ISSN 1070-4272, Russian Journal of Applied Chemistry, 2020, Vol. 93, No. 11, pp. 1737–1742.

© Pleiades Publishing, Ltd., 2020.

Russian Text © The Author(s), 2020, published in Zhurnal Prikladnoi Khimii, 2020, Vol. 93, No. 11, pp. 1642–1648.

HYDROGEN TECHNOLOGIES

Choosing a Microspherical Catalyst for Partial Oxidation

of Methane to a Hydrogen-Containing Gas
I. M. Gerzelieva,*, E. V. Podoprigoraa, and A. A. Pimenovb
a Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991 Russia
b Samara State Technical University, ul. Molodogvardeiskaya 244, main building, Samara, 443100 Russia

*e-mail: gerzeliev@ips.ac.ru

Received October 7, 2020; revised October 8, 2020; accepted October 13, 2020

Abstract—The influence of the chemical composition of microspherical nickel–cobalt catalysts on aluminosilicate

and aluminum oxide supports on the catalytic characteristics of methane oxidative conversion to a hydrogen-
containing gas was studied on a pulse laboratory installation with separate supply of the feed and oxidant. The
physicochemical and catalytic studies show that the total content of nickel and cobalt oxides on the level of 10 wt %
is sufficient for preparing a catalyst capable of repeated redox transitions.
Keywords: metal oxide catalyst, hydrogen-containing gas, syngas, methane oxidative conversion, methane–
hydrogen mixture
DOI: 10.1134/S1070427220110154

Partial catalytic oxidation of methane with oxygen is
one of promising methods of syngas production [1, 2].
However, the practical implementation of this
technology is hindered by the facts that, on the one
hand, separation of oxygen from air is expensive and
oxygen–hydrocarbon mixtures are dangerously
explosive and, on the other hand, the use of air instead
of pure oxygen leads to dilution (by 40%) of the product
with nitrogen and decreases the productive capacity of
the equipment; furthermore, reliable and selective
catalysts for this process are lacking [3].
The possibility of performing the methane conversion
in the system with circulating metal oxide catalyst was
demonstrated at the Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences [4]. Such
system includes two main mutually connected vessels: a
reactor and a regenerator. A solid metal oxide catalyst
continuously circulates between these vessels,
transferring oxygen incorporated in it from the
regenerator to the reactor and oxidizing the hydrocarbon
feedstock to hydrogen and carbon monoxide. In the
process, there is no direct contact of the feed with the
gaseous oxidant and the reaction products contain no
nitrogen. The advantages of the suggested procedure for
the syngas production are high explosion safety and
reduction of capital expenditures because of no need for
air separation.
Metal oxide catalysts intended for use in the above
system should meet the following requirements: capa-
bility for repeated redox transitions, presence of active
oxygen determining the catalyst performance, and wear
resistance, which depends on the support and on the
catalyst preparation procedure. As a whole, the catalyst
should ensure high conversion of the hydrocarbon feed-
stock [5]. The most widely used catalyst supports are
α- and γ-alumina. The properties of various crystalline
forms of aluminum oxide are described in detail in [6].
The most promising metals for use in metal oxide
systems capable of repeated alternation of oxidation–re-
duction cycles are Cu, Fe, Ni, and Co. Metal oxide cata-
lysts based on Cu show high activity in methane conver-
sion and good ability for redox transitions [7]. The main
factor preventing the use of copper in metal oxide sys-
tems is its low melting point [8]. Metal oxide systems
based on iron show unsatisfactory redox characteristics,
but the use of Fe reduces the catalyst cost [9]. The great-
est attention is paid to metal oxide systems based on
nickel supported on aluminum oxide. Such systems ex-

1737
1738 GERZELIEV et al.
hibit high activity in reaction with alkanes and low wear
rate in a fluidized bed. However, when using γ-Al2O3 as
a support, the redox reactions of nickel can be hindered
by partial transformation of NiO into low-reactive spi-
nel NiAl2O4 [10]. The spinel formation can be avoided
by performing the γ-Al2O3 to α-Al2O3 phase transition
at 1150°С or by passivating nickel by coating with Mg,
Ca, La, or Co compounds [11]. The use of combinations
of metal oxides in the catalysts may improve their char-
acteristics. For example, as noted in [12], the CoO–
NiO/Y–ZrO2 system, despite a slight decrease in the
oxidation and reduction rates due to formation of the
NiCoO2 solid solution, is regenerated in the course of
alternation of the redox cycles considerably better com-
pared to the individual oxides. The CoO–NiO/Al2O3
bimetallic system was studied by Hossain and de Lasa
[13]. They concluded that cobalt exerted a positive effect
on the redox properties of the system due to a decrease
in the nickel aluminate formation. Bimetallic Ni–Co-
containing catalysts are prepared, as a rule, by joint or
successive impregnation [14]. Because of importance of
oxidative dehydrogenation of lower alkanes with the
participation of lattice oxygen [15], studies aimed at op-
timizing the composition of oxide systems and proce-
dure for their preparation are being continued at many
research centers.
In this study, we analyzed the relationships of the
methane conversion on bimetallic CoO–NiO catalysts
of various compositions on various supports with the
aim of choosing the best catalyst for enlarged trials.
EXPERIMENTAL
Catalysts were prepared by impregnation of
microspherical (50–160 μm) γ-alumina. In the first step,
the microspheres were impregnated with an aqueous
solution of a mixture of Ni(NO3)2·6H2O and
Co(NO3)2·6H2O (both analytically pure grade, OOO
Laboratornaya Tekhnika, Russia), taken in an amount
corresponding to the moisture absorption capacity.
After drying at 100°С for 2 h, the material was
impregnated with a modifier solution and again dried at
100°С to constant weight. The last step of the catalyst
preparation involved its calcination at 460°С for 2 h and
at 650°С for 2 h.
Sample nos. 1, 2, and 3 were prepared so as to obtain
10, 25, and 50 wt % content of the active phase of Ni–Co
oxides. Microspherical γ-Al2O3 (AO SKTB Katalizator,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 93 No. 11 2020
Novosibirsk, Russia) was as a support. Sample no. 4 was
prepared so as to obtain approximately 10 wt % content
of the active phase of Ni–Co oxides using REDUXION
DMS microspherical catalyst for catalytic cracking
(BASF) as a support.
The physicochemical properties of catalyst samples
were determined by temperature-programmed reduction
(TPR) with hydrogen and by X-ray fluorescence and
X-ray diffraction (XRD) analysis.
X-ray diffraction analysis was performed with a
DRON-3M X-ray diffractometer (Cu Kα radiation, nickel
filter) at a scanning rate of 1 deg min–1 in the 2θ range
5°–75°. The X-ray diffraction patterns were processed
by the Rietveld method using the RIETAN-2000
program. The particle size was estimated from the peak
full width at half-maximum using the Scherrer equation.
Experiments on temperature-programmed reduction
with hydrogen were performed on a flow-through
installation equipped with a thermal conductivity
detector. Prior to reduction, the samples were subjected
to oxidation in an О2/Не flow under the conditions of
heating to 500°С at a rate of 15 deg min–1, keeping for
30 min at the final temperature, and cooling to room
temperature, also in an О2/Не flow.
The flow rate of the reducing mixture 10% H2 + 90%
Ar was 40 cm3 min–1 with programmed heating to
1000°С.
The catalyst trials were performed on a laboratory
pulse installation for methane oxidative conversion with
separate supply of the feed and oxidant and alternation
of the catalyst treatment cycles (three cycles) under the
following conditions: temperature 850°С, catalyst/feed
ratio 80, feed/catalyst contact time 3 s.
The main principles of our experiments were as
follows:
– catalytic oxidative conversion of methane occurs
on a metal oxide catalyst containing lattice oxygen;
– the lattice oxygen is replenished in the step of the
catalyst oxidation with air;
– the methane conversion and lattice oxygen
replenishment are performed successively with dosed
supply (pulses) of the reactants using a special dosing
valve;
– three methane pulses and three air pulses are fed in
turns in each experiment;
– the carrier gas containing reaction products is fed
from the reactor directly for analysis into the separating
 CHOOSING A MICROSPHERICAL CATALYST
Table 1. Chemical composition of metal oxide catalyst samples
Chemical composition, wt %, of indicated sample
Component
no. 1
Al2O3 89.59
SiO2 0.32
NiO 4.88
Co3O4 4.61
Na2O 0.29
SO3 0.20
Fe2O3 0.11
column of a chromatograph, where the reaction products
are analyzed, and then discharged into the atmosphere.
When a methane pulse is passed through a catalyst
bed in the reactor, the methane undergoes conversion to
form a hydrogen-containing gas.
RESULTS AND DISCUSSION
According to the XRD data (Table 1), the theoretically
possible content of active lattice oxygen [O]act,
corresponding to the amount of nickel and cobalt in
catalyst sample nos. 1, 2, 3, and 4, is 1.36, 5.14, 9.76, and
2.40 wt %, respectively.
The TPR curves (Fig. 1) show that the reduction with
hydrogen occurs in different temperature ranges, which
may be associated both with diversity of the forms of
surface and lattice oxygen in the catalysts and with their
complex microstructure.
Three main ranges of hydrogen uptake can be
distinguished:
– low-temperature range (up to 300°С), quantitatively
corresponding to the removal of the multilayer oxygen
coating of the surface; it is observed for all the samples
except no. 3;
– range with maxima at temperatures of up to 550°С,
quantitatively corresponding to the reduction of Со4+
and Со2+ to Со2+ and Со0 [16] and of Ni2+ to Ni0;
– high-temperature (>550°C) range quantitatively
corresponding to the reduction of Со2+ to Со0 and of
Ni2+ to Ni0.
The high-temperature peak can be attributed to the
presence of NiAl2O4 and CoAl2O4 formed by the
reaction of nickel and cobalt oxides with the support.
These compounds are characterized by strong oxygen–
catalyst bonding. On the other hand, partial oxidation of
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 93 No. 11 2020
1739
no. 2 no. 3 no. 4
70.43 43.51 43.44
0.23 0.89 41.56
14.13 27.32 7.19
14.29 26.61 6.50
0.47 0.88 0.32
0.43 0.70 0.31
0.02 0.09 0.68
methane in the presence of the catalysts under
consideration is performed at temperatures higher than
800°С because of high dissociation energy of the С–H
bond. This fact suggests that, despite the presence of
strongly bound oxygen, catalyst nos. 1, 2, and 4 will be
active in the methane conversion to syngas.
Oxidative conversion of methane occurs with the
formation of carbon monoxide and hydrogen, CH4 +
MeO → CO + 2H2 + nMe, and is accompanied by the
formation of carbon dioxide and water. When feeding
air, the reduced metal is oxidized again to the higher
oxide, O2 + 2Me → 2MeO; the catalyst is thus
regenerated, and the cycle is repeated.
The methane conversion (Fig. 2) on sample no. 1 of
the composition 10% (NiO + Co3O4)/γ-Al2O3 varies in
the range 55–66%; the maximal selectivity with respect
to hydrogen, 81.6%, is reached in the third pulse of the
feed. The selectivity with respect to carbon monoxide
and carbon dioxide is about 50% throughout the run.
The selectivity with respect to water reaches 40% in the
second pulse of methane, after which in the third pulse
of the feed it decreases to 18%. That is, complete
oxidation of methane prevails.
The influence of the content of active metals in the
metal oxide catalysts is demonstrated by the following
examples. In oxidative conversion on sample no. 2, 28%
(NiO + Co3O4)/γ-Al2O3, the СН4 conversion gradually
increases in the course of the experiment, reaching
80%. The selectivity with respect to Н2 remains on the
level of 100% throughout the experiment. The selectivity
with respect to СО increases with each pulse from 83.7
to 92.8%; correspondingly, the selectivity with respect
to СО2 gradually decreases from 16.3% in the first pulse
of methane to 7.2% in the third pulse.
 1740
(a)
Signal, mV
Time, min
(c)
Signal, mV
Time, min
Fig. 1. Curves of temperature-programmed reduction with hydrogen. Sample: (a) no. 1 [10% (NiO + Co3O4)/γ-Al2O3], (b) no. 2 [28%
(NiO + Co3O4)/γ-Al2O3], (c) no. 3 [50% (NiO + Co3O4)/γ-Al2O3], and (d) no. 4 [14% (NiO + Co3O4)/AlSiOx].
Sample no. 3 of the composition 50% (NiO + Co3O4)/
γ-Al2O3, prepared with a larger amount of the catalyst
active phase supported on aluminum oxide, is
characterized by lower conversion of methane compared
to the catalysts with lower content of nickel and cobalt
oxides (Fig. 2). Namely, the СН4 conversion is about
50%. The selectivity with respect to hydrogen in the
first and second pulses of methane is low, about 17%,
although in the third pulse of the feed it increases to
40%. The catalyst effects active complete oxidation of
methane, as indicated by high selectivity with respect to
Н2О, about 82% in the first and second pulses of methane
and 59% in the third pulse, and 92% selectivity with
respect to СО2 in the first pulse of the feed (by the third
pulse, it decreases only to 85.5%). The selectivity with
respect to carbon monoxide, though increasing with
each СН4 pulse, does not exceed 20%. The possible
cause of this effect is oversaturation of the support
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 93 No. 11 2020
GERZELIEV et al.
(b)
Temperature, °C
Temperature, °C
Signal, mV
Time, min
(d)
Temperature, °C
Signal, mV
Temperature, °C
Time, min
surface with the modifying metal oxides and formation
of agglomerates with the lower activity of the phase.
A commercial catalyst for catalytic cracking was used
as a support for sample no. 4. This sample had the
composition 14% NiO + Co3O4/AlSiOx.
The feed conversion on this catalyst gradually
decreases (though insignificantly): from 63% in the first
pulse of methane to 53.8% in the third pulse (Fig. 1).
The selectivity with respect to hydrogen is 100%. The
selectivity with respect to carbon monoxide is about
72%, and with respect to carbon dioxide, about 25%.
Hence, a catalyst for catalytic cracking can be used as a
support for preparing a metal oxide catalyst for methane
oxidative conversion.
On sample no. 1, the hydrogen content somewhat in-
creases and the methane concentration decreases in suc-
cessive methane conversion cycles. The methane–hy-
drogen mixture obtained on sample no. 2 consists main-
 CHOOSING A MICROSPHERICAL CATALYST 1741
(b)
(a)

Conversion, selectivity, %
Conversion, selectivity, %

Pulse no. Pulse no.

(c) (d)
Conversion, selectivity, %

Conversion, selectivity, %

Pulse no. Pulse no.

Fig. 2. Methane conversion and product composition as functions of the number of СH4 pulses. Sample: (a) no. 1 [10% (NiO + Co3O4)/
γ-Al2O3], (b) no. 2 [28% (NiO + Co3O4)/γ-Al2O3], (c) no. 3 [50% (NiO + Co3O4)/γ-Al2O3)], and (d) no. 4 [14% NiO + Co3O4/AlSiOx).

ly of hydrogen. The compositions of the methane–hy- Table 2. Composition of the methane–hydrogen mixture formed
drogen mixture in the second and third methane pulses by methane oxidative conversion on metal oxide samples
are close. On metal oxide catalyst no. 3, the products of Component, mol %
CH4 pulse no.
methane oxidative conversion contain mainly methane Н2 CH4
with a small amount of hydrogen (Table 2). Sample no. 1
The Н2 amount increases in successive methane 1 52.19 47.81
feeding pulses but does not exceed 11 mol %. The meth- 2 43.32 56.68
ane–hydrogen mixture obtained in methane oxidative 3 63.69 36.31
Sample no. 2
conversion on sample no. 4 contains almost two times
1 71.83 28.17
larger amount of hydrogen compared to methane: more
2 86.61 13.39
than 60 mol %, compared to approximately 35 mol %
3 87.88 12.12
(the remainder) СН4. The composition of the methane– Sample no. 3
hydrogen mixture in the third pulse of the feed is virtu- 1 5.16 94.84
ally identical to that obtained on sample no. 1. 2 8.07 91.93
3 10.67 89.33
CONCLUSIONS Sample no. 4
1 65.81 34.19
The results of experiments on methane oxidative 2 67.42 32.58
conversion in comparison with the data on temperature- 3 61.98 38.02

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 93 No. 11 2020

1742 GERZELIEV et al.
programmed reduction with hydrogen show that the
synthesized samples of the Ni–Co oxide system are
capable of repeated redox transitions (alternation of
reaction–regeneration cycles). Samples of the
composition 10% (NiO + Co3O4)/γ-Al2O3 and 14%
(NiO + Co3O4)/AlSiOx with optimum content of active
metals can be recommended for preparing methane
conversion catalysts for processes with separate supply
of the feed and oxidant on enlarged scale.
FUNDING
The study was financially supported by the Ministry of
Education and Science of the Russian Federation, agreement
no. 05.607.21.0311 of December 2, 2019, unique project
identifier RFMEFI60719X0311.
CONFLICT OF INTEREST
The authors declare that they have no conflict of interest.
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