Partial oxidation of methane with Cu-Zn-Al catalyst in

a dielectric barrier discharge

Antonius Indarto1,2,†, Dae Ryook Yang2, Jelliarko Palgunadi3,

Jae-Wook Choi1, Hwaung Lee1, Hyung Keun Song1

1
Clean Technology Research Center, Korea Institute of Science and Technology

2
Department of Chemical and Biological Engineering, Korea University

3
Hydrogen Energy Research Center, Korea Institute of Science and Technology

†
Correspondence address: e-mail: indarto_antonius@yahoo.com, tel:+82-10-2296-3748

1
Abstract- A series of methanol synthesis catalyst containing Cu-Zn-Al (CZA) were

prepared by co-precipitation method and applied for partial oxidation of methane into

methanol using dielectric barrier discharge (DBD). The methanol synthesis process was

occurred at ambient temperature and atmospheric pressure. In our experiment, CZA

showed a high catalytic activity to increase the production of methanol. The methanol

selectivity of CZA-assisted plasma process was twice higher than that of non-catalytic

plasma process. The addition of other metals on CZA catalyst also 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. 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.

Keywords: Methane oxidation; methanol synthesis; dielectric barrier discharge; Cu-Zn-

Al; heterogeneous catalyst.

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1. Introduction

The catalytic conversion of methane into methanol is one of the major challenges for

chemists. Methane, as the major part of natural gas, is the cheapest and promising

source for direct conversion chemical process to produce methanol. Nowadays, the need

for methanol increases due to its importance as an intermediate material for industries.

Well-established methanol production process is occurred via synthesis gas (CO, CO 2,

and H2) using Cu-Zn-Al2O3 (CZA) catalyst. However, this process route can be changed

drastically when the effective method to oxidize methane to methanol is found.

Catalytic oxidation of methane at low temperatures is economically interesting, but,

very difficult to achieve as a result of the high stability of C-H bonds.

The investigations of methane oxidation to methanol in non-thermal plasmas have been

made worldwide by corona discharges, spark discharges, gliding arc, or dielectric

barrier discharges (DBD) at atmospheric pressure and ambient temperature. Some

researchers have tried to add auxiliary gases in the process, such as hydrogen [1], air [1-

3], oxygen [2-5], noble gas [3, 6]. Some others used the different types of plasma

discharges in order to produce different types of products [7-8]. However, the

production of methanol was still low and not economically meets the market

requirement.

In the present research, comprehensive study on the performance of plasma process

combined with Cu-Zn-Al (CZA)-based catalyst for methane partial oxidation has been

undertaken. Dielectric barrier discharge was chosen as the plasma media due to mild

characteristics which probably offers better process for methanol synthesis. In methanol

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synthesis via synthesis gas, CZA has been claimed as the active component for

methanol production [9-10]. Although the catalytic reaction mechanism is still not clear,

the existence of CZA in the process was proved to be better material catalyst than other

metals. The synergy of Cu-Zn-Al was able to absorb the molecules and conducted a

series of surface reactions on the catalyst surface [11-13]. It is well-known that for the

hydrogenation of CO to methanol on Cu-Zn catalysts, Cu acts as the active center for

the CO adsorption and activation. Although there are many studies concerning the role

of Zn, the ideas that have been proposed are widely diversified, ranging from hydrogen

activation center, structural-electronic promoter, to bifunctional Cu-Zn interfacial active

center [11]. The similar mechanisms are hopefully occurred in the plasma environment

and due to abundant amounts of radicals and ions and the production of methanol can be

higher than that of conventional thermal process.

In accordance with the above discussion, this study investigates the influence of CZA

on direct partial oxidation of methane to produce methanol. CZA and metal-supported

CZA catalysts were prepared by co-precipitation method and the efficiencies were

measured by calculating the production of methanol.

2. Experimental setup

Figure 1

Figure 1 shows a schematic diagram of the experimental setup. Methane and oxygen

were introduced to the reactor at room temperature and atmospheric pressure. The

products were analyzed by a gas chromatography (GC). Details of each parts of the

system are described in the next sections.

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2.1. Reactor

The reactor is a cylindrical pyrex tube (ID of 7.5 mm) with 2 parallel-straight wires

(0.2-mm diameter, stainless steel) as the inner metal electrode and silver film coated at

the outer side of tube as the outer electrode. The effective volume and length of the

reactor were 8.8 mL and 200 mm, respectively. In order to maintain the similarity of the

reactor configuration, e.g. electrodes gap distance, the reactor capacitance was checked

first by an RCL meter (Fluke PM6304) before and after experiments.

2.2. Power supply

Plasma was generated by an alternating current (AC) power supply (Auto electric,

model A1831) which has a maximum voltage and current of 10 kV and 100mA,

respectively. A digital power meter (Metex, model M-3860M) was inserted to the

electricity line of the AC power supply in order to measure the total supplied power to

the reactor.

2.3. Materials

All experiments were carried out by introducing methane (CH4, purity >99.99%) and

oxygen (O2, purity >99.9%) at fixed methane to oxygen ratio of 4:1 (volume basis). The

input gases were controlled by calibrated mass flow controllers (Milipore, model FC-

280SAV). Analysis of the products was done by a gas chromatography (YoungLin,

model M600D, Column: 10ft Hayesep D 80/100 + 10ft Carbowax 10% 80/100) with a

5
thermal conductivity detector (TCD) for measuring H2 and CH4 and a flame ionized

detector (FID) for measuring CH4, methanol, and higher hydrocarbons.

The performance evaluation of the process was calculated on the basis of products

selectivity and methane conversion, formulated as:

moles of H 2 produced
Selectivity of H 2 = × 100% (1)
2 × moles of CH 4 converted

x × moles of C x H y produced
Selectivity of C x H y = × 100% (2)
moles of CH 4 converted

moles of CH 3 OH produced
Selectivity of CH 3 OH = × 100% (3)
moles of CH 4 converted

moles of CO x produced
Selectivity of CO x = × 100% (4)
moles of CH 4 converted

moles of CH 4 converted
Conversion of CH 4 = × 100% (5)
moles of initial CH 4

2.4. Preparation and characterization of catalyst

The precursors of methanol synthesis catalysts, denoted as CZA and CZA-[Pt Ni

Fe Y], with the % mol ratios of Cu:Zn:Al = 6:2.5:1.5 were prepared by simultaneous co-

precipitation method from their nitrates solution at a pH about 7.0. A buffer solution

with a pH 8.50 containing a mixture of NaHCO3 and Na2CO3 was used as the

precipitation agents throughout the works. In a typical catalyst preparation, metal

nitrates of Cu(NO3)2⋅3H2O, Zn(NO3)2⋅6H2O, and Al(NO3)⋅9H2O were dissolved in H2O

to get 250 mL of metal nitrate solution with total molar concentration of 0.3 M. In a

6
1000 mL beaker glass initially filled with 200 mL of distilled water, a solution of metal

nitrates and a solution of precipitation agent were dropt simultaneously for 1.5 hours

under vigorous agitation at room temperature while the pH of the slurry was maintained

in a range from 6.90 to 7.10. Following the completion of co-precipitation process, the

slurry was stirred further, which is so-called aging, for 2 hours at room temperature.

The formed precipitate was filtered and washed with distilled water under stirring for 12

hours. This procedure was repeated 6 times which were found to be sufficient for the

slurry reached pH about 7.0. The cake was dried at room temperature for 24 hours and

then oven dried at 110 C for 24 hours. The catalyst precursor was calcined under air

condition at 350oC for 2 hours. The catalyst for methanol synthesis was grinded to about

0.18 mm and physically mixed with a weight ratio of 1 with the same particle size of γ-

Al2O3 as the methanol dehydration catalyst. In order to compare the performance of

prepared catalyst with commercial CZA catalysts, the CZA produced by ICI (ICI

Katalco 51-8; noted as CZAi) and BASF (BASF K3-110; noted as CZAb) was ordered.

Moreover, using the same method, some other metals, e.g. Pt, Ni Fe, and Y, were also

doped to CZA to increase the activity of pure CZA.

2.4.1. XRD patterns

Crystal structures were identified by powder X-ray diffraction spectroscopy on

a Shimadzu 6000 X-ray diffractometer system (Cu Kα radiation, 40 kV, 30 mA). Figure

2a presents the XRD pattern changes of the prepared CZA at various conditions. The

CZA structure was greatly changed before and after calcinations. After oven drying, the

catalyst shows clearly a hydorotalcite-like (HTlc) and malachite phases. This result is

7
consistent with the previous report which suggested that HTlc phase coexists with a

malachite phase when the atomic ration of Cu/(Cu+Zn) is in the range from 0.5 to 0.9.

CuO also appears due to the high Cu/Zn ratio. The presence of CuO along with HTlc

occurs due to the Jahn-Taller effect. The existence of those phases on the fresh

uncalcined CZA catalyst will guaranty its activity of the after calcinations treatment.

Those forms were also appeared at all series CZA catalyst with addition of Pt, Ni, Fe,

and Y as shown in figure 2b. The catalyst structure was greatly changed after

calcinations treatment which mostly produced CuO and ZnO as the most dominant

phases. However, in figure 2a, the structure of catalyst before and after 6 hours plasma

process was not so much different. The results also showed the stable production of

methanol during that operation period. It concludes that the deactivation of catalyst was

not occurred during 6 hours operation due to plasma reactions.

2.4.2. SEM, EDS, and Cu surface area

Dispersed copper, incorporated with ZnO structure, is believed as the active

side on the catalyst [11]. In this experiment, the copper surface areas were determined

by N2O titration using pulse flow experiment following to the previous method [11]. In

a typical experiment about 50 mg of sample was loaded and reduced using 5 vol % H 2

in Ar at 250 °C for 1 h and purged the reactor in a He stream at 250 °C for 30 min and

cooled down to 90 °C at which the N2O titrations were carried out. A surface copper

density of 1.47.1019 atoms/m2 assuming Cu:O = 2:1 was used in this investigation.

Surface analysis was done using Hitachi FE-SEM S-400 microscope at an accelerating

voltage 0.5~30 kV. Figure 3 shows the surface images of the CZA catalyst. Figure 3 also

8
present that there is no significant different of the catalyst structure before plasma

reaction (figure 3b) and after plasma reaction (figure 3c). The elemental compositions

of the samples were determined by an energy dispersive spectrometer (EDS) analysis

using the same instrument. The typical result of EDS analysis of the catalyst is shown in

figure 3d.

3. Results and discussion

3.1. Plasma stability and products distribution

Figure 4, Table 1

The direct methane oxidation using dielectric barrier discharge (DBD) was conducted at

room temperature and atmospheric pressure. The total flow rate and the volumetric ratio

of methane to oxygen were maintained constant at 30 ml/min and 4:1, respectively. The

supplied power to the reactor was also fixed at 50 watt. Our previous study showed that

in this region, the selectivity of methanol, the most profitable products, reached the

highest value for non-catalytic partial oxidation of methane by dielectric barrier

discharge [14]. The products were analyzed at three different sampling times to ensure

the reproducibility data and each point of the experimental variables was repeated twice.

Figure 4 shows the comparison of the catalyst performance between CZA made by co-

precipitation method with the commercialized one. By addition of CZA catalyst, the

selectivity of methanol was sharply increased, almost 2 times higher compared to non-

catalytic plasma reaction. In non catalyst reaction, the most products were dominated by

9
CO, CO2, and H2. The selectivity of methanol was less than 11%. From the result of non

catalytic process, it can be said that the non-catalytic plasma will convert methane and

O2 into synthesis gas (CO, CO2, and H2). C2H6 was found as the single major product of

higher hydrocarbon.

Based on our previous kinetics calculation [14], the methanol from methane oxygen

plasma reaction can be possible produced from two reaction mechanisms:

CH3 + OH  CH3OH (6)

CH2 + H2O  CH3OH (7)

Insertion reaction of single atom oxygen to methane was rarely occurred because

methane is easily dissociated to CH3 and H or C and H2 in the bulk plasma.

CH4  CH3 + H (8)

CH4  C + 2 H2 (9)

Between above two reactions, the second reaction of methanol synthesis was higher

chance to be occurred.

By employing CZA catalyst, which is well-known catalyst for converting synthesis gas

to methanol, the selectivity of methanol was higher. We can conclude here that the

plasma-catalytic process of methane and oxygen is a 2-stages process which consists of

methane and oxygen conversion to synthesis gas then with catalyst, it will be converted

to methanol.

Figure 4 shows that the value difference among the catalysts was relatively small means

that the performance of CZA catalyst made by co-precipitation method was satisfying

enough to be used for further experiments as the selectivity to produce methanol was

10
similar to the commercialized catalysts. The stability of the catalyst used in long-time

process was also good represented by small fluctuations of methanol production. The

deactivation of catalyst, e.g. by carbon deposition or coke formation, was not occurred.

Our previous kinetic model results that at the ratio of CH4:O2 = 4:1, the produced solid

carbon from CH4 fragmentation will react with oxygen radical to form CO [14].

C + O  CO (10)

Figure 3c also proves that there is no significant amount of carbon attached on the

surface of the catalyst after plasma reactions. The catalyst should turn into dark or black

color when the carbon or coke deposit on the surface of the catalyst. However, our

physical observation found the similar catalyst color between before and after 6 hours

operation.

3.2. Effect of catalyst loading

Figure 5, Table 2

The effects of catalyst loading on the methanol selectivity were shown in Figure 5 and

table 2. The experimental results represented that the methanol selectivity was increased

with the increase of catalyst loading. The methanol selectivity was increase from 24% to

27.4% when the catalyst loading increased from 0.5 gram to 1.5 gram. However, the

catalyst loading was also affecting the conversion of methane. The methane conversion

was increased from 28% to 33% when the catalyst loading was changed from 0.5 to 1.5

gram. Increasing amount of catalyst in the reactor will increase the methanol selectivity

means that more catalytic reactions of methanol production will be occurred on the

11
surface of the catalyst. Although the selectivity increased, the efficiency of the catalyst,

defined as a ratio of methanol production per weight of catalyst loading, was

decreasing.

The selectivity of other products is listed in Table 2. The main products were dominated

by CO, CO2, and H2. The selectivity of C2H6 was between 3% and 9% or around 80% of

the total C2 hydrocarbons. Similar with previous results, the increment of methanol

production was followed by reducing concentration of CO, CO2 and H2 in the products

stream. Compared to non-catalytic process, the CO and CO2 decreased around 20-30%

while H2 around 30%.

3.3. Effect of power increment

Figure 6, Table 3

In order to increase the methane conversion and probably the yield of methanol, the

supplied power to the reactor was increased from 80 to 120W. The effects of applied

power to the products are shown in figure 6 and table 3. The conversion rate of methane

increased from 27% at 50W to 45% at 140W. It can be deduced trivially that by

supplying more energy to the reactor, the conversion of reactant will increased. As

conversion of methane and supplied power increased, the methanol selectivity of non-

catalytic process tends to decrease. In other words, fragmentation reactions of molecules

were preferable than re-combination or higher molecule synthesis reactions [15-17].

This idea was supported by the result presented in Table 3 which the concentration of

CO, CO2, and H2 also increased. In non catalytic plasma reaction, this condition resulted

lower production of methanol. The existence of CZA catalyst will help maintaining the

12
production of methanol from synthesis gas produced by fragmentation reactions of

methane and oxygen. As shown in figure, although the selectivity of methanol decreases

as power increases, the decrement rate of plasma with CZA catalyst is lower than that of

non-catalytic plasma process.

3.1. Effect of metal addition on CZA

Figure 7, Table 4

In order to increase the activity of the catalyst, other transition metals, e.g. Pt, Ni, Fe,

and Y, have been to the CZA catalyst. The percentage of additional metal loading was

only 3%, except for Pt which is only 1%. Meanwhile, the total catalyst weight loaded in

the reactor was only 0.5 gram.

As shown in Figure 5, except Ni, the addition of metal catalysts on CZA gives a positive

effect by increasing the selectivity of methanol around 15 to 20% compared to the

methanol selectivity of CZA catalyst. Among those, yttrium produced the highest value

of methanol selectivity that able to convert methane to methanol around 31%. The

addition of Y, also Pt and Fe, gave a significant effect on the direction of oxidation

reaction. From table 4, the addition of Pt decreases the selectivity of CO2 and CO. The

probability of methane conversion to methanol would be higher as there is no

significant different found on the remaining products, e.g. C2 and higher hydrocarbons.

Instead of above reaction mechanism of methanol production, another mechanism of

methanol by CH3 and OH reaction could be occurred. Pt and Fe are well-know metal

catalysts which were able to activate CH4 [18-19] and adsorb OH [20]. Methanol can be

13
formed by surface reaction between methyl methane with OH:

CHx  CHx (surf) (11)

CHx (surf) + OH(surf) + (3-x) H(surf) CH3OH (surf) (12)

For the case of yttrium addition, the above mechanism is not proved yet. Our

calculation of the CO and CO2 and the ratio of CO2 to CO in the product stream for

yttrium/CZA catalyst are the lowest value compared to other catalysts. The existence of

yttrium inhibits the second-stage oxidation of carbon from CO to CO2. However, this

will create a chance for CO to be converted into methanol. The detail phenomena of

partial oxidation of methane with yttrium stabilized zirconia were observed thoroughly

in our previous research [21].

Different phenomena could be found in case of Ni-CZA catalyst. The selectivity of

methanol production decreased compared to pure CZA catalyst. In this case, we can

think about different response of Ni on the reaction. Ni catalyst is also able to

decompose methanol by oxidation reaction [22-23].

4. Conclusions

The well-known methanol catalyst – copper-zinc-alumna – was tested to produce

methanol by direct methane conversion in a dielectric barrier discharge. The CZAs

catalysts displayed higher activity and better performance to produce methanol than

non-catalytic plasma process. The existence of CZA increased the selectivity and yields

of methanol. Yttrium, also Pt and Fe, was found to be the best addition for the

14
conventional CZA system in the plasma process for methanol synthesis.

Acknowledgements

The authors thank to the Korea Institute of Science and Technology for supports.

15
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