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CO2 reforming of CH4 by atmospheric pressure


glow discharge plasma: A high conversion
ability

Article in International Journal of Hydrogen Energy January 2009


DOI: 10.1016/j.ijhydene.2008.10.053

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international journal of hydrogen energy 34 (2009) 308313

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

CO2 reforming of CH4 by atmospheric pressure glow


discharge plasma: A high conversion ability5

Daihong Li, Xiang Li, Meigui Bai, Xumei Tao, Shuyong Shang,
Xiaoyan Dai, Yongxiang Yin*
School of Chemical Engineering, Sichuan University, Chengdu 610065, Sichuan, China

article info abstract

Article history: CO2 reforming of CH4 to syngas has been investigated by a special designed plasma reactor
Received 2 September 2008 of atmospheric pressure glow discharge. High conversion of CH4, CO2, and high selectivity
Received in revised form of CO, H2, as well as high conversion ability are carried out. The experiment is operated in
16 October 2008 wider parameter region, such as CH4/CO2 from 3/7 to 6/4, input power from 49.50 W to
Accepted 16 October 2008 88.40 W and total feed flux from 360 mL/min to 4000 mL/min. The highest conversion of
Available online 25 November 2008 CH4 and CO2 is 98.52% and 90.30%, respectively. Under the experimental conditions of CH4/
CO2 rate at 4/6, input power at 69.85 W and total feed flux at 2200 mL/min, the conversion
Keywords: ability achieves a maximum of 12.21 mmol/kJ with the conversion of CH4 and CO2 is 60.97%
Plasma and 49.91%, the selectivity of H2 and CO is 89.30% and 72.58%, H2/CO rate is 1.5, respec-
Methane tively. This process has advantages of relatively large treatment and high conversion
Carbon dioxide ability, which is a benefit from a special designed plasma reactor.
Syngas 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
Conversion ability reserved.

1. Introduction mechanism [1315] were paid for seeking catalysts that have
good anti-carbon deposition performance.
The reaction of CO2 reforming of CH4 to syngas is widely Plasma process offers a unique way to induce gas phase
researched for great benefit to both environment and reaction, which is utilized in many chemical reactions. Several
economy. This conversion would not only reduce the atmo- plasma methods were employed to convert CO2 and CH4, such
spheric emissions of CO2 and the consumption of CH4, but also as thermal plasma (TP) [16], dielectric barrier discharge (DBD)
meet the special requirement in many synthesis processes [1720], corona discharge (CD) [2124], AC arc discharge (AD)
with its proper rate of H/C. Several technologies were [25] and glow discharge (GD) [26]. Plasma process showed to be
proposed to CO2 and CH4 conversion, such as catalysis a fast conversion and easy realization, its conversion ability
conversion [115], plasma conversion [1628] and combination still needed to be improved for future commercial use, though
of catalyst and plasma [2934]. some researchers attempted to combine catalyst and plasma
In the catalytic reforming of CO2 and CH4, carbon deposi- in CO2 and CH4 reforming system [2934] in recent years.
tion, leading to the deactivation of catalysts, was an intrac- In this paper, CO2 reforming of CH4 to syngas by atmo-
table problem. Therefore, a lot of efforts including addition spheric pressure glow discharge plasma is studied. With its
of promoters [17], selection of the supports [810], changes special characteristic of electron density, electron energies,
in preparation conditions [11,12] and studies of reaction 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).
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
international journal of hydrogen energy 34 (2009) 308313 309

0.18

0.16

current (A)
0.14

0.12

0.10

0.08
400 450 500 550 600

Fig. 1 Schematic configuration of the plasma reactor. Discharge voltage(V)

Fig. 3 Diagram of the VI characteristic discharge


P [ 1 atm, discharge gas: CH4 and CO2.
nonthermal plasma such as DBD and corona discharge, as
well as feed gases (CO2 and CH4) served as direct discharge
gas, atmospheric pressure glow discharge plasma process discharge current information in the circuit is from a resis-
brings out a high conversion ability, which is several times tance of 100 U (R1). All the measurements are made by a digital
higher than that of other discharge plasmas before. oscilloscope (RIGOL DS5022M). The details of the measure-
ment are shown in Fig. 2.
The principle and characteristic of discharge in this
2. Experiment experiment are similar to our previous studies [35]. When ac
voltage is risen to about 7000 V (mean-root-square value), the
2.1. Plasma apparatus gas between two electrodes are broken. After breaking, due to
the negative feedback of impedance of transformer, the
Fig. 1 shows the schematic configuration of the plasma voltage on the generator automatically falls down to several
reactor. An inside stainless steel stick with the outer diameter hundred volts, when a stable discharge is maintained. A
of 8 mm is connected to the high voltage supply and the typical VI characteristic for stable discharge is shown in
coaxial iron crust with the inner diameter of 30 mm serves as Fig. 3. As a result, the discharge current increases with
the grounded electrode. The stainless steel stick has an increasing the voltage from booster, while the voltage
ellipse-like discharge tip. An iron plate with a hole of 3 mm between two electrodes almost keeps at 500 V. Because the
diameter in the center is located at the contracted exit with discharge has this typical characteristic and operates at
the inner diameter of 10 mm. The discharge zone is formed atmospheric pressure, we call it atmospheric pressure glow
within a gap of 7 mm between the stainless steel stick and the discharge. This kind of plasma reactor has a special charac-
iron plate. Two electrodes are separated by nonconductor. teristic of electron temperature, electron density, plasma gas
As shown in Fig. 2, 50 Hz AC high voltage is connected on temperature which are about 2.5 eV, 3.5  1012/cm3, 900 K,
a booster. Adjusting booster, the voltage from the 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 (R3)/100 kU (R2), and the

Fig. 4 Schematic diagram of experimental process 1.CH4;


2. CO2; 3. needle valve; 4. rotormeter; 5. mixer; 6. plasma
Fig. 2 Sketch of measure circuit for voltage and current in reactor; 7. cold trap; 8. bubble meter; 9. electrical source;
the discharge experiment. and 10. GC7900.
310 international journal of hydrogen energy 34 (2009) 308313

respectively. And also can keep the feed gas absolutely pass H2 selectivity (%) [moles of H2 produced/(2  moles of
through the discharge space. CH4 converted)]  100%

CO selectivity (%) [moles of CO produced/(moles of CH4


2.2. Experimental system and analysis converted moles of CO2 converted)]  100%

The schematic diagram of experimental process is shown in H2/CO moles of H2 produced/moles of CO produced.
Fig. 4. The system is assembled with four major parts: a feed
gas system, a plasma reactor, AC high voltage power supply, Conversion ability shows the energy efficiency of CO2
and a gas analysis system. The feed and products are reforming of CH4 by plasma. It is defined as:
measured by a bubble meter and analyzed by a gas chro-
E (mmol/kJ) (millimoles of CH4 and CO2 converted per
matographic (GC7900) equipped with a thermal conductivity
second)  1000/(input power on plasma reactor).
detector (TCD). TDX-01 is used in GC column, the column
temperature is 100  C, the TCD current is 30 mA, and the flow
rate of the carrying gas (Ar) is 25 mL/min.
3. Results and discussions

2.3. Calculations 3.1. Effects of CH4/CO2 rate on reaction

By gas chromatographic analysis, it is found that the products In the experiments, the discharge gas is composed of CH4 and
consisted of H2, CO, CH4, CO2 and H2O. After reaction, there is CO2. Keeping CH4 CO2 total flow flux of 1000 mL/min, input
still a little carbon powder left in the reactor. According to the power of 68.95 W, the effect of CH4/CO2 rate on reaction is
analysis of the products, the overall conversions and selec- investigated by varying the CH4/CO2 rate from 3/7 to 6/4. The
tivity are defined as results are shown in Fig. 5.
CH4 conversion (%) (moles of CH4 converted/moles of CH4 In the experiment, When the CH4/CO2 rate is from 3/7 to 6/
introduced)  100% 4, the discharge could be obtained steadily for a long time. But
when the rate reaches at 7/3, serious carbon deposition on
CO2 conversion (%) (moles of CO2 converted/moles of CO2 electrodes affects the discharge stability. As shown in Fig. 5,
introduced)  100% with the CH4/CO2 mole rate increases from 3/7 to 6/4, the

a 100
b 100
90 90
80 80
Conversion( )

70 70
Selectivity( )

60 60
50 50
40 40
30 30
20 20
10 CH4 CO2 10 H2 CO
0 0
3:7 4:6 5:5 6:4 3:7 4:6 5:5 6:4
CH4/CO2 CH4/CO2

c 1.4

1.2

1
H2/CO

0.8

0.6

0.4

0.2

0
3:7 4:6 5:5 6:4
CH4/CO2

Fig. 5 Effects of CH4/CO2 rate on reaction (a) Conversion of CH4 and CO2; (b) Selectivity of H2 and CO; (c) H2/CO mole rate. The
input power is 68.95 W and total feed flux is 1000 mL/min.
international journal of hydrogen energy 34 (2009) 308313 311

conversion of CH4 decreases from 94.61% to 87.47% while that 14


of CO2 increases from 77.62% to 87.48%, the selectivity of H2
increases from 72.80% to 87.53% while that of CO decreases 12
from 88.87% to 68.90%, and H2/CO mole rate increases from
10
1.00 to 1.28, respectively. These could be interpreted by

E(mmol/kJ
amount of O atoms. The lower the CH4/CO2 rate is, the more O 8
atoms are in excess, which conduces to the reactions of
C O CO and H2 O H2O, the higher CO selectivity and 6
lower H2 electivity is obtained. Vice versa, the similar analysis
is for the results gotten at higher CH4/CO2 rate. 4
Concerning about CO selectivity and carbon deposition, it
2
would be better to choose the CH4/CO2 ratio in the range less
than 5/5. In the following investigation CH4/CO2 4/6 is chosen. 0
5 10 15 20 25 30 35 40 45 50 55 60
(mL/min/W)
3.2. Effects of feed flux treated per power
Fig. 7 Conversion abilities on various V.
Define V F/P. F is the total feed flux of H2 and CO2 (mL/min); P
is the power on plasma reactor (W). V is an important
parameter to express the feed flux treated per power (W).
Experiments are conducted by keeping CH4/CO2 rate of 4/6,
thermodynamic equilibrium of CO2 reforming of methane, the
varying the V from 5 mL/min/W to 60 mL/min/W. The exper-
results also showed that coke elimination should be done by
imental results are shown in Fig. 6.
increasing the reaction temperatures.
As shown in Fig. 6, the conversion of CH4 and CO2 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 3.3. Conversion ability
each molecule is reduced. The selectivity of H2 increases from
76.33% to 98.60% while that of CO decreases from 85.71% to Conversion ability is important because it expresses the
54.50% and H2/CO mole rate increases from 0.99 to 2.52 with V economic value of the process. Fig. 7 shows conversion abili-
increases from 5 mL/min/W to 60 mL/min/W. Thats because ties of all the experiments investigated. It is interesting that
the larger feed flux treated per power is, the lower the the optimal conversion ability locates at the region of
temperature of reaction system is, which prevents H2 and C V 20w40 mL/min/W, where the conversion abilities are all
atoms from further oxidation. Yunhua Li [36] analyzed bigger than 10 mmol/kJ.

100
90 CH4 CO2 100
80 90
)

70 80
Selectivity( )

70
Conversion(

60
60
50 50
40 40
30 30
20 20
10 10 H2 CO
0 0
5 10 15 20 25 30 35 40 45 50 55 60 5 10 15 20 25 30 35 40 45 50 55 60
(mL/min/W) (mL/min/W)

2.8
2.4
2.0
H2/CO

1.6
1.2
0.8
0.4
0.0
5 10 15 20 25 30 35 40 45 50 55 60
(mL/min/W)

Fig. 6 Effects of feed flux treated per power. (a) Conversion of CH4 and CO2; (b) Selectivity of H2 and CO; (c) H2/CO mole rate
vs.V. The experimental condition: CH4/CO2 rate 4/6, input power 49.5w88.4 W, feed flux 360w4000 mL/min.
312 international journal of hydrogen energy 34 (2009) 308313

Table 1 Comparison of specific energy with different plasmas.


Plasma Feed flux (mL/min) P (W) Conversion (%) Selectivity (%) E (mmol/kJ) Refs.

CH4 CO2 H2 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 3.67  104 9.6  103 88.28 76.05 72.48 89.06 2.3 [33]
and catalyst
Present experiment 2.2  103 69.85 60.97 49.91 89.30 72.58 12.21 This paper

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