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Methane conversion in low-temperature plasma

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DOI: 10.1134/S0018143909030023

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ISSN 0018-1439, High Energy Chemistry, 2009, Vol. 43, No. 3, pp. 156–162. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.I. Pushkarev, Ai-Min Zhu, Xiao-Song Li, R.V. Sazonov, 2009, published in Khimiya Vysokikh Energii, 2009, Vol. 43, No. 3, pp. 202–208.

PLENARY REPORTS FROM THE 5th INTERNATIONAL SYMPOSIUM ON THEORETICAL

AND APPLIED PLASMA CHEMISTRY
(September 3–8, 2008, Ivanovo, Russia)

Methane Conversion in Low-Temperature Plasma

A. I. Pushkareva, Ai-Min Zhub, Xiao-Song Lib, and R. V. Sazonova
Tomsk Polytechnic University, pr. Lenina 2a, Tomsk, 634028 Russia
e-mail: aipush@mail.ru
State Key Laboratory of Materials Modification by Laser, Ion, and Electron Beams; Dalian University, Dalian, China
Received October 20, 2008

Abstract—The conversion of methane in electric discharges of different types and under electron beam irradi-
ation are considered. The influence of nonequilibrium conditions of conversion in low-temperature plasma on
the energy consumption, product composition, and selectivity is analyzed. The results of works on plasma
pyrolysis, partial plasma oxidation, and steam and carbon dioxide reforming of methane in a low-temperature
plasma are discussed. It is shown that the use of chain processes makes it possible to substantially reduce the
power consumption for methane conversion by an electrophysical device.
DOI: 10.1134/S0018143909030023

Processing of natural gas and associated hydrocar- 95–98% at an acetylene selectivity of 90–95% and an
bon gas is one of the most important tasks of contem- energy consumption of 2.5–3 eV/molecule [1]. Under
porary gas chemistry. Geological studies have shown equilibrium conditions, an energy consumption of
that not only biogenic methane formation processes, 1.8 eV per methane molecule is required for the reac-
but also the continuing degassing of the Earth play tion 2ëç4 = ë2ç2 + 3ç2, regardless of the energy
dominating role in the formation of natural gas source.
reserves. As a result, up to 2 trillion cubic meters of gas
(its world production level) a year get into the Earth Numerous studies of hydrocarbon decomposition
crust. This allows us to treat natural gas as a partially upon heating have shown that the process is chain in
renewable material and energy source. character (thermal cracking). At low temperatures
when thermal initiation of cracking is impossible, an
A wealth of studies on methane conversion in vari- electric discharge generates active centers—free radi-
ous electric discharges and under continuous and cals, ions, or excited molecules—which can initiate
pulsed electron-beam irradiation have been performed chain hydrocarbon cracking processes. The chain
to date, thus making it possible to reveal the specifics of mechanism of methane pyrolysis in pulsed microwave-
methane degradation reactions in a low-temperature discharge plasma (9 GHz, 100 kW) was experimentally
plasma. The aim of this review is to analyze the influ- studied in [2, 3]. In the case of methane preheating to
ence of the nonequilibrium conditions in plasma on the 700–1100 K, the expenditure of plasma energy for
energy consumption, selectivity, and the product com- hydrogen synthesis does not exceed 1 eV/molecule.
position. The studies of the pyrolysis, partial oxidation, Similar results were obtained in a study of methane
and carbon dioxide and steam reforming of methane in pyrolysis in a gliding alternating-current (50 Hz, 3 kW)
a low-temperature plasma are considered. arc discharge [4]. At a gas flow rate of 2 m3/h, a pressure
of 6 atm, and a temperature of 1400 K, 34% of ëç4 was
converted into hydrogen and acetylene. The arc-dis-
PLASMA PYROLYSIS OF METHANE charge energy consumption for methane pyrolysis was
0.82 eV/molecule.
The pyrolysis of methane (conversion without addi-
tion of oxygenated compounds) is the most attractive The pyrolysis of ëç4 in atmospheric-pressure
process of natural gas reforming in which compounds spark, pulsed streamer, and dielectric-barrier (dc and
with a higher molecular mass of the motor fuel range ac) discharges at room temperature requires quite a
can be synthesized. The plasma synthesis of acetylene considerable consumption of energy [5]. For methane
by methane pyrolysis in arc discharge has been studied degradation, the energy costs (eV/molecule) are 14–25
and worked out on the engineering scale to the greatest in spark discharge, 17–21 in streamer discharge, 28–57
extent. The degree of conversion in this process reaches in dc dielectric-barrier discharge, and 116–175 in ac

156
 METHANE CONVERSION IN LOW-TEMPERATURE PLASMA 157

C, %
H2
80 C2H2
C2H4 C9−C10
C2H4
C8

60 C8H8
C6H6

CH4

40 C4−C5
C3

20

0
1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6

Fig. 1. Methane conversion and product composition (1) in the absence of catalyst and in the presence of the (2) HZSM-5,
(3) Fe+HZSM-5, (4) Co+HZSM-5, (5) Ni+HZSM-5, (6) Cu+HZSM-5, and (7) Zn+HZSM-5 catalysts.

barrier discharge. Pulsed spark discharge results in a and the maximal degree of conversion were obtained
high yield of acetylene (54%) and hydrogen (51%) at a under equilibrium conditions, in dc arc discharge (3
ëH4 conversion of 69%. In the case of barrier dis- eV/s, 95%). The use of different types of pulsed dis-
charge, ethane prevails in the conversion products. charge for ëç4 pyrolysis neither reduces the specific
energy consumption nor increases the conversion. The
A high efficiency and selectivity of thermocatalytic best results were obtained in pulsed spark discharge
processes of conversion of methane and other hydro- (3.8 eV/molecule, 28.5%), but they are worse than the
carbons stimulated studies on the plasma pyrolysis of results of methane pyrolysis in arc discharge plasma.
ëç4 in the presence of catalysts. Li et al. [6] reported The main degradation products are ë2 hydrocarbons
the results of study of the two-stage pyrolysis process with the highest proportion of acetylene.
in pulsed spark discharge (first step) and further in a
reactor with a catalyst (second step), which was Fe-, The nonequilbrium character of plasma interaction
Co-, Ni-, Cu-, or Zn-coated grains of the HZSM-5 cat- was revealed only in the case of microwave-discharge
alyst (SiO2/Al2O3 = 35). The catalyst temperature was or gliding arc discharge treatment of methane preheated
623 K. In the absence of the catalyst (Fig. 1), the meth- to the thermal degradation onset temperature. In this
ane conversion was 41% at an energy consumption of case, the plasma energy consumption for decomposi-
17 eV/molecule and the product composition was 84% tion is lower than that under the equilibrium conditions
acetylene and 75% hydrogen (percent of the maximal and does not exceed 1 eV/molecule.
theoretical yield). The addition of the (uncoated)
HZSM-5 catalyst increases the yield of aromatic hydro- PARTIAL OXIDATION OF METHANE
carbons (primarily, benzene, toluene, and xylene) to
15% with rise in the energy costs to 19 eV/molecule. At present, the overwhelming bulk of natural gas is
The Ni coating of grains provides for the highest yield processed into synthetic liquid fuel via the Fischer–
of aromatic hydrocarbons (47%) and a stable catalytic Tropsch process designed in 1923. For manufacture of
activity for 3 h. Methane pyrolysis in plasma is compre- liquid fuel, carbon compounds (natural gas, black and
hensively surveyed in [7, 8], and the data are collated in brown coals, heavy petroleum fractions, etc.) are con-
Table 1. verted into synthesis gas (mixture of CO and ç2) and,
then, into synthetic crude oil. The liquid fuel manufac-
Analysis of studies on the plasma pyrolysis of meth- ture technology requires high capital and operation
ane has shown that the minimal energy consumption costs at the syngas production step.

HIGH ENERGY CHEMISTRY Vol. 43 No. 3 2009

158 PUSHKAREV et al.

Table 1. Plasma pyrolysis of methane

Energy
Conversion,
Discharge type Reactant mixture Main products consumption,
%
eV/molecule
Pulsed microwave, 700–1100 K CH4 C2H2, H2 90–100 1
Gliding arc, 50 Hz, 1400 K CH4 C2H2, H2 34 0.82
Gliding, 50 Hz CH4 + H2 + Ar (75–84)% C2 18 1.6–4.4
Direct-current arc, 60 kW CH4 + H2 C2H2 95 4.2
Direct-current arc, 160 V, 75 A CH4 + N2 33% H2 80 8–10
Pulsed, 8 kHz CH4 – – 8.5
Pulsed glow, 50–200 Hz CH4 – – 9.1–10.3
Pulsed double-pointed, 2–20 kHz CH4 85% C2H2 23.5 3.8
Corona, 0.2–10 kHz CH4 – 25 52
Spark, 50 Hz; 5 kV CH4 C2H2 70 6.1
Streamer, 4.6 W CH4 C *2 19–41 17–21
Dielectric-barrier, 75 kHz, 17 W CH4 C2H6 6–13 38–57
Pulsed electron beam, 450 kV, 10 kA CH4 C 2* 5–7 18
Gliding radiofrequency, 13.56 MHz, 60 torr CH4 + Ar C2H2, C2H4 75 12
Dielectric-barrier with SiO2 catalyst CH4 C2H6+H2 45 52
Spark with Fe, Co, or Ni catalyst on HZSM-5 CH4 46% (C6H6, C7H8 C8H10) 40 19
Gliding (50 Hz) with Al2O3 catalyst CH4 + H2 + Ar (83–100)% C *2 18 2.4–7.3
* C2 includes ethane, ethylene, and acetylene.

The methane oxidation process is a branched-chain increased from 20 to 44%, the energy consumption for
process; it has been thoroughly studied under equilib- conversion increased from 1.4 to 5 eV/molecule.
rium conditions and is described in [9, 10]. The use of In the case of pulsed electron-beam irradiation
low-temperature plasma in the partial oxidation of CH4 (350–450 keV, 10 kA, 60 ns), partial methane oxidation
holds promise primarily for initiation of the chain pro- in a mixture with oxygen and hydrogen occurred in the
cess. Data on the partial oxidation of methane via the nonequilibrium mode [15]. The process of incomplete
chain process in microwave discharges of two types are oxidation of ëç4 was effective at a high initial concen-
reported in [11]. The plasma energy consumption was tration of oxygen (>30%) in the reactant mixture. As
0.25 eV/molecule at a methane conversion of 70% and the initial pressure of methane in the ç2 + é2 + ëç4
increased to 0.5 eV/molecule when the conversion mixture was increased at a constant oxygen pressure,
increased to 100%. the proportion of CO and ç2 in the products increased.
Data that are interesting from the viewpoint of The energy consumption for ëç4 conversion did not
industrial implementation were obtained in a study of exceed 0.05 eV/molecule.
the partial oxidation of methane in arc discharges of It was experimentally shown that the joint action of
different types. In a two-electrode arc plasma reactor, low-temperature plasma and catalyst substantially
the partial oxidation of CH4 in a stoichiometric mixture alters the composition of the products of methane par-
with oxygen is characterized by an energy consumption tial oxidation. Indarto et al. [16] studied the conversion
of at most 1 eV/molecule [12]. of methane in a 4 : 1 mixture with oxygen into methanol
Methane conversion in a mixture with oxygen in a dielectric-barrier discharge plasma (10 kV, 50 W).
(ëç4 : O2 = 1 : 2) in a rotating-arc plasma reactor also To increase the conversion efficiency, the CZA (cop-
showed a low energy consumption [13]. As the dis- per–zinc–aluminum) catalyst placed at the end of the
charge energy input to the gas increased from 2.6 to 4.8 plasma reactor was used without additional heating. In
kJ/l at a gas flow rate of 15–30 l/s, the consumption for the absence of the catalyst, the main products of partial
methane conversion increased from 1.6 to 2.2 eV/mol- methane oxidation in the barrier discharge were CO,
ecule. Similar results were obtained during the partial ëO2, and ç2, and the methanol content did not exceed
oxidation of ëç4 in its mixture with air in vortex glid- 11%. In the presence of the catalyst, the yield of meth-
ing arc discharge (10 kV, 15–20 kHz) [14]. As the initial anol increased by a factor of 2. The process comprised
methane concentration in the reactant mixture was two steps; the production of synthesis gas in low-tem-

HIGH ENERGY CHEMISTRY Vol. 43 No. 3 2009

 METHANE CONVERSION IN LOW-TEMPERATURE PLASMA 159

perature plasma and the subsequent formation of meth- C, %

anol on the catalyst. At ëç4 conversion of 28–33% and 30
a feed-mixture flow rate of 30 ml/min, the energy con-
sumption for methane conversion was 88–100 eV/mol-
ecule. Promoting the catalyst with different metals 20
made it possible to increase the selectivity for methanol
(Fig. 2). The data on the partial oxidation of ëH4 in dif- 10
ferent discharges are summarized in Table 2, and a
more detailed review is presented in [7, 8].
Thus, the highest yield of the synthesis gas at a low 0
no catalyst CZA CZA + Pt CZA + Ni CZA +Fe CZA + Y
energy consumption was obtained in various arc dis-
charges, which provide a high methane conversion
capacity per unit volume of the reactor and do not Fig. 2. Concentration of methanol in the products of plasma
require a high-voltage power source. The use of com- reforming of the CH4 + O2 mixture in the presence of dif-
ferent catalysts.
bined (plasma + catalyst) reactors makes it possible to
control the composition of conversion products, in par-
ticular, to increase the selectivity for ëç3éç from 3 to exceed 0.7 eV/molecule, thereby indicating the chain
35%. mechanism of the conversion [17].
The conversion of methane in a mixture with carbon
CARBON DIOXIDE REFORMING OF METHANE dioxide (ëç4/ëO2 = 1) in dielectric-barrier discharge
Methane conversion in the presence of carbon diox- plasma requires high energy consumption [18, 19]. The
ide is considered by many investigators to be an alter- study of the degree of conversion depending on the
native ëé2 utilization process aimed to mitigate the voltage pulse amplitude, pulse repetition frequency,
greenhouse effect and to simultaneously synthesize and the form (uni- or bipolar pulses, 4–12 kV, 0.4–
useful products. Under equilibrium conditions, the 2 kHz) shows that the conversion depends only on the
reaction ëç4 + ëé2 + 2.5 eV = 2CO + 2ç2 is run over specific energy input to the discharge. Variations in the
a Ni catalyst at a temperature of 850°ë and a pressure energy input by changing the voltage (pulsed power)
of 2–3 MPa [10]. and pulse repetition frequency (average power) have
Plasma methane conversion in a controlled arc dis- the same effect on the conversion. As the energy input
charge was studied in [12]. In the case of conversion of was varied from 16 to 70 J/cm3, the degree of ëH4 con-
the ëç4 + ëé2 mixture at atmospheric pressure, the version in the case of the bipolar pulse form increased
energy consumption for decomposition was 15 eV per from 9.8 to 22.8%, and the energy consumption
methane molecule. The use of an improved reactor increased from 38 to 70 eV/molecule. The data on car-
design with gliding arc discharge (480 V, 20 A) made it bon dioxide reforming of methane in different dis-
possible to reduce the energy consumption to 1.5– charges are collated in Table 3.
2.3 eV/molecule [12]. At a gas flow rate of 1.8– The results that hold promise for industrial imple-
4.7 m3/h, atmospheric pressure, and ambient tempera- mentation were obtained only for methane conversion
ture, the main products were ç2, CO, and ç2O. in a gliding discharge. In discharges of other types, the
When the reactant gas mixture was heated to 1200 separate conversion of ëO2 into CO and ëç4 into
K, the energy consumption of a pulsed corona dis- hydrocarbons (ë2ç6, ë2ç4, ë2ç2, etc.) takes place. The
charge for carbon dioxide methane reforming did not electrode material and the catalyst have a great effect on

Table 2. Partial oxidation of methane in plasma

Energy
Reactant Conversion,
Discharge type Products consumption,
mixture %
eV/molecule
Direct-current arc, 10 kW CH4 + O2 + Ar CO + H2 – 1
Rotating arc, 2 kW, 5–20 kHz CH4 + O2 50–60% H2 80 1.6–2.2
Vortex rotating arc CH4 + air H2/CO = 1.1–2.7 30 1.4–5
Microwave, 2.45 GHz, 1–5 kW CH4 + O2 CO + H2 100 0.5
Dielectric-barrier, 75 kHz CH4 + O2 CO, CH3OH 14–27 5–13
Dielectric-barrier, 20 kHz CH4 + O2 22% CH3OH 24 11
Dielectric-barrier with CZA catalyst CH4 + O2 30−35% CH3OH 28–33 88–100
Dielectric-barrier with Yt + Zr catalyst CH4 + O2 20–23% CH3OH 50 88

HIGH ENERGY CHEMISTRY Vol. 43 No. 3 2009

160 PUSHKAREV et al.

Table 3. Carbon dioxide reforming of methane in plasma

Conversion, Energy
Reactant Main
Discharge type consumption,
mixture products % eV/molecule
Direct-current gliding arc CH4 + CO2 CO + H2 – 1.5–3.3
Pulsed corona, 1200 K CH4 + CO2 CO2 + CO + H2 16 0.7
Alternating-current gliding arc CH4 + C2H6 + CO2 H2 + C2 8 20
Dielectric-barrier, 0.4–2 kHz CH4 + CO2 CO + H2 9.8–22.8 38–70
Dielectric-barrier, 2–40 kHz CH4 + CO2 CO + H2 25–65 73–100
Dielectric-barrier, 30 kHz CH4 + CO2 CO + H2 + C2H6 35–75 52–85
Dielectric-barrier with (Ir, Pd, Re)/γ-Al2O3 catalyst CH4 + CO2 CO + H2 + C2 30–50 –
Dielectric-barrier with catalyst (starch) CH4 + CO2 HCOH, CH3OH 48 16

the composition of the conversion products of the ëH4 the total energy consumption for ç2 synthesis of
+ ëO2 mixture. 4.2 eV/molecule.
Sekine et al. [23] examined the dependence of the
STEAM REFORMING OF METHANE conversion and the product composition on the spark-
discharge pulse repetition frequency (20–300 Hz) and
Steam methane reforming provides the maximal the proportion of ëç4 in a mixture with water vapor. At
yield of hydrogen and, therefore, holds promise for a methane conversion of 55%, a discharge power of
hydrogen economy and is being intensively studied. 2.1 W, and a feed mixture flow rate of 10 cm3/min, the
Under equilibrium conditions, the steam reforming of energy consumption for conversion was 5.2 eV/mole-
methane proceeds in accordance with the reaction cule. A distinguishing feature was a high ç2/ëé ratio,
ëç4 + ç2O +2.1 eV = CO + 3ç2 at a temperature of 4–4.5. This value is noticeably higher than the ratio
1300–1900 K and a pressure above l5 MPa [10]. characteristic of steam reforming under equilibrium
The conversion of methane in a mixture with steam conditions, ç2/ëé = 3. The cited authors [23] noted
in gliding discharge plasma is characterized in that the that the energy utilization efficiency of the pulse dis-
energy consumption for ëç4 decomposition does not charge for the synthesis of hydrogen and CO reached
exceed 0.92 eV/molecule [20]. A specific feature of the 60%.
reactor design is the rotation of the plasma string by an Zhdanok et al. [24] reported the results of study of
external magnetic field. At a discharge power of 1 kW, steam and steam–air methane reforming in a combined
a feed mixture flow rate of 30 l/min, a temperature of reactor employing a high-voltage atmospheric-pressure
150°ë, a pressure of 0.1 MPa, and a ëç4/ç2é ratio of discharge and catalysts (Ni or Fe2O3). The use of nickel
0.67, the degree of conversion reaches 50%. The main made it possible to reduce the discharge energy con-
products are hydrogen (55 vol %) and CO (10 vol %); sumption for ç2 production by a factor of 2.5. Data on
the amount of ëO2 and ë2ç2 does not exceed 1 vol %. steam reforming in discharges of different types are
Energy consumptions close to the enthalpy of the collated in Table 4.
process were achieved in the case of steam methane From the data presented in the table, it is seen that
reforming in a rotating gliding arc plasma reactor [21]. steam methane reforming in most low-temperature dis-
For the ëç4/ç2é = 0.2 mixture, a 44% conversion was charge plasmas requires a low energy consumption,
attained at an energy cost of 2.6 eV per methane mole- equal to or lower than the enthalpy of the process. This
cule. mode of plasma-assisted conversion of methane is the
The results of investigation of ëç4 conversion in a most promising for industrial implementation; how-
mixture with steam via the chain mechanism are ever, it has been little studied.
reported in [22]. The experiments were conducted in a
microwave plasma generator (915 MHz; pulse power,
200 kW) with preheating the reactant mixture to 500– COMBINED PROCESSES OF METHANE
570°ë; the ëç4/ç2é ratio was varied from 0.5 to 1. The CONVERSION IN PLASMA
gaseous products of the process were syngas and ëé2. The combination of the endoergonic reactions of
Azizov et al. [22] note that the total energy consump- carbon dioxide and steam reforming with the exother-
tion of the process is reduced by 30–60% when the dis- mic reactions of partial oxidation of methane makes it
charge is switched on, although the discharge energy possible to substantially reduce the energy consump-
does not exceed 5% of the thermal energy. At a cumu- tion for ëH4 conversion. The carbon dioxide reforming
lative energy input of 2 J/cm3, the concentration of the of natural gas in gliding ac arc discharge was studied by
product hydrogen was 11%, a value that corresponds to Chavadej et al. [25]. The addition of O2 to the ëç4 +

HIGH ENERGY CHEMISTRY Vol. 43 No. 3 2009

 METHANE CONVERSION IN LOW-TEMPERATURE PLASMA 161

Table 4. Steam methane reforming in plasma

Energy consumption,
Discharge type Main products Conversion, %
eV/molecule
Direct-current gliding arc H2 + CO 50 0.92
Direct-current rotating gliding arc H2 + CO 44 2.6
Microwave discharge, 915 MHz, 500–570°C H2 + CO + CO2 – 2.1
Spark discharge, 20–300 Hz H2 + CO 55 5.3
Spark discharge with Ni catalyst H2 + CO + CO2 70 1.6

Table 5. Combined reforming of methane in plasma

Energy
Conversion,
Discharge type Reactant mixture Main products consumption,
%
eV/molecule
Gliding arc, 17.5 kV, 300 Hz CH4 + C2H6 + C3H8 + CO2 + O2 H2, C2H4, C2H2, CO 30–70 14.3
Direct-current arc, 3.5 kW CH4 + H2O + air H2 80 4.2
Direct-current arc and NiO/Al2O3 catalyst CH4 + H2O + air H2, CO, CO2 70 0.35
Rotating, 10 kV, 50 Hz CH4 + H2O + air – 2–4 6
Microwave discharge, 915 MHz, 200 kW CH4 + H2O + O2 – 90 0.9–1

ë2ç6 + ë3ç8 + ëé2 mixture at a 75% hydrocarbon CONCLUSIONS

content of the initial reactant mixture reduced the
energy consumption for the decomposition of reactant Thus, the most important parameter from the view-
molecules from 19.4 to 14.3 eV/molecule, and the point of commercialization of the plasma reforming of
energy consumption for ç2 production decreased from methane is the energy consumption for its decomposi-
32 to 19.4 eV/molecule. tion. All types of discharge can be divided into two
groups in accordance with the energy consumption,
In a study of the plasma reforming of methane in a degree of conversion, and selectivity for products,
mixture of steam and air in a direct-current plasmatron, namely, inhomogeneous (arc, spark, gliding) and space
a 40% hydrogen yield (on a hydrogen content in meth- (dielectric-barrier, and corona) discharges.
ane basis) and an energy consumption of 2.1 eV/mole-
cule were achieved [26]. The use of the Nié/Äl2é3 cat- In inhomogeneous discharges, the methane conver-
alyst in combined methane reforming in the plasmatron sion efficiency is higher, the energy consumption for
made it possible to increase the yield of ç2 to 100% and decomposition is below 10 eV/molecule; the conver-
to reduce the energy consumption to 0.9 eV/molecule at sion in arc discharges exceeds 90% and the selectivity
a 70% methane conversion. reaches 90% for certain products (ë2ç2 in plasma
pyrolysis, ç2 and CO in steam reforming). In space dis-
To reduce the energy consumption for ëç4 conver- charges, a high degree of conversion (>50%) is reached
sion in a mixture with air and steam in an arc plasma- only at high energy consumptions for methane decom-
tron, the Ni/Äl2é3 catalyst (United Catalyst C-11) was position (>40–50 eV/molecule) and a broad range of
used [27]. At a 70% methane conversion, the energy products with a low selectivity are synthesized.
consumption for hydrogen production was reduced
from 1 eV/molecule (in the absence of catalyst) to A substantial reduction in the discharge energy con-
0.35 eV/molecule. sumption for methane decomposition is attained if the
conversion is conducted in the chain mode; in this case,
Steam methane conversion with a an admixture of the energy consumption does not exceed 1 eV/mole-
5% oxygen in a continuous microwave discharge cule. A promising line in the plasma reforming of meth-
(915 MHz, 200 kW) is described in [3]. At a gas flow ane is its conversion in a mixture with steam. In this
rate of 200 m3/h and a pressure of 0.1–1 atm, a 90% case, the energy consumption of gliding discharge for
conversion of ëç4 was achieved with an energy con- ëH4 decomposition is lower than the enthalpy of the
sumption for ç2 0.9–1 production of 0.9–1.0 eV/mole- steam methane reforming under the equilibrium condi-
cule. The data on combined methane reforming in tions. The yield of ç2 considerably exceeds the equilib-
plasma are presented in Table 5. rium values, and the ç2/ëé ratio is 5–10.

HIGH ENERGY CHEMISTRY Vol. 43 No. 3 2009

 162 PUSHKAREV et al.

ACKNOWLEDGEMENTS 11. Rusanov, V.D., Babaritskii, A.I., Gerasimov, E.N., Demin- 1

skii, M.A., Demkin, S.A., Zhivotov, V.K, Moskovskii, A.S.,
This work was supported by the Russian Foundation Potapkin, B.V., Smirnov, R.V., and Strelkova, M.I., Dokl.
for Basic Research, project no. 06-08-00147; the Akad. Nauk, 2003, vol. 389, no. 3, p. 324.
National Natural Science Foundation of China, grant 12. Lesueur, H., Czernichowski, A., Chapelle, A., Int. J.
nos. 10 775 028 and 20†106†003; the Program for New Hydrogen Energy, 1994, vol. 19, no. 2, p. 139.
Century Excellent Talents in University, NCET-06- 13. Lee, D.H., Kim, K.T., Song, Y.-H, and Cha, M.S., Proc.
0282, and the FokYing Tung Education Foundation, 18th Int. Symp. on Plasma Chemistry, Kyoto, 2007, p.
grant no. 94015. 153.
14. Heo, J., Choi, J.-W., Lee, H., Sekiguchi, H., and Song, H.K.,
Proc. 18th Int. Symp. on Plasma Chemistry, Kyoto, 2007,
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