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1 Journal of the Chinese Institute of Chemical Engineers xxx (2007) xxx–xxx

www.elsevier.com/locate/jcice

3 Hydrogen production from methane in a dielectric barrier

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discharge using oxide zinc and chromium as catalyst
4

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5
Antonius Indarto a,b,*
a
6 Q1 Clean Technology Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul, Republic of Korea
7 b
Plasma-Catalyst Process Laboratory, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650, Republic of Korea
8 Received 4 June 2007; accepted 9 October 2007
9
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Abstract
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13 The hydrogen fuel cell is a promising option as a future energy resource; however, the nature of the gas is such that the conversion process of
14 other fuels to hydrogen on board is necessary. Among the raw fuel resources, methane could be the best candidate as it is plentiful. In this
15 experiment, the possibility of producing hydrogen with less carbon formation from methane by a dielectric barrier discharge (DBD) was
16
17
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investigated. Without the addition of a catalyst, the formation of hydrogen reached between 30% and 35% at methane residence time of 0.22 min
and supplied powers in the range of 60–130 W. The hydrogen selectivity increased at higher supplied power, but the process efficiency, defined as a
18 ratio of the produced hydrogen to the supplied power, decreased slightly. In order to boost the hydrogen production with less carbon formation, a
19 mixed oxide catalyst of zinc and chromium was added to the reactor. It was shown that the production of hydrogen was ca. 40% higher than the non-
20 catalytic plasma process.
21 # 2007 Published by Elsevier B.V. on behalf of Taiwan Institute of Chemical Engineers.
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22
Keywords: Plasma; Dielectric barrier discharge; Methane; Hydrogen production
23

24 42
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1. Introduction Currently, attention has been focused on the design and 43

25 operation of compact and efficient devices designed to generate 44
26 The development of fuel-efficient engines that produce hydrogen on board a vehicle. Jamal and Wyszynski (1994) 45
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27 fewer pollutants has been a major objective for many years. reviewed many possible onboard hydrogen generators and the 46
28 Regulatory requirements have been and will be of major alternative fuels for spark ignition engines. Hydrogen produc- 47
29 importance in defining the standards (Cooper, 1994). Increas- tion from methane (CH4) and methanol has attracted the 48
30 ingly stringent legislation directs attention at factors that reduce consideration of many experts. Although methanol has more 49
31 polluting emissions, such as a cold-start process and lowering advantages than methane, e.g. easier storage and safety, along 50
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32 Q3 sulfur levels in fuel (Matsumoto et al., 2000). Among many with the by-product of carbon monoxide being annoying for 51
33 selective compound candidates, hydrogen and methanol have both environmental and human health (Velu et al., 1999; Liu 52
34 been considered as green fuel starting materials. Compared to a et al., 2004). On the other hand, nowadays, methane for fuel is 53
35 hydrogen-based process, the kinetics of methanol conversion gaining popularity and widespread use, especially in the 54
36 was relatively slower and catalyst deactivation occurred transportation sector. 55
37 simultaneously. As a result, hydrogen is preferred (Cameron, In order to produce hydrogen from methane, a methane 56
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38 1999; Ralph and Hards, 1998; Hoogers and Thompsett, 1999), cracking process is necessary. However, the conventional 57
39 but presents obvious problems with generation, storage, and thermal method requires a high temperature condition to 58
40 distribution of the gas. Pressurized vessels or metal hydrides of achieve high methane conversion (Indarto et al., 2006a) and 59
41 hydrogen in a vehicle are relatively dangerous because can be very costly for the onboard process. In particular, 60
42 hydrogen is categorized as a highly flammable material. decomposition of methane using plasma could be a candidate 61
for this purpose as the existence of high-energy electrons 62
were able to decompose methane conversion at lower 63

Q2 * Tel.: +82 10 2296 3748; fax: +82 19 352 1981.

temperature. Yao et al. (2001) investigated the methane 64
E-mail address: indarto_antonius@yahoo.com. conversion using non-thermal plasma and showed that the 65

0368-1653/$ – see front matter # 2007 Published by Elsevier B.V. on behalf of Taiwan Institute of Chemical Engineers.
doi:10.1016/j.jcice.2007.10.001

Please cite this article in press as: Indarto, A., Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and
chromium as catalyst, Journal of the Chinese Institute of Chemical Engineers (2007), doi:10.1016/j.jcice.2007.10.001
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2 A. Indarto / Journal of the Chinese Institute of Chemical Engineers xxx (2007) xxx–xxx
65
66 methane conversion could be dramatically improved through
67 this method.
68 As high hydrogen production is the goal of the process,
69 process modification, e.g. by the addition of a catalyst, is
70 necessary to change the nature of the product distribution. In
71 thermal-based processes, the catalytic conversion of methane to
72 hydrogen is usually carried out by the catalyst of Ni or Pt (Peña
73 et al., 1996; Twigg, 1989; Rostrup-Nielsen, 1984). Our

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74 previous research using Pt/g-Al2O3 catalyst to convert CH4
75 in a DBD showed a negative effect on the production of

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76 hydrogen, as higher hydrocarbon transformation was the more Fig. 1. Experimental setup.
77 dominant phenomena (Kim et al., 2004). Better results 120
78 employing Ru and Rh catalysts were obtained in a catalytic supplied power to the reactor was manipulated by varying the 121
79 thermal process (Rostrup-Nielsen and Hansen, 1993). That voltages and currents. The measurement of applied power was 122
80 result was supported by our investigation that Ru and Rh were done by a watt-meter (Metex, model M-3860M). 123
81 also active metal catalysts for converting methane to hydrogen All experiments were carried out under atmospheric 124

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82 in a non-thermal plasma (Indarto et al., in press-a, in press-b), pressure and ambient temperature. The flow rates of methane 125
83 but, as the price in the market is relatively expensive, this gas were controlled by a mass flow controller. The output of the 126
84 material has been rarely used in the industry. reactor was connected to a gas chromatograph (YoungLin, 127
85 Bridger et al. (1970) developed a relatively cheaper mixture model M600D, column: 30 ft of Hayesep D) equipped with two 128
86 catalyst based on Zn and Cr oxide metal for hydrogen detectors (thermal conductivity and flame ionized detector). 129
87 production. Using a mixture of CH4 and CO2 as the reactants, EDConsidering the volume expansion and/or compression of the 130
88 the production of hydrogen yielded 35% at a relatively low product stream, the flow difference between the input and 131
89 temperature (ca. 100 8C). Davies and Hall (1976) thoroughly output line was measured by a bubble flow meter (Hewlett 132
90 investigated the activity of Zn catalyst for H2 production. Packard) referring to the condition before and after plasma 133
91 Recent experiments by Liu et al. (2004) showed that the reaction. The formulation of methane conversion and product 134
92 existence of ZnO-based catalyst increased the production of selectivity follows:
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93 hydrogen from methanol. The activity of ZnO–Cr2O3 catalyst
94 at low temperature condition has been investigated by Ohta moles of CH4 converted
Conversion of CH4 ¼  100 (1)
95 et al. (2004) for the dehydrogenation of isobutane. However, no moles of initial CH4 135
96 publication was found for the use of mixed oxide of Zn–Cr
97 catalyst for methane conversion to produce hydrogen both by Selectivity of Cm Hn
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98 thermal and plasma methods. n moles of Cm Hn produced

99 In this research, the direct methane conversion to hydrogen ¼   100 (2) 136
137
138
2 moles of CH4 converted
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100 was investigated using a dielectric barrier discharge (DBD). 139

101 DBD is a widely used plasma technique for many applications The atom balance of carbon and hydrogen was calculated in 140
102 because it is an easily installed and low-cost of operation each experiment to gain the quantitative satisfaction detection 141
103 instrument. In accordance with the above discussion, a catalyst of products by our analysis instruments. 142
104 based on Zn and Cr oxide metal was made and employed in In order to increase the production of hydrogen, a mixed 143
105 order to boost the production of hydrogen. In order to increase oxide catalyst of zinc (Zn) and chromium (Cr) was added on the 144
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106 the lifetime of the catalyst, the research would like to suppress plasma system. The catalyst was made by liquid mixing of 145
107 the production of carbon. The deposition of carbon by covering Zn(NO3)26H2O and Cr(NO3)39H2O precursor with distillated 146
108 the surface of catalyst is a major reason of the catalyst water. The detailed procedure of the catalyst preparation was 147
109 deactivation (Venugopal et al., 2007). described clearly in the patent paper of Bridger et al. (1970). 148
Before it was used, the dried gel catalyst was crushed and 149
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2. Experimental setup sieved until it reached uniform size of ca. 60–90 mesh. The 150
110 fresh catalyst was then calcined at 300 8C for 2 h in 151
111 The schematic diagram of the experimental setup is shown atmospheric air. The XRD spectrum of the catalyst after the 152
112 in Fig. 1. The reactor was a quartz tube with an inside diameter calcinations is presented in Fig. 2, which shows the dominant 153
113 of 6 mm and length of 20 cm. A thin silver film, serving as the ZnO and ZnCr2O4 crystal phase. Simard et al. (1995) 154
114 outer electrode, coated the outer wall of the reactor. The inner mentioned that those two phases were more active compared 155
115 electrode was two stainless wires (1 = 0.2 mm) located in the to single ZnC2O4 or Cr2O3 for the transformation of synthetic 156
116 center of the reactor. The plasma was generated by a high- gas. Those crystal phases could be active for the case of H2 157
117 voltage alternating current (AC) generator (Auto electric, production from methane. Only 0.5 g of catalyst was added in 158
118 model A1831) that has maximum voltage of 10.0 kV and the reactor and put 1.5–2 cm before the end of the plasma 159
119 maximum frequency of 20 kHz. In this experiment, the power zone in order to avoid the product’s decomposition by plasma. 160
frequency was maintained fixed at 20 kHz, while the output In this experiment, the catalyst treatments, e.g. calcinations and

Please cite this article in press as: Indarto, A., Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and
chromium as catalyst, Journal of the Chinese Institute of Chemical Engineers (2007), doi:10.1016/j.jcice.2007.10.001
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A. Indarto / Journal of the Chinese Institute of Chemical Engineers xxx (2007) xxx–xxx 3

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Fig. 2. XRD spectra of calcined catalyst.
160
161 regeneration, were used as the variable to investigate the
162 activity of the catalyst and its durability.

3. Results and discussion ED

163
3.1. Non-catalytic plasma reaction
164
165 The conversion of methane using non-thermal plasma
166 devices, especially dielectric barrier discharge, has been
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167 commonly used. Numerous reports and papers have been Fig. 3. Effects of supplied power variation on (a) methane conversion and (b)
168 published with differing results and conclusions as many products distribution.
169 aspects and variables exist in a DBD (Yao et al., 2001; Yang, 196
170 2003; Kim et al., 2004; Indarto et al., 2005, 2006a,b). Although The gaseous products of non-catalytic plasma of methane 197
171 plasma reaction is known as one of the most difficult reactions conversion were dominated by H2, C2 (mostly C2H6), C3, and 198
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172 to determine the kinetics, the tendency to follow a certain small amount of C4H10. Liquid product was not detected in all 199
173 pattern could be studied (Indarto et al., in press-a). The pathway ranges of experiment, and a small amount of solid carbon was 200
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174 pattern can easily change under different conditions as the found deposited on the reactor wall and the surface of inner 201
175 reactions are very sensitive to the population of active species, electrodes. The production of hydrogen was relatively stable 202
176 ions, and electrons. This is the reason the optimization of the in the range between 30% and 35%. Fig. 3b shows that the 203
177 parameters is necessary to obtain the optimum conditions for maximum production of C3 hydrocarbons occurred at a 204
178 the best results. supplied power of 90 W or at the minimum C4 hydrocarbon 205
179 Supplied power from an electrical generator to the reactor is production. On the other hand, production of C4 reached the 206
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180 one of the most important parameters in the plasma chemical highest value at higher supplied power (130 W) and 207
181 reaction to activate or decompose the methane molecule. The suppressed the production of C3. Similar to the trend of 208
182 magnitude of the external supplied power is related to the H2, the production of C2 compounds was not affected much 209
183 intensity of the internal electric field inside the reactor. An by supplied power variation. A previous paper by Kim et al. 210
184 increase of power could produce more energy to activate (2004) reported the similar situations when methane was 211
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185 molecules to higher energy levels and result in more energetic treated by a DBD. 212
186 electrons. In this condition, the possibility of breaking the C–H The effect of the residence time of methane in the reactor 213
187 bond in the molecule of methane could be initiated. Fig. 3 was also examined. Fig. 4 shows the results on methane 214
188 shows the effect of supplied power variation on the methane conversion (Fig. 4a) and the selectivity of products (Fig. 4b) vs. 215
189 conversion and product selectivity at the fixed input flow rate of residence time variation at a fixed supplied power of 80 W. 216
190 15 ml/min or residence time of 0.6 min. Methane conversion Different from the previous parameter, the effect of residence 217
191 was raised from 30% to 45% when the power was increased time gives more clear results in terms of product distribution. 218
192 from 60 to 130 W. It can be deduced, trivially, that supplying Methane conversion was significantly increased with an 219
193 more energy will increase the molecules’ instability inside the increase in residence time, as shown in Fig. 4a. Longer 220
194 reactor and cause more conversion of methane. Increasing periods of methane inside the reactor will create more 221
195 energy will also increase the density of electron and radical opportunities for methane molecules to collide with other 222
species inside the plasma zone. energetic species, e.g. electrons or radicals.

Please cite this article in press as: Indarto, A., Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and
chromium as catalyst, Journal of the Chinese Institute of Chemical Engineers (2007), doi:10.1016/j.jcice.2007.10.001
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4 A. Indarto / Journal of the Chinese Institute of Chemical Engineers xxx (2007) xxx–xxx

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Fig. 5. The Gibbs energy different (DG) profile of dehydrogenation of C2
hydrocarbons in the present of hydrogen atom.

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245
of 0.22 min. Under similar conditions, the production of C4 also 246
reached maximum 15% total selectivity. At a very short 247
residence time, it showed that the probability of higher 248
hydrocarbon formation was greater and that the dehydrogena- 249
tion reactions could be avoided. Eliasson et al. (2000) reported
ED 250
that methane chain reaction could occur following:

CH3 þ  CH3 ! C2 H6 (3) 251
 
C2 H6 þ e ! C2 H5 þ H þ e (4) 252
 
C2 H5 þ C2 H5 ! C4 H10 (5)
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254
253
255
Fig. 4. Effects of methane residence time on (a) methane conversion and (b)
products distribution.
As all of the above reactions have almost zero reaction 256
energy barriers (0 kcal/mol), a longer residence time is not 257
223 necessary to form higher hydrocarbons. Moreover, the 258
224 Fig. 4b shows that the production of H2 was clearly longer the higher hydrocarbons stay in the plasma zone, 259
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225 increased when the residence time was increased. As the the greater the probability of being attacked by hydrogen or 260
226 production of H2 increased, it reduced the selectivity of other electrons. 261
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227 products containing an H atom in their molecules. Our previous

228 research on gliding arc plasma also produced the similar results 3.2. Plasma with oxide of Zn and Cr catalyst
229 (Indarto et al., 2005, 2006b). At a longer residence time, 262
230 produced higher hydrocarbon (CxHy) from adduct reactions The use of a catalyst is necessary in order to control the 263
231 will be easily decomposed in the presence of a single atom of chemical reactions of plasma and increase the product yield. 264
232 hydrogen and transform into hydrogen molecules (H2) and Some papers have reported some results related to the use of 265
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233 other molecules (CxHy1) by a dehydrogenation reaction. Ab- catalysts (usually metal oxide catalyst) for hydrogen 266
234 initio1 calculation of Gibbs energy (DGT = 298 K) shows the production. Most authors preferred Pt, Ru, and Rh catalysts, 267
235 products of dehydrogenation reactions are more stable than the owing to their good activity and stability. Meanwhile, Ni- 268
236 reactants, which means that H2 production is preferable. Fig. 5 based catalysts are commercially more interesting but suffer 269
237 shows the Gibbs energy diagram of dehydrogenation reactions the disadvantage of a high rate of deactivation. Moreover, 270
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238 sequence occurring in C2 hydrocarbons. Although, at longer exploration to find the best catalyst is still challenging, 271
239 residence times, the selectivity of hydrogen reaches the highest especially as far as the perspective of reasonable price and 272
240 value, the power efficiency to H2 production (calculated as ratio good availability. In this experiment, a catalyst based on Zn 273
241 of H2 production to the total supplied power) decreased. In this and Cr oxide will be used combined with plasma to convert 274
242 condition, the process could be said to be not very efficient and methane and produce H2 as the product. Low production of 275
243 rather costly to apply. carbon is also necessary to prevent the catalyst from fast 276
244 The maximum selectivity of C2 and C3 hydrocarbons was deactivation. 277
245 35% and 20% respectively, both occurring at a residence time In order to find the best region where the catalyst was able 278
to show the activity significantly, we did a set of ‘screening’ 279
experiments. As the reaction temperature was relatively low 280
1
Ab-inito calculation was done by using Gaussian 03 software (Frisch et al., (ca. room temperature), some catalysts did not show any 281
2004) with DFT (UB3LYP) method and basis set of 6-31G(d). activity (Indarto et al., in press-b). In this case, increasing the

Please cite this article in press as: Indarto, A., Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and
chromium as catalyst, Journal of the Chinese Institute of Chemical Engineers (2007), doi:10.1016/j.jcice.2007.10.001
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A. Indarto / Journal of the Chinese Institute of Chemical Engineers xxx (2007) xxx–xxx 5
282
283 supplied power to increase the density of active species
284 could be a way of activating the surface property of the
285 catalyst.
286 At relatively low supplied powers or higher input flow rates,
287 the product distribution was not much different compared to the
288 distribution from the non-catalytic plasma process. The
289 existence of radicals and/or ions from methane fragmentation
290 was low due to the low conversion of methane. The optimal

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291 point of hydrogen production occurred at a flow rate of 30 ml/
292 min and power of 80 W.

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293 Before the catalyst was used, we treated it with two different
294 activation methods. The first catalyst was calcined at 300 8C
295 using atmospheric air for 2 h, noted as 1a, and the second one
296 was not calcined, noted as 3a. After around 2 h and 40 min
297 operation, all catalysts were taken out of the reactor and dried
298 for one night to remove any possible moisture (probably liquid

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299 hydrocarbons) attached to the surface of the catalyst. The dried
300 catalysts were then re-used for the similar experiment. They
301 were noted as 1b (for the catalyst coming from 1a) and 3b (for
302 the dried catalyst coming from 3a). However, a half portion of
303 the dried catalyst from 1b was reactivated by calcination at
304 300 8C for 2 h, noted as 2a. After 2a was used in the experiment ED
305 for around 2 h and 40 min, the catalyst was then dried for one
306 night and used again for the similar plasma reaction, and noted
307 as 2b. This method is proposed to know the effect of the
308 calcinations to the catalyst activity and to investigate the
309 durability of the catalyst, i.e. whether or not it is re-useable.
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310 As shown in Fig. 6a and b, the existence of the catalyst,
311 especially the calcined catalyst, increased the conversion of
312 methane. The methane conversion of the catalytic plasma
313 process was higher 50% than non-catalytic plasma process at
314 the beginning of the operation but decreased slightly as the
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315 operating time increased (1a). We found that the catalyst began
316 losing its activity after around 8 h of operation. After that time,
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317 the H2 selectivity and methane conversion were similar to the

318 non-catalytic plasma process. Fig. 6a shows that the activity the
319 catalyst could not be regenerated by only by drying the catalyst,
320 as the conversion of methane was similar to the non-catalytic
321 plasma process but it could slightly recover the activity of H2
Fig. 6. Effect of the catalyst on (a) methane conversion, (b) hydrogen selec-
322 selectivity. This means that the moisture or liquids which
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tivity, and (c) hydrocarbon selectivity. Data was obtained at gas flow rate of
323 possibly existed on the surface were not affecting the catalyst 30 ml/min and supplied power of 80 W.
324 activity or that the moisture or liquid was not present during the
325 process. However, the catalytic activity significantly reap- 339
326 peared when the used catalyst was re-calcined. The activity of The above phenomenon also occurred for the H2 selectivity. 340
327 2a catalyst was nearly similar to the activity of the 1a catalyst The addition of the catalyst increased the H2 selectivity 40% 341
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328 for both methane conversion and H2 selectivity. It is good news for the first time operation of the catalyst. Different from the 342
329 that the catalyst can be re-used with almost similar activity by catalyst activity in the methane conversion, the selectivity of H2 343
330 re-calcination. It is necessary to calcine the catalyst to oxidize production was relatively stable both for 1a and 2a catalyst. For 344
331 the adsorbed carbon by oxygen. Moreover, in another point of the 3a catalyst, the H2 selectivity was also stable but in lower 345
332 view, the calcination could be an important factor, as shown by values (ca. 30%). After the first hour of operation of the ‘‘b’’ 346
333 the different trend of 1a (catalyst with calcinations) and 3a catalyst (both 1b and 2b), the production of H2 was slightly 347
334 (catalyst without calcinations). The activity of uncalcined lower than the ‘‘a’’ catalyst (i.e. 1a and 2a), and the production 348
335 catalyst was shown to be very low as compared to the calcined decreased rapidly after 2 h operation with the ‘‘b’’ catalyst. The 349
336 catalyst, and this could refer to the crystal phases present in the interesting point, similar to the case of methane conversion, is 350
337 catalyst. The effect of re-calcination on the activity of the catalyst activity can be regenerated by calcination. 351
338 converting methane is still being studied further by analyzing One can conclude that the catalytic plasma process is more 352
the XRD, TEM, and SEM picture. efficient as compared to the non-catalytic process for H2

Please cite this article in press as: Indarto, A., Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and
chromium as catalyst, Journal of the Chinese Institute of Chemical Engineers (2007), doi:10.1016/j.jcice.2007.10.001
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6 A. Indarto / Journal of the Chinese Institute of Chemical Engineers xxx (2007) xxx–xxx
353 402
354 production as the catalytic plasma process produces higher H2 Bridger, G. W., D. O. Hughes, and P. W. Young, ‘‘Process for Producing Carbon 403
Dioxide and Hydrogen from Carbon Monoxide and Steam using Mixed 404
355 when compared to the non-catalytic process at similar supplied
Oxide of Copper, Zinc and Chromium as Catalyst and Process for Producing 405
356 power to the reactor. However, Ohta et al. (2004) and Said Catalyst,’’ U.S. Patent, 3, 514, 261 (1970). 406
357 Venugopal et al. (2007) mentioned the problem of the ZnO– Cameron, D. S., ‘‘The Sixth Grove Fuel Cell Symposium,’’ Plat. Metals Rev., 407
358 Cr2O3 catalyst being easily deactivated by coke deposition. In 43, 149 (1999). 408
359 the plasma process, nano-sized carbon can be formed in non- Cooper, B. J., ‘‘Challenges in Emission Control Catalysis for the Next 409
360 thermal plasma by methane fragmentation (Indarto, 2006c). Decade,’’ Plat. Metal Rev., 38, 2 (1994). 410
Davies, P. and A. J. Hall, ‘‘Process for Forming Hydrogen and Carbon Dioxide 411
361 Calcination of the catalyst using air could remove the carbon by Using a Catalyst Consisting Essentially of Oxide of Copper, Zinc and 412

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362 oxidizing it to form CO or CO2. Alumina or Magnesium,’’ U.S. Patent, 3, 961, 037 (1976). 413
363 Other hydrocarbon product selectivity is shown in Fig. 6c. Eliasson, B., C. J. Liu, and U. Kogelschatz, ‘‘Direct Conversion of Methane and 414

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364 The phenomenon is similar to the case of residence time effect Carbon Dioxide to Higher Hydrocarbons Using Catalytic Dielectric-Barrier 415
Discharges with Zeolites,’’ Ind. Eng. Chem. Res., 39, 1221 (2000). 416
365 in non-catalytic experiments. When the H2 selectivity rose, it
Frisch, M. J., G. W. Trucks, Schegel, H. B., et al., ‘‘Gaussian 03 Revision C. 417
366 sacrificed the other hydrocarbon products by suppressing their 02. Gaussian Inc., Wallingford, CT (2004). 418
367 selectivity. It is proposed that the existence of a catalyst will Hoogers, G. and D. Thompsett, ‘‘Releasing the Potential of Clean Power,’’ 419
368 ease the H2 production reactions, by adsorbing hydrogen Chem. Ind., 20, 796 (1999). 420
369 produced from dehydrogenation of hydrocarbons (shown in Indarto, A., J. W. Choi, H. Lee, and H. K. Song, ‘‘Kinetic Modeling of Plasma 421

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370 Fig. 5). Although it is still ambiguous, the existence of Cr on the Methane Conversion using Gliding Arc Plasma,’’ J. Nat. Gas Chem., 14, 13 422
(2005). 423
371 surface of catalyst seemed able to affect the kinetics of the H2 Indarto, A., J. W. Choi, H. Lee, and H. K. Song, ‘‘Methane Conversion Using 424
372 reaction (Kato et al., 2006). This finding also mentioned that Cr Dielectric Barrier Discharge: Comparison with Thermal Process and Cat- 425
373 could adsorb more hydrogen atoms than Co and Ni and possibly alyst Effects,’’ J. Nat. Gas Chem., 15, 87 (2006a). 426
374 perform H2 formation on the surface of the catalyst. Higher Indarto, A., J. W. Choi, H. Lee, and H. K. Song, ‘‘Effect of Additive Gases on 427
375 distributed Cr, acting as active site, would increase the Methane Conversion Using Gliding Arc Discharge,’’ Energy, 31, 2650 428
ED (2006b). 429
376 production of H2, and ZnO could disperse the Cr during the Indarto, A., ‘‘Chemical Reactions by Gliding Arc Plasma,’’ Thesis, Division of 430
377 catalyst formation (Thomas and Thomas, 1996). Environmental and Process, Korea Institute of Science and Technology, 431
Seoul, Korea (2006c). 432
4. Conclusions Indarto A., N. Coowanitwong, J. W. Choi, H. Lee, and H. K. Song, ‘‘Kinetic Q5 433
Modeling of Plasma Methane Conversion in a Dielectric Barrier Dis- 434
378
charge,’’ Fuel Process. Technol., in press-a. 435
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379 The production of hydrogen from methane by a dielectric Indarto A., J. W. Choi, H. Lee, and H. K. Song, ‘‘A Brief Catalyst Study on 436
380 barrier discharge with mixed oxide catalyst of zinc and Direct Methane Conversion Using a Dielectric Barrier Discharge,’’ J. Chin. 437
381 chromium was investigated. Non-catalytic plasma reactions Chem. Soc., in press-b. 438
382 resulted in hydrogen with selectivity of ca. 30–35%. The Jamal, Y. and M. L. Wyszynski, ‘‘On-board Generation of Hydrogen Rich 439
Fuels—A Review,’’ Int. J. Hydrogen Energy, 19, 557 (1994). 440
383 selectivity of hydrogen increased with increasing the power
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Kato, S., R. Suzuki, Y. Kawamoto, and H. Uchida, ‘‘Reactivities of H2, O2 and 441
384 supplied to the reactor. The addition of calcined mixed Zn–Cr H2O with the Cr Surface Between 77 K and 298 K,’’ J. Alloy Comp., 413, 442
385 oxide catalyst increased the hydrogen production 40% higher 214 (2006). 443
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386 than the non-catalytic reaction. The existence of a catalyst also Kim, S. S., H. Lee, B. K. Na, and H. K. Song, ‘‘Plasma-Assisted Reduction of 444
387 increased the methane conversion, but the conversion decreased Supported Metal Catalyst Using Atmospheric Dielectric-Barrier 445
Discharge,’’ Catal. Today, 89, 193 (2004). 446
388 slightly over a longer operation time. Carbon deposition could
Liu, S., K. Takahashi, K. Uematsu, and M. Ayabe, ‘‘Hydrogen Production by 447
389 be proposed as the main reason for catalyst deactivation, but Oxidative Methanol Reforming on Pd/ZnO Catalyst: Effects of the 448
390 catalyst activity can be regenerated by catalyst re-calcination. Addition of a Third Metal Component,’’ Appl. Catal. A: Gen., 277, 449
256 (2004). 450
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chromium as catalyst, Journal of the Chinese Institute of Chemical Engineers (2007), doi:10.1016/j.jcice.2007.10.001
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Please cite this article in press as: Indarto, A., Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and
chromium as catalyst, Journal of the Chinese Institute of Chemical Engineers (2007), doi:10.1016/j.jcice.2007.10.001