar-
bon; therefore, it can be concluded that hexadecane
interacts with two nickel atoms. Because the complete
decomposition of hexadecane does not occur, there
are no large multiplet active centers necessary for the
0
000
2
1800
1600
1400
1200
Wavenumber, cm–1
Fig. 5. IR spectra of the surface compounds of hexadecane
on the 4 wt % Ni/Al O catalyst measured upon passing
2
3
the reaction mixture through the reactor cell with a catalyst
sample at 300°C for (1) 1, (2) 3, (3) 10, and (4) 30 min.
From the IR-spectroscopic and catalytic data, it
follows that the activity of the alumina–nickel catalyst adsorption of the entire hexadecane molecule on the
increased as the temperature was increased from 150 to surface of metallic nickel.
2
00°C. When the reaction temperature was increased
For comparison, we carried out tests on the con-
version of hexadecane in the presence of aluminum
oxide at temperatures of 250–450°C. It follows from
the results presented in Table 3 that aluminum oxide
above 200°C, the activity decreased as a result of the
gradual deactivation of the catalyst due to coke depo-
sition on the catalyst. Thus, the 4 wt % Ni/Al O cat-
2
3
alyst exhibited a maximum activity at a temperature of has a much lower activity in the conversion of hexade-
2
00°C.
cane compared to that of the 4 wt % Ni/Al
O catalyst
2 3
(Table 2).
Previously, Chesnokov et al. [23] studied the prop-
erties of Ni/Al O and NiO/Sibunit catalysts in the
formation of carbon nanofibers from high-molecular-
weight alkanes (hexane, undecane, and hexadecane)
and found that the interaction of a paraffin molecule
with the surface of metallic nickel was a rate-con-
Saturated hydrocarbons do not carbonize alumina.
2
3
However, mass transfer processes are improved with
increasing reaction temperature and upon the transi-
tion of hexadecane from a liquid to a gaseous state.
This may lead to the onset of the interaction of olefins
desorbed from the surface of metallic nickel with the
trolling step of the reaction in a temperature range of surface of aluminum oxide. It is well known [25] that,
4
50–600°C. However, it remained unclear why the upon the adsorption of olefins on the surface of Al O ,
2 3
reactivity of the test hydrocarbons significantly carbonate–carboxylate groups and then coke deposits
×
106
6
5
5
4
4
3
3
2
2
.0
.5
.0
.5
.0
.5
.0
.5
.0
37
42
36
23
1
.5
15
29
9
1
.0
4
3
4
35
44
2
0
.5
1
7
12
20
26
32
0
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23
Time, min
Fig. 6. Chromatogram of the products of hexadecane conversion on the 4 wt % Ni/Al O catalyst obtained at a temperature of
2
3
200°C.
KINETICS AND CATALYSIS Vol. 60 No. 4 2019

4
44
CHESNOKOV et al.
Table 1. Composition of the products of hexadecane conversion on the 4 wt % Ni/Al O catalyst at a temperature of 200°C
2
3
Entry
Hydrocarbon
Concentration, % Entry
23
24 2-Dodecene
25
26 Hexylbenzene
Hydrocarbon
Concentration, %
1
2
3
4
5
6
7
8
9
Heptane
Octane
0.05
0.14
0.05
0.24
0.03
0.01
0.08
0.07
0.29
0.05
0.02
0.09
0.12
0.03
0.38
0.05
0.01
0.03
0.06
0.07
0.12
0.03
Dodecane
0.45
0.05
0.03
0.08
0.08
0.09
0.48
0.08
0.03
0.07
0.08
0.37
0.62
2.39
93.2
0.97
0.62
0.59
0.27
0.78
0.14
0.2
para-Xylene
Nonane
3-Nonene
2-Nonene
meta-Ethyltpluene
1-Decene
*
27
28
*
*
29 Tridecene
30 Isotetradecane
Decane
31
*
1
0
3-Decene
4-Decene
para-Propyltoluene
*
1-Undecene
Undecane
2-Undecene
1-Undecene
para-(1-Methylpropyl)-toluene
Pentylbenzene
para-Butyltoluene
Dodecene
32 Heptylbenzene
33 (1-Methylhexyl)-benzene
34 Tetradecane
35 Pentadecane
36 1-Hexadecene
1
1
1
2
1
3
1
4
1
5
37
38
39
Hexadecane
*
*
1
6
1
7
1
8
40 (1-Ethyloxyl)-benzene
41 Decylbenzene
42 (1-Methylnonyl)-benzene
43 Heptadecane **
1
9
20
2
1
22
*
44 Octadecane **
*
Unidentified hydrocarbons.
*
* Heptadecane and octadecane were present as impurities in the starting hexadecane.
Table 2. Effect of reaction temperature on the conversion and the group composition of the reaction products of hexade-
cane on the 4 wt % Ni/Al O catalyst
2
3
Aromatic
hydrocarbons, %
Temperature, °С
Conversion, %
Paraffins, %
Olefins*, %
1-Hexadecene, %
200
250
300
6.8
2.22
1.40
3.02
1.18
0.81
0.75
0.23
0.03
0.64
0.20
0.04
2.39
0.61
0.52
*
Without 1-hexadecene.
are formed. As a result, the surface of aluminum oxide
is carbonized by a consecutive mechanism. It is likely
that, for this reason, selectivity for 1-hexadecene on
CONCLUSIONS
Thus, dehydrogenation is the main direction of
hexadecane conversion on the surface of a nickel-con-
the 4 wt % Ni/Al O catalyst decreased at reaction taining catalyst. At room temperature, dehydrogena-
2
3
tion takes place with the subsequent formation of aro-
matic products, but the rate of these processes is very
low. With an increase in the reaction temperature to
temperatures above 300°C (Table 2).
Table 3. Effect of reaction temperature on the conversion 100°C, the rate of these reactions slightly increases. At
of hexadecane in the presence of aluminum oxide
T = 200°C, a maximum activity and high selectivity of
the 4 wt % Ni/Al O catalyst in the dehydrogenation of
2
3
Temperature, °С
Conversion, %
250
0.2
350
0.3
450
hexadecane into 1-hexadecene were observed. Aro-
matic compounds and cracking products were deter-
mined in the reaction products; this was probably due
0.48
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HEXADECANE CONVERSION ON AN ALUMINA–NICKEL
445
to the presence of the acid sites of aluminum oxide.
With a further increase in the temperature, the cata-
and Galiakbarov, M.F., Khim. Tekhnol. Topl. Masel,
1966, no. 9, p. 31.
lytic activity of the sample significantly decreased. 10. Levinter, M.E., Medvedeva, M.I., Panchenkov, G.M.,
This was due to the fact that polyaromatic deposits
gradually accumulated on the surface of the catalyst in
and Agapov, G.I., Khim. Tekhnol. Topl. Masel, 1966,
no. 11, p. 25.
a temperature range of 200–300°C. The results of the 11. Rudenko, A.P., Sovremennye problemy fizicheskoi kh-
catalytic studies are consistent with spectral data,
which indicate that coke products were formed on the
imii (Modern Problems of Physical Chemistry), Mos-
cow: Moscow State University, 1968, vol. 3, p. 263.
surface of the 4 wt % Ni/Al O catalyst at T > 300°C, 12. Buyanov, R.A., Zakoksovanie katalizatorov (Coking of
2
3
Catalysts), Novosibirsk: Nauka, 1983, p. 16.
as evidenced by the presence of an absorption band at
–1
1
3. Wu, G., Katsumura, Y., Matsuura, C., and Ishigure, K.,
about 1590 cm in the IR spectrum of the samples.
Ind. Eng. Chem. Res., 1996, vol. 35, p. 4747.
1
4. Wangen, E.S., McCaffrey, W.C., Kuznicki, S., Hoff, A.,
and Blekkan, E.A., Top. Catal., 2007, vol. 45, nos. 1–4,
p. 213.
FUNDING
This work was supported by the Russian Science Foun-
dation (project no. 17-73-30032).
https://doi.org/10.1007/s11244-007-0268-x
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Translated by V. Makhlyarchuk
KINETICS AND CATALYSIS Vol. 60 No. 4 2019