CO

2
reforming of CH
4
by atmospheric pressure glow
discharge plasma: A high conversion ability
5
Daihong Li, Xiang Li, Meigui Bai, Xumei Tao, Shuyong Shang,
Xiaoyan Dai, Yongxiang Yin*
School of Chemical Engineering, Sichuan University, Chengdu 610065, Sichuan, China
a r t i c l e i n f o
Article history:
Received 2 September 2008
Received in revised form
16 October 2008
Accepted 16 October 2008
Available online 25 November 2008
Keywords:
Plasma
Methane
Carbon dioxide
Syngas
Conversion ability
a b s t r a c t
CO
2
reforming of CH
4
to syngas has been investigated by a special designed plasma reactor
of atmospheric pressure glow discharge. High conversion of CH
4
, CO
2
, and high selectivity
of CO, H
2
, as well as high conversion ability are carried out. The experiment is operated in
wider parameter region, such as CH
4
/CO
2
from 3/7 to 6/4, input power from 49.50 W to
88.40 W and total feed ux from 360 mL/min to 4000 mL/min. The highest conversion of
CH
4
and CO
2
is 98.52% and 90.30%, respectively. Under the experimental conditions of CH
4
/
CO
2
rate at 4/6, input power at 69.85 W and total feed ux at 2200 mL/min, the conversion
ability achieves a maximum of 12.21 mmol/kJ with the conversion of CH
4
and CO
2
is 60.97%
and 49.91%, the selectivity of H
2
and CO is 89.30% and 72.58%, H
2
/CO rate is 1.5, respec-
tively. This process has advantages of relatively large treatment and high conversion
ability, which is a benet from a special designed plasma reactor.
2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
The reaction of CO
2
reforming of CH
4
to syngas is widely
researched for great benet to both environment and
economy. This conversion would not only reduce the atmo-
spheric emissions of CO
2
and the consumption of CH
4,
but also
meet the special requirement in many synthesis processes
with its proper rate of H/C. Several technologies were
proposed to CO
2
and CH
4
conversion, such as catalysis
conversion [115], plasma conversion [1628] and combination
of catalyst and plasma [2934].
In the catalytic reforming of CO
2
and CH
4
, carbon deposi-
tion, leading to the deactivation of catalysts, was an intrac-
table problem. Therefore, a lot of efforts including addition
of promoters [17], selection of the supports [810], changes
in preparation conditions [11,12] and studies of reaction
mechanism [1315] were paid for seeking catalysts that have
good anti-carbon deposition performance.
Plasma process offers a unique way to induce gas phase
reaction, whichis utilizedinmany chemical reactions. Several
plasma methods were employed to convert CO
2
and CH
4
, such
as thermal plasma (TP) [16], dielectric barrier discharge (DBD)
[1720], corona discharge (CD) [2124], AC arc discharge (AD)
[25] and glowdischarge (GD) [26]. Plasma process showed to be
a fast conversion and easy realization, its conversion ability
still needed to be improved for future commercial use, though
some researchers attempted to combine catalyst and plasma
in CO
2
and CH
4
reforming system [2934] in recent years.
In this paper, CO
2
reforming of CH
4
to syngas by atmo-
spheric pressure glow discharge plasma is studied. With its
special characteristic of electron density, electron energies,
plasma temperature lower than thermal plasma, higher than
5
The project was supported by the National Natural Science Foundation of China (No.10475060).
* Corresponding author.
E-mail address: hyyx0675@sina.com (Y. Yin).
Avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ he
0360-3199/$ see front matter 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.10.053
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 4 ( 2 0 0 9 ) 3 0 8 3 1 3
nonthermal plasma such as DBD and corona discharge, as
well as feed gases (CO
2
and CH
4
) served as direct discharge
gas, atmospheric pressure glow discharge plasma process
brings out a high conversion ability, which is several times
higher than that of other discharge plasmas before.
2. Experiment
2.1. Plasma apparatus
Fig. 1 shows the schematic conguration of the plasma
reactor. An inside stainless steel stick with the outer diameter
of 8 mm is connected to the high voltage supply and the
coaxial iron crust with the inner diameter of 30 mm serves as
the grounded electrode. The stainless steel stick has an
ellipse-like discharge tip. An iron plate with a hole of 3 mm
diameter in the center is located at the contracted exit with
the inner diameter of 10 mm. The discharge zone is formed
within a gap of 7 mm between the stainless steel stick and the
iron plate. Two electrodes are separated by nonconductor.
As shown in Fig. 2, 50 Hz AC high voltage is connected on
a booster. Adjusting booster, the voltage fromthe transformer
of 1:500 is applied on two electrodes. By the impedance of
transformer with high transformation ratio, a stable atmo-
spheric pressure discharge mode is achieved without any
added ballast element.
The voltage information between the two electrodes is
from a potentiometer of 10 MU (R
3
)/100 kU (R
2
), and the
discharge current information in the circuit is from a resis-
tance of 100 U(R
1
). All the measurements are made by a digital
oscilloscope (RIGOL DS5022M). The details of the measure-
ment are shown in Fig. 2.
The principle and characteristic of discharge in this
experiment are similar to our previous studies [35]. When ac
voltage is risen to about 7000 V (mean-root-square value), the
gas between two electrodes are broken. After breaking, due to
the negative feedback of impedance of transformer, the
voltage on the generator automatically falls down to several
hundred volts, when a stable discharge is maintained. A
typical VI characteristic for stable discharge is shown in
Fig. 3. As a result, the discharge current increases with
increasing the voltage from booster, while the voltage
between two electrodes almost keeps at 500 V. Because the
discharge has this typical characteristic and operates at
atmospheric pressure, we call it atmospheric pressure glow
discharge. This kind of plasma reactor has a special charac-
teristic of electron temperature, electron density, plasma gas
temperature which are about 2.5 eV, 3.5 10
12
/cm
3
, 900 K,
Fig. 1 Schematic conguration of the plasma reactor.
Fig. 2 Sketch of measure circuit for voltage and current in
the discharge experiment.
0.08
0.10
0.12
0.14
0.16
0.18
400 450 500 550 600
Discharge voltage(V)
c
u
r
r
e
n
t

(
A
)
Fig. 3 Diagram of the VI characteristic discharge
P [1 atm, discharge gas: CH
4
and CO
2
.
Fig. 4 Schematic diagram of experimental process 1.CH
4
;
2. CO
2
; 3. needle valve; 4. rotormeter; 5. mixer; 6. plasma
reactor; 7. cold trap; 8. bubble meter; 9. electrical source;
and 10. GC7900.
i nt e r na t i o na l j o ur na l o f hy d r og e n e ne r gy 3 4 ( 2 0 0 9 ) 3 0 8 3 1 3 309
respectively. And also can keep the feed gas absolutely pass
through the discharge space.
2.2. Experimental system and analysis
The schematic diagram of experimental process is shown in
Fig. 4. The system is assembled with four major parts: a feed
gas system, a plasma reactor, AC high voltage power supply,
and a gas analysis system. The feed and products are
measured by a bubble meter and analyzed by a gas chro-
matographic (GC7900) equipped with a thermal conductivity
detector (TCD). TDX-01 is used in GC column, the column
temperature is 100

C, the TCD current is 30 mA, and the ow
rate of the carrying gas (Ar) is 25 mL/min.
2.3. Calculations
By gas chromatographic analysis, it is found that the products
consisted of H
2
, CO, CH
4
, CO
2
and H
2
O. After reaction, there is
still a little carbon powder left in the reactor. According to the
analysis of the products, the overall conversions and selec-
tivity are dened as
CH
4
conversion (%) (moles of CH
4
converted/moles of CH
4
introduced) 100%
CO
2
conversion (%) (moles of CO
2
converted/moles of CO
2
introduced) 100%
H
2
selectivity (%) [moles of H
2
produced/(2 moles of
CH
4
converted)] 100%
CO selectivity (%) [moles of CO produced/(moles of CH
4
converted moles of CO
2
converted)] 100%
H
2
/COmoles of H
2
produced/moles of CO produced.
Conversion ability shows the energy efciency of CO
2
reforming of CH
4
by plasma. It is dened as:
E (mmol/kJ) (millimoles of CH
4
and CO
2
converted per
second) 1000/(input power on plasma reactor).
3. Results and discussions
3.1. Effects of CH
4
/CO
2
rate on reaction
In the experiments, the discharge gas is composed of CH
4
and
CO
2
. Keeping CH
4
CO
2
total ow ux of 1000 mL/min, input
power of 68.95 W, the effect of CH
4
/CO
2
rate on reaction is
investigated by varying the CH
4
/CO
2
rate from 3/7 to 6/4. The
results are shown in Fig. 5.
In the experiment, When the CH
4
/CO
2
rate is from 3/7 to 6/
4, the discharge could be obtained steadily for a long time. But
when the rate reaches at 7/3, serious carbon deposition on
electrodes affects the discharge stability. As shown in Fig. 5,
with the CH
4
/CO
2
mole rate increases from 3/7 to 6/4, the
0
10
20
30
40
50
60
70
80
90
100
3 : 7 4 : 6 5 : 5 6 : 4
CH
4
/CO
2
CH4 CO2
0
10
20
30
40
50
60
70
80
90
100
3 : 7 4 : 6 5 : 5 6 : 4
CH
4
/CO
2
H2 CO
C
o
n
v
e
r
s
i
o
n
(



)
S
e
l
e
c
t
i
v
i
t
y
(



)
a
b
0
0.2
0.4
0.6
0.8
1
1.2
1.4
3 : 7 4 : 6 5 : 5 6 : 4
CH
4
/CO
2
H
2
/
C
O
c
Fig. 5 Effects of CH
4
/CO
2
rate on reaction (a) Conversion of CH
4
and CO
2
; (b) Selectivity of H
2
and CO; (c) H
2
/CO mole rate. The
input power is 68.95 W and total feed ux is 1000 mL/min.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 4 ( 2 0 0 9 ) 3 0 8 3 1 3 310
conversion of CH
4
decreases from 94.61% to 87.47% while that
of CO
2
increases from 77.62% to 87.48%, the selectivity of H
2
increases from 72.80% to 87.53% while that of CO decreases
from 88.87% to 68.90%, and H
2
/CO mole rate increases from
1.00 to 1.28, respectively. These could be interpreted by
amount of O atoms. The lower the CH
4
/CO
2
rate is, the more O
atoms are in excess, which conduces to the reactions of
COCO and H
2
OH
2
O, the higher CO selectivity and
lower H
2
electivity is obtained. Vice versa, the similar analysis
is for the results gotten at higher CH
4
/CO
2
rate.
Concerning about CO selectivity and carbon deposition, it
would be better to choose the CH
4
/CO
2
ratio in the range less
than5/5. Inthe following investigationCH
4
/CO
2
4/6 is chosen.
3.2. Effects of feed ux treated per power
Dene VF/P. F is the total feed ux of H
2
and CO
2
(mL/min); P
is the power on plasma reactor (W). V is an important
parameter to express the feed ux treated per power (W).
Experiments are conducted by keeping CH
4
/CO
2
rate of 4/6,
varying the V from 5 mL/min/W to 60 mL/min/W. The exper-
imental results are shown in Fig. 6.
As shown in Fig. 6, the conversion of CH
4
and CO
2
decrease
from 96.68% to 13.49% and from 87.40% to 9.67%, respectively.
For an increasing V implied the average energy obtained by
each molecule is reduced. The selectivity of H
2
increases from
76.33% to 98.60% while that of CO decreases from 85.71% to
54.50%and H
2
/COmole rate increases from0.99 to 2.52 with V
increases from 5 mL/min/W to 60 mL/min/W. Thats because
the larger feed ux treated per power is, the lower the
temperature of reaction system is, which prevents H
2
and C
atoms from further oxidation. Yunhua Li [36] analyzed
thermodynamic equilibriumof CO
2
reforming of methane, the
results also showed that coke elimination should be done by
increasing the reaction temperatures.
3.3. Conversion ability
Conversion ability is important because it expresses the
economic value of the process. Fig. 7 shows conversion abili-
ties of all the experiments investigated. It is interesting that
the optimal conversion ability locates at the region of
V20w40 mL/min/W, where the conversion abilities are all
bigger than 10 mmol/kJ.
0
10
20
30
40
50
60
70
80
90
100
5 10 15 20 25 30 35 40 45 50 55 60
(mL/min/W)
CH4 CO2
0.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
5 10 15 20 25 30 35 40 45 50 55 60
(mL/min/W)
H
2
/
C
O
0
10
20
30
40
50
60
70
80
90
100
5 10 15 20 25 30 35 40 45 50 55 60
(mL/min/W)
H2 CO
S
e
l
e
c
t
i
v
i
t
y
(



)
C
o
n
v
e
r
s
i
o
n
(




)
Fig. 6 Effects of feed ux treated per power. (a) Conversion of CH
4
and CO
2
; (b) Selectivity of H
2
and CO; (c) H
2
/CO mole rate
vs.V. The experimental condition: CH
4
/CO
2
rate 4/6, input power 49.5w88.4 W, feed ux 360w4000 mL/min.
0
2
4
6
8
10
12
14
5 10 15 20 25 30 35 40 45 50 55 60
(mL/min/W)
E
(
m
m
o
l
/
k
J
Fig. 7 Conversion abilities on various V.
i nt e r na t i o na l j o ur na l o f hy d r og e n e ne r gy 3 4 ( 2 0 0 9 ) 3 0 8 3 1 3 311
Conversion abilities in this work are much higher than
plasma reactions. A comparison is shown in Table 1.
4. Summary and conclusions
In this work, CO
2
reforming of CH
4
to syngas has been inves-
tigated using atmospheric pressure glow discharge plasma.
Some conclusions can be given as following:
1. The process is effective in converting CH
4
and CO
2
into
syngas. The products are simple, including H
2
, CO, and
a small amount of H
2
O. The highest conversion of CH
4
and
CO
2
is 98.52% and 90.30%, respectively, and the highest
conversion ability is 12.21 mmol/kJ.
2. Both the CH
4
/CO
2
rate and the V (feed ux treated per
power) inuence CH
4
and CO
2
conversions and H
2
and CO
selectivity. Proper H
2
/CO rate could be gained by modu-
lating the CH
4
/CO
2
rate and V.
3. Compared with other plasma process, the plasma used in
present experiment has advantages of larger treatment and
higher conversion ability. It benets from its special
characteristic.
r e f e r e n c e s
[1] Seok SH, Choi SH, Park ED, Han SH, Lee JS. Mn-promoted Ni/
Al
2
O
3
catalysts for stable carbon dioxide reforming of
methane. Journal of Catalysis 2002;209(1):615.
[2] Valentini A, Carreno NLV, Probst LFD, Probst LFD, Filho PNL,
Schreiner WH, et al. Role of vanadium in Ni:Al
2
O
3
catalysts
for carbon dioxide reforming of methane. Applied Catalysis
A 2003;255(2):21120.
[3] Chen HW, Wang CY, Yu CH, Tseng LT, Liao PH. Carbon
dioxide reforming of methane reaction catalyzed by stable
nickel copper catalysts. Catalysis Today 2004;97(23):17380.
[4] Martinez R, Romero E, Guimon C, Bilbao R. CO
2
reforming of
methane over coprecipitated NiAl catalysts modied with
lanthanum. Applied Catalysis A 2004;274(12):13949.
[5] Jozwiak WK, Nowosielska M, Rynkowski J. Reforming of
methane with carbon dioxide over supported bimetallic
catalysts containing Ni and noble metal I. Characterization
and activity of SiO
2
supported NiRh catalysts. Applied
Catalysis A 2005;280(2):23344.
[6] Nimwattanakul W, Luengnaruemitchai A, Jitkamka S.
Potential of Ni supported on clinoptilolite catalysts for
carbon dioxide reforming of methane. International Journal
of Hydrogen Energy 2006;31(1):93100.
[7] Supaporn T, Apichai T, Chairut S, Sarayut Y. Synthesis gas
production from dry reforming of methane over Ni/Al
2
O
3
stabilized by ZrO
2
. International Journal of Hydrogen Energy
2008;33(3):9919.
[8] Verykios XE. Catalytic dry reforming of natural gas for the
production of chemicals and hydrogen. International Journal
of Hydrogen Energy 2003;28(10):104563.
[9] Souza MDMVM, Clave L, Dubois V, Perez CACP, Scmal M.
Activation of supported nickel catalysts for carbon dioxide
reformingof methane. AppliedCatalysisA2004;272(12):1339.
[10] Pompeo F, Nichio NN, Ferretti OA, Resasco D. Study of Ni
catalysts on different supports to obtain synthesis gas.
International Journal of Hydrogen Energy 2005;30(1314):
1399405.
[11] Liu GH, Chu W, Long HL, Dai XY, Yin YX. A novel reduction
method for Ni/gAl
2
O
3
catalyst by a high frequency cold
plasma jet at atmospheric pressure. Chinese Journal of
Catalysis 2007;28(7):5824.
[12] Liu GH, Li YL, Chu W, Shi XY, Dai XY, Yin YX. Plasma-
assisted preparation of Ni/SiO
2
catalyst using atmospheric
high frequency cold plasma jet. Catalysis Communications
2008;9(6):108791.
[13] Tsang SC, Claridge JB, Green MLH. Recent advances in the
conversion of methane to synthesis gas. Catalysis Today
1995;23(1):315.
[14] Wang SB, Lu GQ. Carbon dioxide reforming of methane to
produce synthesis gas over metal-supported catalysts: state
of the art. Energy Fuels 1996;10(4):896904.
[15] Li DH, Xi M, Tao XM, Shi XY, Dai XY, Yin YX. TPD Studies on
Ni/gAl
2
O
3
catalysts reduced by atmosphere plasma.
Chinese Journal of Catalysis 2008;29(3):28791.
[16] Fincke JR, Anderson RP, Hyde T, Detering BA, Wright R,
Bewley RL, et al. Plasma thermal conversion to acetylene.
Plasma Chemistry and Plasma Processing 2002;22(1):10536.
[17] Zhou LM, Xue B, Kogelschatz U, Eliasson B. Nonequilibrium
Plasma reforming of greenhouse gases to synthesis gas.
Energy Fuels 1998;12(6):11919.
[18] Zhang YP, Li Y, Wang Y, Liu CJ, Eliasson B. Plasma methane
conversion in the presence of carbon dioxide using
dielectric-barrier discharges. Fuel Processing Technology
2003;83(13):1019.
[19] Li Y, Xu GH, Liu CJ, Eliasson B, Xue BZ. Co-generation of
syngas and higher hydrocarbons from CO
2
and CH
4
using
dielectric-barrier discharge: effect of electrode materials.
Energy Fuels 2001;15(2):299302.
[20] Li Y, Liu CJ, Eliasson B, Wang Y. Synthesis of oxygenates and
higher hydrocarbons directly from methane and carbon
Table 1 Comparison of specic energy with different plasmas.
Plasma Feed ux (mL/min) P (W) Conversion (%) Selectivity (%) E (mmol/kJ) Refs.
CH
4
CO
2
H
2
CO
Ac dielectric barrier 500 500 40 20 88.5 0.18 [17]
Dielectric barrier discharge 60 100 64.3 43.1 32.2 0.26 [18]
Pulsed corona plasma 25 42 63.7 60.2 62.6 0.26 [21]
Ac arc 75 30 88.9 53.2 81.5 0.15 [25]
Radio-frequency plasma 2920PPS 100 30.6 31.8 23.9 22.1 0.68 [27]
Radio-frequency plasma 10.3 kPPS 200 36.2 65.9 57.8 85.9 2.4 [28]
Thermal plasma
and catalyst
3.67 10
4
9.6 10
3
88.28 76.05 72.48 89.06 2.3 [33]
Present experiment 2.2 10
3
69.85 60.97 49.91 89.30 72.58 12.21 This paper
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 4 ( 2 0 0 9 ) 3 0 8 3 1 3 312
dioxide using dielectric-barrier discharges: product
distribution. Energy Fuels 2002;16(4):86470.
[21] Dai B, Zhang XL, Gong WM, He R. Study on the methane
coupling under pulse corona plasma by using CO
2
as oxidant.
Plasma Science and Technology 2000;2(6):57780.
[22] Li MW, Xu GH, Tian YL, Chen L, Fu HF. Carbon dioxide
reforming of methane using dc corona discharge plasma
reaction. Journal of Physical Chemistry A2004;108(10):168793.
[23] Le H, Lobban LL, Mallinson RG. Some temperature effects on
stability and carbon formation in low temperature ac plasma
conversion of methane. Catalysis Today 2004;89(1-2):1520.
[24] Zhao GB, John S, Zhang JJ, Wang LN, Muknahallipatna S,
Hamann JC, et al. Methane conversion in pulsed corona
discharge reactors. The Chemical Engineering Journal 2006;
125(2):6779.
[25] Huang A, Xia GG, Wang JY, Suib SL, Hayashi Y, Matsumoto H.
CO
2
reforming of CH
4
by atmospheric pressure ac discharge
plasmas. Journal of Catalysis 2000;189(2):34959.
[26] Chen Q, Dai W, Tao XM, Yu H, Dai XY, Yin YX. CO
2
reforming
of CH
4
by atmospheric pressure abnormal glow plasma.
Plasma Science and Technology 2006;8(2):1814.
[27] Yao SL, Ouyang F, Nakayama A, Suzuki E, Okumoto M,
Mizuno A. Oxidative coupling and reforming of methane
with carbon dioxide using a high-frequency pulsed plasma.
Energy Fuels 2000;14(4):9104.
[28] Yao SL, Okumoto M, Nakayama A, Suzuki E. Plasma
reforming and coupling of methane with carbon dioxide.
Energy Fuels 2001;15(5):12959.
[29] Jiang T, Li Y, Liu CJ, Xu GH, Eliasson B, Xue BZ.
Plasma methane conversion using dielectric-barrier
discharges with zeolite A. Catalysis Today 2002;72(34):
22935.
[30] Zhang XL, Zhu AM, Liu ZF, Li XH, Gong WM. Catalytic activity
of metal and metal-oxide catalysts in oxidative coupling of
CH
4
with CO
2
under pulse corona plasma. Chinese Journal of
Catalysis 2003;24(10):7256.
[31] Song HK, Choi JW, Sung HY, Lee H, Na BK. Synthesis gas
production via dielectric barrier discharge over Ni/gAl
2
O
3
catalyst. Catalysis Today 2004;89(12):2733.
[32] Cheng DG, Zhu XL, Ben YH, He F, Cui L, Liu CJ. Carbon
dioxide reforming of methane over Ni/Al
2
O
3
treated
with glow discharge plasma. Catalysis Today 2006;115(14):
20510.
[33] Tao XM, Qi FW, Yin YX, Dai XY. CO
2
reforming of CH
4
by
combination of thermal plasma and catalyst. International
Journal of Hydrogen Energy 2008;33(4):12625.
[34] Fidalgo B, Dominguez A, Pis JJ, Menendez JA. Microwave-
assisted dry reforming of methane. International Journal of
Hydrogen Energy 2008;33(15):433744.
[35] Li X, Tang JC, Dai XY, Yin YX. Study of atmospheric pressure
abnormal glow discharge. Plasma Science and Technology
2008;10(2):1858.
[36] Li YH, Wang YQ, Zhang XW, Mi ZT. Thermodynamic
analysis of auto thermal steam and CO
2
reforming of
methane. International Journal of Hydrogen Energy 2008;
33(10):250714.
i nt e r na t i o na l j o ur na l o f hy d r og e n e ne r gy 3 4 ( 2 0 0 9 ) 3 0 8 3 1 3 313