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CEP 5280 1–7 ARTICLE IN PRESS

Chemical Engineering and Processing xxx (2007) xxx–xxx

3 Partial oxidation of methane with Cu–Zn–Al catalyst

4 in a dielectric barrier discharge
5 Antonius Indarto a,b,∗ , Dae Ryook Yang b , Jelliarko Palgunadi c , Jae-Wook Choi a ,

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6 Hwaung Lee a , Hyung Keun Song a
7
a Clean Technology Research Center, Korea Institute of Science and Technology, Republic of Korea
8
b Department of Chemical and Biological Engineering, Korea University, Republic of Korea

9
c Hydrogen Energy Research Center, Korea Institute of Science and Technology,

10 Republic of Korea

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Received 20 November 2006; received in revised form 23 December 2006; accepted 24 December 2006

11

12 Abstract
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13 A series of methanol synthesis catalyst containing Cu–Zn–Al (CZA) were prepared by co-precipitation method and applied for partial oxidation
14 of methane into methanol using dielectric barrier discharge (DBD). The methanol synthesis process was occurred at ambient temperature and
15 atmospheric pressure. In our experiment, CZA showed a high catalytic activity to increase the production of methanol. The methanol selectivity
16 of CZA-assisted plasma process was twice higher than that of non-catalytic plasma process. The addition of other metals on CZA catalyst also
17 produced a significant effect on the methanol production and it was found that yttrium could the best addition metal compared to Pt, Fe, and Ni.
18 Instead of methanol, the reaction products of plasma reactions were dominated by H2 , CO, CO2 , C2 and water. The optimum methanol selectivity
reached 27% when 3% yttrium metal was doped over CZA.
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19

20 © 2007 Published by Elsevier B.V.

21 Keywords: Methane oxidation; Methanol synthesis; Dielectric barrier discharge; Cu–Zn–Al; Heterogeneous catalyst
22
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1 1. Introduction The investigations of methane oxidation to methanol in 15

non-thermal plasmas have been made worldwide by corona 16

2 The catalytic conversion of methane into methanol is one of discharges, spark discharges, gliding arc, or dielectric barrier 17

3 the major challenges for chemists. Methane, as the major part discharges (DBD) at atmospheric pressure and ambient temper- 18
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4 of natural gas, is the cheapest and promising source for direct ature. Some researchers have tried to add auxiliary gases in the 19

5 conversion chemical process to produce methanol. Nowadays, process, such as hydrogen [1], air [1–3], oxygen [2–5], noble gas 20

6 the need for methanol increases due to its importance as an [3,6]. Some others used the different types of plasma discharges 21

7 intermediate material for industries. Well-established methanol in order to produce different types of products [7,8]. However, 22

8 production process is occurred via synthesis gas (CO, CO2 , and the production of methanol was still low and not economically 23
CO

9 H2 ) using Cu–Zn–Al2 O3 (CZA) catalyst. However, this process meets the market requirement. 24

10 route can be changed drastically when the effective method to In the present research, comprehensive study on the 25

11 oxidize methane to methanol is found. Catalytic oxidation of performance of plasma process combined with Cu–Zn–Al 26

12 methane at low temperatures is economically interesting, but, (CZA)-based catalyst for methane partial oxidation has been 27

13 very difficult to achieve as a result of the high stability of C–H undertaken. Dielectric barrier discharge was chosen as the 28

bonds. plasma media due to mild characteristics which probably offers

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14 29

better process for methanol synthesis. In methanol synthesis via 30

synthesis gas, CZA has been claimed as the active component 31

∗ Corresponding author at: Clean Technology Research Center, Korea Institute

for methanol production [9,10]. Although the catalytic reaction 32

of Science and Technology, Republic of Korea. Tel.: +82 10 2296 3748. mechanism is still not clear, the existence of CZA in the pro- 33

E-mail address: indarto antonius@yahoo.com (A. Indarto). cess was proved to be better material catalyst than other metals. 34

1 0255-2701/$ – see front matter © 2007 Published by Elsevier B.V.

2 doi:10.1016/j.cep.2006.12.015

Please cite this article in press as: A. Indarto et al., Partial oxidation of methane with Cu–Zn–Al catalyst in a dielectric barrier discharge, Chem.
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35 The synergy of Cu–Zn–Al was able to absorb the molecules voltage and current of 10 kV and 100 mA, respectively. A dig- 70

36 and conducted a series of surface reactions on the catalyst sur- ital power meter (Metex, model M-3860M) was inserted to the 71

37 face [11–13]. It is well known that for the hydrogenation of electricity line of the ac power supply in order to measure the 72

38 CO to methanol on Cu–Zn catalysts, Cu acts as the active cen- total supplied power to the reactor. 73

39 ter for the CO adsorption and activation. Although there are

40 many studies concerning the role of Zn, the ideas that have 2.3. Materials 74

41 been proposed are widely diversified, ranging from hydrogen

42 activation center, structural-electronic promoter, to bifunctional All experiments were carried out by introducing methane 75

43 Cu–Zn interfacial active center [11]. The similar mechanisms are (CH4 , purity >99.99%) and oxygen (O2 , purity >99.9%) 76

44 hopefully occurred in the plasma environment and due to abun- at fixed methane to oxygen ratio of 4:1 (volume basis). 77

45 dant amounts of radicals and ions and the production of methanol The input gases were controlled by calibrated mass flow 78

can be higher than that of conventional thermal process. controllers (Milipore, model FC-280SAV). Analysis of the

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46 79

47 In accordance with the above discussion, this study investi- products was done by a gas chromatography (YoungLin, 80

48 gates the influence of CZA on direct partial oxidation of methane model M600D, Column: 10 ft Hayesep D 80/100 + 10 ft Car- 81

49 to produce methanol. CZA and metal-supported CZA catalysts bowax 10% 80/100) with a thermal conductivity detector 82

50 were prepared by co-precipitation method and the efficiencies (TCD) for measuring H2 and CH4 and a flame ionized 83

were measured by calculating the production of methanol. detector (FID) for measuring CH4 , methanol, and higher 84

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51

hydrocarbons. 85

52 2. Experimental set-up The performance evaluation of the process was calculated 86

on the basis of products selectivity and methane conversion, 87

53 Fig. 1 shows a schematic diagram of the experimental set- formulated as

88

54 up. Methane and oxygen were introduced to the reactor at room

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55 temperature and atmospheric pressure. The products were ana- selectivity of H2 (%) 89

56 lyzed by a gas chromatography (GC). Details of each parts of moles of H2 produced

the system are described in the next sections. = × 100 (1) 90
57
2 × moles of CH4 converted
91
58 2.1. Reactor
selectivity of Cx Hy (%)
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92

59 The reactor is a cylindrical pyrex tube (i.d. of 7.5 mm) with x × moles of Cx Hy produced
60 two parallel-straight wires (0.2 mm diameter, stainless steel) as = × 100 (2) 93
moles of CH4 converted
61 the inner metal electrode and silver film coated at the outer side
62 of tube as the outer electrode. The effective volume and length 94
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63 of the reactor were 8.8 mL and 200 mm, respectively. In order

selectivity of CH3 OH (%) 95
64 to maintain the similarity of the reactor configuration, e.g. elec-
trodes gap distance, the reactor capacitance was checked first by moles of CH3 OH produced
= × 100
65
(3) 96
66 an RCL meter (Fluke PM6304) before and after experiments. moles of CH4 converted
97
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67 2.2. Power supply

selectivity of COx (%) 98

68 Plasma was generated by an alternating current (ac) power moles of COx produced
supply (Auto electric, model A1831) which has a maximum = × 100 (4) 99
69 moles of CH4 converted
CO
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Fig. 1. Experimental set-up.

Please cite this article in press as: A. Indarto et al., Partial oxidation of methane with Cu–Zn–Al catalyst in a dielectric barrier discharge, Chem.
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100
102 conversion of CH4 (%)
moles of CH4 converted
103 = × 100 (5)
104 moles of initial CH4

105 2.4. Preparation and characterization of catalyst

106 The precursors of methanol synthesis catalysts, denoted

107 as CZA and CZA–[Pt Ni Fe Y], with the % mole ratios
108 of Cu:Zn:Al = 6:2.5:1.5 were prepared by simultaneous co-
109 precipitation method from their nitrates solution at a pH about
110 7.0. A buffer solution with a pH 8.50 containing a mix-

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111 ture of NaHCO3 and Na2 CO3 was used as the precipitation
112 agents throughout the works. In a typical catalyst prepara-
113 tion, metal nitrates of Cu(NO3 )2 ·3H2 O, Zn(NO3 )2 ·6H2 O, and
114 Al(NO3 )·9H2 O were dissolved in H2 O to get 250 mL of metal
115 nitrate solution with total molar concentration of 0.3 M. In a

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116 1000 mL beaker glass initially filled with 200 mL of distilled
117 water, a solution of metal nitrates and a solution of precipita-
118 tion agent were dropt simultaneously for 1.5 h under vigorous
119 agitation at room temperature while the pH of the slurry was
120 maintained in a range from 6.90 to 7.10. Following the comple-
tion of co-precipitation process, the slurry was stirred further,
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121

122 which is so-called aging, for 2 h at room temperature.

123 The formed precipitate was filtered and washed with distilled
124 water under stirring for 12 h. This procedure was repeated six
125 times which were found to be sufficient for the slurry reached
126 pH about 7.0. The cake was dried at room temperature for 24 h
and then oven dried at 110 C for 24 h. The catalyst precursor
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127

128 was calcined under air condition at 350 ◦ C for 2 h. The cata-
129 lyst for methanol synthesis was grinded to about 0.18 mm and
130 physically mixed with a weight ratio of 1 with the same particle
131 size of ␥-Al2 O3 as the methanol dehydration catalyst. In order
Fig. 2. The XRD patterns of the catalyst: (a) the XRD phases change of CZA at
EC

132 to compare the performance of prepared catalyst with commer-

various catalyst treatments; (b) the uncalcined XRD pattern of CZA as function
133 cial CZA catalysts, the CZA produced by ICI (ICI Katalco 51-8; of various types of metal loading.
134 noted as CZAi) and BASF (BASF K3-110; noted as CZAb) was
135 ordered. Moreover, using the same method, some other metals,
136 e.g. Pt, Ni Fe, and Y, were also doped to CZA to increase the nations treatment which mostly produced CuO and ZnO as the 155

most dominant phases. However, in (a), the structure of catalyst

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137 activity of pure CZA. 156

before and after 6 h plasma process was not so much different. 157

138 2.4.1. XRD patterns The results also showed the stable production of methanol dur- 158

139 Crystal structures were identified by powder X-ray diffraction ing that operation period. It concludes that the deactivation of 159

140 spectroscopy on a Shimadzu 6000 X-ray diffractometer system catalyst was not occurred during 6 h operation due to plasma 160

(Cu K␣ radiation, 40 kV, 30 mA). Fig. 2a presents the XRD reactions. 161
CO

141

142 pattern changes of the prepared CZA at various conditions. The

143 CZA structure was greatly changed before and after calcinations. 2.5. SEM, EDS, and Cu surface area 162

144 After oven drying, the catalyst shows clearly a hydorotalcite-like

145 (HTlc) and malachite phases. This result is consistent with the Dispersed copper, incorporated with ZnO structure, is 163

146 previous report which suggested that HTlc phase coexists with a believed as the active side on the catalyst [11]. In this experi- 164
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147 malachite phase when the atomic ration of Cu/(Cu + Zn) is in the ment, the copper surface areas were determined by N2 O titration 165

148 range from 0.5 to 0.9. CuO also appears due to the high Cu/Zn using pulse flow experiment following to the previous method 166

149 ratio. The presence of CuO along with HTlc occurs due to the [11]. In a typical experiment about 50 mg of sample was loaded 167

150 Jahn–Taller effect. The existence of those phases on the fresh and reduced using 5 vol.% H2 in Ar at 250 ◦ C for 1 h and purged 168

151 uncalcined CZA catalyst will guaranty its activity of the after the reactor in a He stream at 250 ◦ C for 30 min and cooled down 169

152 calcinations treatment. Those forms were also appeared at all to 90 ◦ C at which the N2 O titrations were carried out. A surface 170

153 series CZA catalyst with addition of Pt, Ni, Fe, and Y as shown copper density of 1.47 × 1019 atoms/m2 assuming Cu:O = 2:1 171

154 in (b). The catalyst structure was greatly changed after calci- was used in this investigation. Surface analysis was done using 172

Please cite this article in press as: A. Indarto et al., Partial oxidation of methane with Cu–Zn–Al catalyst in a dielectric barrier discharge, Chem.
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Fig. 3. (a–c) SEM surface picture of CZA: (a and b) after calcinations; (c) after 6 h plasma reaction; (d) EDS elemental analysis.

173 Hitachi FE-SEM S-400 microscope at an accelerating voltage Fig. 4 shows the comparison of the catalyst performance 195

174 0.5–30 kV. Fig. 3 shows the surface images of the CZA catalyst. between CZA made by co-precipitation method with the com- 196
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175 Fig. 3 also present that there is no significant different of the mercialized one. By addition of CZA catalyst, the selectivity 197

176 catalyst structure before plasma reaction (b) and after plasma of methanol was sharply increased, almost two times higher 198

177 reaction (c). The elemental compositions of the samples were compared to non-catalytic plasma reaction. In non-catalyst reac- 199

178 determined by an energy dispersive spectrometer (EDS) analy- tion, the most products were dominated by CO, CO2 , and H2 . 200

179 sis using the same instrument. The typical result of EDS analysis The selectivity of methanol was less than 11%. From the result 201
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180 of the catalyst is shown in (d).

181 3. Results and discussion

3.1. Plasma stability and products distribution

CO

182

183 The direct methane oxidation using dielectric barrier dis-

184 charge (DBD) was conducted at room temperature and
185 atmospheric pressure. The total flow rate and the volumetric ratio
186 of methane to oxygen were maintained constant at 30 ml/min
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187 and 4:1, respectively. The supplied power to the reactor was also
188 fixed at 50 W. Our previous study showed that in this region, the
189 selectivity of methanol, the most profitable products, reached
190 the highest value for non-catalytic partial oxidation of methane
191 by dielectric barrier discharge [14]. The products were analyzed
192 at three different sampling times to ensure the reproducibility
193 data and each point of the experimental variables was repeated Fig. 4. Methanol increment selectivity and its stability as comparison between
194 twice. prepared CZA catalyst and commercialized CZA catalysts.

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Table 1
Products distribution as a function of various CZA catalyst
Catalyst Conversion Selectivity (%)
CH4 (%)
H2 CO CO2 C2 C3 C4

Blank 28.1 17.0 45.5 21.5 9.3 1.3 1.7

CZA 25.3 10.9 36.8 12.0 5.6 0.0 0.0
CZAi 31.0 11.2 35.7 10.6 6.7 0.0 0.0
CZAb 29.8 14.6 34.8 12.3 7.5 0.0 0.0

202 of non-catalytic process, it can be said that the non-catalytic

Fig. 5. Methanol selectivity as a function of catalyst loading.
plasma will convert methane and O2 into synthesis gas (CO,

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203

204 CO2 , and H2 ). C2 H6 was found as the single major product of

205 higher hydrocarbon (Table 1). 3.2. Effect of catalyst loading 241

206 Based on our previous kinetics calculation [14], the methanol

207 from methane oxygen plasma reaction can be possible produced The effects of catalyst loading on the methanol selectivity 242

from two reaction mechanisms: were shown in Fig. 5 and Table 2. The experimental results 243

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208
represented that the methanol selectivity was increased with 244

209 CH3 + OH → CH3 OH (6) the increase of catalyst loading. The methanol selectivity was 245

increase from 24% to 27.4% when the catalyst loading increased 246

210 CH2 + H2 O → CH3 OH (7) from 0.5 to 1.5 g. However, the catalyst loading was also affect- 247

ing the conversion of methane. The methane conversion was 248

Insertion reaction of single atom oxygen to methane was
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211
increased from 28% to 33% when the catalyst loading was 249
212 rarely occurred because methane is easily dissociated to CH3 changed from 0.5 to 1.5 g. Increasing amount of catalyst in the 250
213 and H or C and H2 in the bulk plasma. reactor will increase the methanol selectivity means that more 251

catalytic reactions of methanol production will be occurred on 252

214 CH4 → CH3 + H (8)
the surface of the catalyst. Although the selectivity increased, 253

215 CH4 → C + 2H2 (9) the efficiency of the catalyst, defined as a ratio of methanol 254
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production per weight of catalyst loading, was decreasing. 255

216 Between above two reactions, the second reaction of methanol The selectivity of other products is listed in Table 2. The main 256

217 synthesis was higher chance to be occurred. products were dominated by CO, CO2 , and H2 . The selectivity 257

218 By employing CZA catalyst, which is well-known catalyst for of C2 H6 was between 3% and 9% or around 80% of the total 258

219 converting synthesis gas to methanol, the selectivity of methanol C2 hydrocarbons. Similar with previous results, the increment 259
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220 was higher. We can conclude here that the plasma-catalytic of methanol production was followed by reducing concentration 260

221 process of methane and oxygen is a two-stage process which of CO, CO2 and H2 in the products stream. Compared to non- 261

222 consists of methane and oxygen conversion to synthesis gas then catalytic process, the CO and CO2 decreased around 20–30% 262

223 with catalyst, it will be converted to methanol. while H2 around 30%. 263

224 Fig. 4 shows that the value difference among the catalysts
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225 was relatively small means that the performance of CZA cat- 3.3. Effect of power increment 264

226 alyst made by co-precipitation method was satisfying enough

227 to be used for further experiments as the selectivity to produce In order to increase the methane conversion and probably 265

228 methanol was similar to the commercialized catalysts. The sta- the yield of methanol, the supplied power to the reactor was 266

229 bility of the catalyst used in long-time process was also good increased from 80 to 120 W. The effects of applied power to the 267
CO

230 represented by small fluctuations of methanol production. The products are shown in Fig. 6 and Table 3. The conversion rate 268

231 deactivation of catalyst, e.g. by carbon deposition or coke forma- of methane increased from 27% at 50 W to 45% at 140 W. It 269

232 tion, was not occurred. Our previous kinetic model results that at can be deduced trivially that by supplying more energy to the 270

233 the ratio of CH4 :O2 = 4:1, the produced solid carbon from CH4 reactor, the conversion of reactant will increased. As conversion 271

234 fragmentation will react with oxygen radical to form CO [14].

Table 2
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235 C + O → CO (10) Products distribution as a function of catalyst loading in the reactor

Metal loading (g) Conversion Selectivity (%)
236 Fig. 3c also proves that there is no significant amount of car- CH4 (%)
H2 CO CO2 C2 C3 C4
237 bon attached on the surface of the catalyst after plasma reactions.
238 The catalyst should turn into dark or black color when the car- Blank 28.1 17.0 45.5 21.5 9.3 1.3 1.7
239 bon or coke deposit on the surface of the catalyst. However, our 0.5 25.3 10.9 36.8 12.0 5.6 0.0 0.0
1 30.6 13.6 34.8 9.7 3.6 0.0 0.0
240 physical observation found the similar catalyst color between
1.5 33.9 12.0 32.9 6.6 6.9 0.0 0.0
before and after 6 h operation.

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Table 4
Products distribution as a function of various metals loading doped on CZA
catalyst
Metal loading Conversion Selectivity (%)
CH4 (%)
H2 CO CO2 C2 C3 C4

Blank 28.1 17.0 45.5 21.5 9.3 1.3 1.7

CZA 25.3 10.9 36.8 12.0 5.6 0.0 0.0
1% Pt/CZA 24.6 15.4 35.6 9.5 3.5 0.0 0.0
3% Ni/CZA 26.0 18.9 35.0 15.7 7.5 2.2 0.0
3% Fe/CZA 30.8 13.7 34.4 12.1 9.5 0.0 0.0
3% Y/CZA 25.3 10.1 33.8 9.0 5.6 0.0 0.0

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a significant effect on the direction of oxidation reaction. From 298

Table 4, the addition of Pt decreases the selectivity of CO2 and 299

CO (Fig. 7). The probability of methane conversion to methanol 300

Fig. 6. Effect of power supply on the conversion of methane and methanol would be higher as there is no significant different found on the 301

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selectivity. remaining products, e.g. C2 and higher hydrocarbons. Instead 302

of above reaction mechanism of methanol production, another 303

272 of methane and supplied power increased, the methanol selec- mechanism of methanol by CH3 and OH reaction could be 304

273 tivity of non-catalytic process tends to decrease. In other words, occurred. Pt and Fe are well-known metal catalysts which were 305

274 fragmentation reactions of molecules were preferable than re- able to activate CH4 [18,19] and adsorb OH [20]. Methanol can 306

combination or higher molecule synthesis reactions [15–17]. be formed by surface reaction between methyl methane with
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275 307

276 This idea was supported by the result presented in Table 3 OH: 308

277 which the concentration of CO, CO2 , and H2 also increased.

278 In non-catalytic plasma reaction, this condition resulted lower CHx → CHx(surf) (11) 309

279 production of methanol. The existence of CZA catalyst will

280 help maintaining the production of methanol from synthesis CHx(surf) + OH(surf) + (3 − x)H(surf) → CH3 OH(surf) (12) 310

gas produced by fragmentation reactions of methane and oxy-

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281

282 gen. As shown in figure, although the selectivity of methanol For the case of yttrium addition, the above mechanism is not 311

283 decreases as power increases, the decrement rate of plasma proved yet. Our calculation of the CO and CO2 and the ratio 312

284 with CZA catalyst is lower than that of non-catalytic plasma of CO2 to CO in the product stream for yttrium/CZA catalyst 313

285 process. are the lowest value compared to other catalysts. The existence 314

of yttrium inhibits the second-stage oxidation of carbon from

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315

CO to CO2 . However, this will create a chance for CO to be 316

286 3.4. Effect of metal addition on CZA
converted into methanol. The detail phenomena of partial oxida- 317

tion of methane with yttrium-stabilized zirconia were observed 318

287 In order to increase the activity of the catalyst, other transition
thoroughly in our previous research [21]. 319
288 metals, e.g. Pt, Ni, Fe, and Y, have been to the CZA catalyst. The
Different phenomena could be found in case of Ni–CZA cata-
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320
289 percentage of additional metal loading was only 3%, except for
lyst. The selectivity of methanol production decreased compared 321
290 Pt which is only 1%. Meanwhile, the total catalyst weight loaded
to pure CZA catalyst. In this case, we can think about differ- 322
291 in the reactor was only 0.5 g.
ent response of Ni on the reaction. Ni catalyst is also able to 323
292 As shown in Fig. 5, except Ni, the addition of metal catalysts
decompose methanol by oxidation reaction [22,23]. 324
293 on CZA gives a positive effect by increasing the selectivity of
methanol around 15–20% compared to the methanol selectivity
CO

294

295 of CZA catalyst. Among those, yttrium produced the highest

296 value of methanol selectivity that able to convert methane to
297 methanol around 31%. The addition of Y, also Pt and Fe, gave

Table 3
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Products distribution as a function of supplied power

Power (W) Conversion Selectivity (%)
CH4 (%)
H2 CO CO2 C2 C3 C4

50 28.5 10.9 36.8 12.0 5.6 0.0 0.0

80 38.0 14.7 39.5 13.3 4.8 0.0 0.0
110 39.5 18.9 40.0 15.2 6.2 0.0 0.0
140 45.0 20.5 42.7 18.3 4.0 0.0 0.0 Fig. 7. Effect of various types of metal loading of CZA catalyst on the methanol
selectivity.

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325 4. Conclusions generated by different electric discharge techniques, Catal. Today 98 (2004) 360
617. 361

[9] W.R.A.M. Robinson, J.C. Mol, Support effects in methanol synthesis over 362
326 The well-known methanol catalyst – copper–zinc–alumna –
copper-containing catalysts, Appl. Catal. 76 (1991) 117–129. 363
327 was tested to produce methanol by direct methane conversion [10] J.C.J. Bart, R.P.A. Sneeden, Alcohols from synthesis gas—a status report, 364
328 in a dielectric barrier discharge. The CZAs catalysts displayed Catal. Today 2 (1987) 1. 365

329 higher activity and better performance to produce methanol than [11] J.M. Thomas, W.J. Thomas, Principles and Practice of Heterogeneous 366

330 non-catalytic plasma process. The existence of CZA increased Catalysis, VCH Publishers, Weinheim, 1996, pp. 515–521. 367

[12] G.C. Chinchen, P.J. Denny, D.G. Parker, M.S. Spencer, D.A. Whan, Mech- 368
331 the selectivity and yields of methanol. Yttrium, also Pt and Fe,
anism of methanol synthesis form CO2 /CO/H2 mixtures over copper/zinc 369
332 was found to be the best addition for the conventional CZA oxide/alumina catalysts: use of 14 C-labelled reactants, Appl. Catal. 30 370
333 system in the plasma process for methanol synthesis. (1987) 333–338. 371

[13] H.H. Kung, Methanol synthesis, Catal. Rev. Sci. Eng. 22 (1980) 235–259. 372

334 Acknowledgement [14] A. Indarto, J.W. Choi, H. Lee, H.K. Song, Partial oxidation of methane 373

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to methanol by dielectric barrier discharge, in: Proceedings of the Spring 374

2006 Korean Chem. Eng. Symposium, 2006. 375

335 The authors thank the Korea Institute of Science and Tech- [15] A. Indarto, J.W. Choi, H. Lee, H.K. Song, Kinetic modeling of plasma 376
336 nology for supports. methane conversion using gliding arc, J. Nat. Gas Chem. 14 (2005) 377

13–21. 378
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Please cite this article in press as: A. Indarto et al., Partial oxidation of methane with Cu–Zn–Al catalyst in a dielectric barrier discharge, Chem.
Eng. Process. (2007), doi:10.1016/j.cep.2006.12.015