Partial oxidation of methane with Yttria-stablized Zirconia catalyst in

a dielectric barrier discharge

Shortened title: Methane oxidation with YSZ in a DBD

Antonius Indarto1,2,†, Hwaung Lee1, Jae-Wook Choi1, Hyung Keun Song1

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

2
Department of Chemical and Biological Engineering, Korea University

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

1
Abstract- Yttria-stabilized Zirconia (YSZ) has been used and studied as a catalyst

material for the direct partial oxidation of methane into methanol using dielectric barrier

discharge (DBD). The methanol synthesis process was occurred at ambient temperature

and atmospheric pressure. It shows that YSZ has an activity to increase the production

of methanol. It was twice higher in methanol selectivity than non-catalytic plasma

process. The YSZ catalyst also showed better performance compared to other commons

catalyst supports, e.g. carbon, Al2O3, TiO2, and SiO2. Instead of methanol, the reaction

products of plasma reactions were dominated by H2, CO, CO2, C2 and water. The

optimum methanol selectivity was reached 23% when Ni metal was doped over YSZ.

Keywords: Methane oxidation; methanol synthesis; dielectric barrier discharge; yttria-

stabilized zirconia; heterogeneous catalyst.

2
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 source for

hydrocarbons, and the need for methanol will increase in the near future. Currently, the

production of methanol is done via synthesis gas (CO, CO2, and H2). However, this

process route can be changed drastically when the effective method to oxidize methane

to methanol is found. Catalytic homogeneous oxidation of methane at low temperatures

is economically interesting, but also 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 (Liu et al.,

1998), air (Liu et al., 1998; Zhou et al., 1998; Indarto et al., 2006b), oxygen (Zhou et al.,

1998; Cormier and Rusu, 2001; Nozaki et al, 2004; Indarto et al., 2006b), noble gas

(Thanyachotpaiboon et al., 2004; Indarto et al., 2006b). Some others used the different

types of plasma discharges that possibly produce different products distribution (Song et

al., 2004b; Lia et al., 2004).

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

yttria-stabilized zirconia (YSZ) catalyst for methane partial oxidation has been

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

temperature condition which probably offers better process for methanol synthesis. In

3
methanol synthesis via syngas, YSZ has been claimed as the active component for

methanol production (Ekerdt, 1988). The YSZ showed better performance compared to

Al2O3 and SiO2 for the catalyst support for methane reforming (Chen et al., 2001).

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

YSZs on direct partial oxidation of methane. YSZ and YSZ-supported metal catalysts

were prepared and characterized, and the efficiencies of these catalysts were

demonstrated by methanol selectivity.

2. Experimental

Figure 1

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

were introduced into reactor at a room temperature and an atmospheric pressure. The

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

system are described in the next sections.

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

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

4
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

electric line of 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 carried out by a gas chromatography

(YoungLin, model M600D, Column: 10ft Hayesep D 80/100 + 10ft Carbowax 10%

80/100) with a 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 done based on products selectivity and

methane conversion which are 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

5
 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 Treatment of Catalyst

The commercialized yttria-stabilized zirconia was ordered from Tosoh Co.

(Japan). To measure the activity of the YSZ, some other materials which usually used as

catalyst support were employed as the comparators. Commercialized Al2O3, SiO2, TiO2,

and solid carbon powder were ordered from Kanto Chemical (Japan). Nano-size TiO2

was ordered from Varian (USA). To study further differences and detail effects of the

existence metal on the surface of the catalyst, 1% of Pt (weight basis) was added on the

powder catalyst by incipient wetness method. The Pt precursor was made by mixing

H2PtCl6.6H2O (Next Chimica, South Africa) with distillated water and dropped slowly

on the catalyst powder. And then, the Pt/[YSZ C Al2O3 TiO2] catalysts were dried at

120oC for 24h and calcined at 600oC for 2h at ambient air. Catalyst reduction was done

later by thermal method by flowing helium-hydrogen of 10 ml/min for 2h at 600oC.

Special treatment was applied for carbon catalyst case which the catalyst was calcined

and reduced using plasma method. Carbon catalyst calcination was done by flowing 6

ml/min of oxygen to the reactor filled with 1 gram of catalyst and applied power of

80W.

3. Results and discussion

6
3.1. Plasma stability and products distribution

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. In

these experiments, the supplied power to the plasma reactor was also fixed at 50 watt.

Our previous research shows that in this region, the selectivity of methanol, the most

profitable products, reached the highest value for partial oxidation of methane by

dielectric barrier discharge (Indarto et al., 2006c). The products were analyzed at three

different sampling times to ensure the reproducibility data and each point of

experimental variables was repeated twice.

Figure 2a shows the effect of applied power to the conversion of methane. It can be

deduced easily from the graph that increasing supplied power will increase the

conversion rate of methane. However, the lower ratios of CH4 to O2 give a lower

conversion of CH4. O2 has higher initial breakdown than CH4 to ignite the plasma.

Although O2 is an effective species to decompose CH4, higher O2 concentration in the

inlet stream will require higher supplied power means lower degree of plasma will

occurred at the same supplied power with higher CH4 concentration. In plasma reaction

process, the higher plasma energy level is more favorable to increase the decomposition

rate of reactant. The maximum conversion of methane reaches 60% at CH 4 to O2 ratio of

5:1 and supplied power of 80W. The gaseous products were mainly dominated by CO

and CO2. The CO and CO2 selectivity reaches ~46% and 22%, respectively. Water and

7
hydrogen were produced mostly as non-carbon products. The selectivity of hydrogen

was around 22% of total products selectivity. The selectivity of hydrogen was increased

drastically when the flow rate was reduced to 20 ml/min. On the other hand, the

selectivity of water was decreased twice than that the flow rate of in 30 ml/min. Our

previous investigation on plasma methane conversion shows that in longer residence

time condition, the plasma reactions tend to be fragmentation reactions into smaller

molecules, e.g. H2, rather than higher molecules combination reactions (Indarto et al.,

2005; 2006a; 2006b).

Significant amounts of methanol and C2 hydrocarbon production were detected. The

maximum methanol selectivity was 10%, occurred at flow rate of 30 ml/min and CH4 to

O2 ratio of 4:1 (figure 3b). This optimum reaction condition was used for the further

experiments using catalyst. Among higher hydrocarbons, ethane (C2H6) was the most

produced in this experiment and the selectivity was 9-12% of the total methane

conversion. The ratio C balance of product to reactant in all experiment ranges was

nearly 1 which shows that the production of carbon (C) was as the solid product was

small.

No significant different of products variation was found as effect of different sampling

times. Table 1 shows the results were almost independent from reaction time or

sampling time and the plasma process stability was reliable to be used in long time

operations.

3.1. Material catalyst comparison

Table 2

8
In order to increase the selectivity of methanol, as the desired product and the most

profitable product in this research, solid materials that probably act as catalyst has been

added at the end of plasma zone. This position was chosen to prevent the catalytic

products decomposition by plasma. The catalyst loaded in the reactor was only 0.5

gram.

In this study, we first compared the influence of different types of material which

commonly used as the catalyst support on the common chemical reaction process. 1%

of platinum was doped on each catalyst supports by incipient wetness method in order

to investigate the further differences affected by metal loading. As shown in table 2,

some material catalysts give a positive effect by increasing the selectivity of methanol.

Among other solid materials, YSZ gave the highest value that the selectivity of

methanol reaches almost 19% of the total methane conversion. Some other solid

materials, for example Al2O3 and TiO2, produced more methanol compared to non

catalytic reaction after the addition of 1% of Pt metal.

The addition of Pt gives a significant influent on the direction of oxidation reaction.

From table 2, it shows that the addition of Pt increases the selectivity of CO2 and

decreases the selectivity of CO. Moreover, no significant different found on the

remaining products, e.g. C2. It concludes that oxidation of CO to CO2 was occurred and

proposed reaction mechanisms can be:

CO  CO(surf) (6)

O  O(surf) (7)

9
 CO(surf) + O(surf)  CO2(surf) (8)

CO2(surf)  CO2 (9)

An interesting phenomena is also found when we look at the calculation of produced

CO and CO2 and also the ratio of CO2 to CO. The total selectivity of methane

conversion to CO and CO2 in YSZ catalyst is the lowest value than that in other

catalysts. This can be a reason for higher oxidation rate of methane to methanol in YSZ

catalyst. More oxygen was consumed to oxidize methane to methanol. Based on our

previous kinetics calculation (Indarto et al., 2006c), the methanol from methane oxygen

plasma reaction can be possible produced from two reaction mechanisms:

CH3 + OH  CH3OH (10)

CH2 + H2O  CH3OH (11)

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 (12)

CH4  C + 2 H2 (13)

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

chance to be occurred. The production of water, as the intermediate species and reactant

of the reaction 11, was produced almost twice higher in YSZ catalyst than other types of

catalyst. The YSZ also has the lower value of CO2 to CO ratio, only 0.2 - 0.4, compared

to non-catalytic reaction or other catalysts, in the range of 0.4 to 0.7. Lower CO 2 to CO

ratio means that YSZ was able to reduce the second oxidation rate of CO, probably by

adsorbing the oxygen radical species in the bulk plasma to the surface of catalyst.

10
YSZ has oxygen vacancy sites which are able to adsorb O- to the surface of the catalyst,

based on this kinetic scheme (Zhu et al., 2005):

O2 + e  O2- (14)

O2- + 2e  O22- (15)

O22-  2 O- (dissociation) (16)

O- + Vo,s + e  Oxo,s (incorporation) (17)

The Kröger-Vink notation is used for lattice defects: Vo,s denotes an oxygen vacancy in

the surface of catalyst, Oxo,s an oxygen ion in the lattice form and e an electron. By this

proposed formulation, YSZ is classified as a material for selective oxidation in thermal

process. This role was not changed in the plasma reaction caused by the dense

population of single oxygen ion and electron. However, only the surface lattice oxygen

will be accessible for the catalytic reaction.

3.2. YSZ catalyst

Table 3

Instead of Pt metal, some other transition metals have been doped to the YSZ powder by

incipient wetness method. Table 3 shows the effect of different doped metal on YSZ for

methane conversion. For methanol production, 3% Ni/YSZ catalyst shows slightly

better selectivity than that of 1% Pt/YSZ and 3% Ni/Al2O3. The existence of Ni catalyst

has proved well to reduce the CO2 molecule into synthesis gas CO and the role of Ni

catalyst has been presented also (Berger and Doesburg, 1996; Khaliq and Foger, 2000; Hou

and Hughes, 2001; Song et al, 2004). The higher concentration of synthesis gas, CO and

11
H2, in the reaction will give positive effect of the methanol production. We have tested

the methanol production from synthesis gas using the same instrumental setting and it

show better selectivity of methanol. In the plasma surface catalyst reaction, the CO will

easily react with attached H2.

CO(surf) + 2 H2(surf)  CH3OH (18)

Although using Ni/Al2O3 catalyst the methanol production increased 20% higher than

that when the reaction was conducted without Ni catalyst, the reactions suffer from the

side reaction that consumes H2 to produce water.

O(surf) + H2(surf)  H2O (19)

The surface of the catalyst got wet after the plasma reaction and the production of water

was higher compared to other catalysts. Regardless the side reaction of water

production, the combination between Ni and YSZ shows a good synergy of solid

material catalyst to increase the selectivity of methane conversion to methanol.

4. Conclusions

The yttria-stabilized zirconia is a promising support candidate for preparing the catalyst

for plasma methane conversion. The YSZs catalysts displayed higher activity and better

performance to produce methanol than that of Al2O3, ZSM 13x, SiO2, TiO2, and C-

supported catalysts. On catalytic reaction of plasma methane oxidation, the addition of

1% Pt on the catalysts produced a transformation reaction of CO into CO2. The optimal

amount of methanol production was around 23% occurred when 3% nickel metal was

12
doped on the YSZ powder.

Acknowledgements

This study was supported by the National Research Laboratory Program of the Korea

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

and Technology for supports.

13
References

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platinum catalysts (Pt/YSZs) for CH4/CO2 reforming. Applied Catal. A: General 217: 23.
Cormier, J. M., and Rusu, I. 2001. Syngas Production via methane steam reforming with
oxygen: plasma reactors versus chemical reactors. J. Phys. D: Appl. Phys. 34: 2798.
Ekerdt, J. G.. 1988. Study of Synthesis gas over metal oxides. Progress Report. DE88014731.
Hou, K. H. and Hughes, R. 2001. The kinetics of methane steam reforming over a Ni/α-Al 2O3
catalyst. Chem. Eng. J. 82 (1-3): 311-328.
Indarto, A., Choi, J. W., Lee, H., and Song, H. K. 2005. Kinetic modeling of plasma methane
conversion using gliding arc. J. Nat. Gas Chem. 14:13.
Indarto A, Choi, J. W., Lee, H., and Song, H. K. 2006a. Methane conversion using dielectric
barrier discharge: comparison with thermal process and catalyst effects. J. Nat. Gas
Chem. 15(2): 87-92.
Indarto, A., Choi, J. W., Lee, H., and Song, H. K. 2006b. Effect of additive gases on methane
conversion using gliding arc discharge. Energy 31: 2650-2659.
Indarto, A., Choi, J. W., Lee, H., and Song, H.K. 2006c. Partial Oxidation of Methane into
methanol using a dielectric barrier discharge. Proc. of 2006 Spring Korean Chem. Eng.
Symposium. Daegu.
Khaliq, A. and Foger, K. 2000. Kinetics of internal steam reforming of methane on Ni/YSZ-
based anodes for solid oxide fuel cells. Catal. Today 63: 479-487.
Lia, X. S., Zhua, A. M., and Wanga, K. J. 2004. Methane conversion to C2 hydrocarbons and
hydrogen in atmospheric non-thermal plasmas generated by different electric discharge
techniques. Catal. Today 98: 617.
Liu, C. J., Mallinson, R., and Lobban, L. 1998. Nonoxidative methane conversion to acetylene
over zeolite in a low temperature plasma. J. Catal. 179: 326.
Nozaki, T., Hattori, A., and Okazaki, K. 2004. Partial oxidation of methane using a microscale
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Song, H. K., Choi, J. W., Yue, S. H., Lee, H., and Na, B. K. 2004a. Synthesis Gas Production via
Dielectric Barrier Discharge over Ni/Al2O3 Catalyst. Cat. Today 89: 27-33.
Song, H. K., Lee, H., Choi, J. W., and Na, B. K. 2004b. Effect of electrical pulse forms on the
CO2 reforming of CH4 using atmospheric barrier discharge. Plasma Chem. Plasma

14
 Process, 24(1): 57.
Thanyachotpaiboon, K., Chavadej, S., and Caldwell, T. A. 2004. Reactors, kinetics, and
catalysis conversion of methane to higher hydrocarbons in AC nonequilibrium plasmas.
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Zhou, L. M., Xue, B., and Kogelschatz, U. 1998. Partial oxidation of methane to methanol with
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15
 CH4
MFC

He AC power
MFC supply

O2
MFC

blow heater
Plasma
Reactor
GC
heating tape

Figure 1. Experimental setup

16
 70
20 ml/min
60

50
30 ml/min
Conversion (%)

40

30
40 ml/min
20

10

0
45 50 55 60 65 70 75 80 85
Power (W)

(a)
80 20 ml/min CH4: O 2 3:1 4:1 5:1
Selectivity (%)

60

40

20

0
H2 CO C2 CO2 C3 C4 CH3OH

80 30 ml/min CH4: O2 3:1 4:1 5 :1 9:1

Selectivity (%)

60

40

20

0
H2 CO C2 CO2 C3 C4 CH3OH
(b)

Figure 2. The variation effect of flowrates and supplied powers on (a) methane conversion and
(b) products distribution.

17
18
 time conversion selectivity (%)
(mins) CH4 (%) H2 CO CO2 C2 C3 C4 CH3OH
15 28.5 33.8 47.7 22.9 9.4 3.4 0.0 10.3
75 28.9 32.9 45.7 23.7 9.9 2.9 0.0 10.0
135 28.8 32.6 48.6 22.6 9.6 3.7 0.0 10.2

Table 1. The stability of plasma process on products distribution. Data was obtained at flow rate of 30 ml/min, CH4 to O2 ratio of 4:1, and
supplied power of 80W.

catalyst conversion selectivity (%)

CH4 (%) H2 CO CO2 C2 C3 C4 CH3OH
blank 27.9 34.3 46.9 22.1 9.6 4.5 1.8 10.8
C 33.9 42.0 36.8 26.4 13.9 3.8 0.0 8.5
1% Pt/ C 30.2 47.7 31.5 30.3 17.8 0.0 0.0 8.2
Al2O3 30.1 38.9 40.0 25.2 9.2 0.0 0.0 11.8
1% Pt/ Al2O3 33.1 40.5 38.7 38.3 9.0 0.0 0.0 17.0
TiO2 34.8 43.9 39.2 18.0 14.2 3.5 0.0 7.7
1% Pt/ TiO2 32.6 42.0 33.6 29.3 17.9 0.0 0.0 14.9
ZSM 13x 27.5 47.5 41.2 27.0 15.8 0.0 0.0 8.6
1% Pt/ ZSM 13x 33.3 42.5 35.4 37.5 15.4 0.9 0.0 10.7
SiO2 33.2 46.0 41.6 19.5 15.5 0.0 0.0 9.3
YSZ 35.3 20.1 46.8 12.0 15.6 0.0 0.0 19.0
1% Pt/ YSZ 34.6 25.4 40.6 19.5 13.5 0.0 0.0 18.8

Table 2. Catalyst material comparison on plasma methane conversion using dielectric barrier discharge. All data was obtained at flow rate of 30
ml/min, CH4 to O2 ratio of 4:1, and supplied power of 80W.

19
 catalyst conversion selectivity (%)
CH4 (%) H2 CO CO2 C2 C3 C4 CH3OH
blank 27.9 34.3 46.9 22.1 9.6 4.5 1.8 10.8
YSZ 35.3 20.1 46.8 12.0 15.6 0.0 0.0 19.0
1% Pt/ YSZ 34.6 25.4 40.6 19.5 13.5 0.0 0.0 18.8
3% Ni/ Al2O3 36.0 38.9 48.0 15.7 7.5 2.2 0.0 13.2
1
3% Ni/ YSZ 30.8 23.7 44.4 12.1 9.5 0.0 0.0 21.4
2
3% Ni/ YSZ 35.3 20.1 46.8 12.0 15.6 0.0 0.0 23.6

Note: 1Prepared by incipient wetness method, 2prepared by co precipitation method

Table 3. Metal loading effects on the performance of yttria-stabilized zirconia catalyst

20
21