Article

Synthesis of Na2WO4-Mn supported YSZ as a

potential anode catalyst for oxidative coupling of
methane in SOFC reactor
Weerinda Appamana1, Sumittra Charojrochkul2, Suttichai Assabumrungrat1,
and Wisitsree Wiyaratn3,*

1 Centre of Excellence in Catalysis and Catalytic Reaction Engineering, Department of Chemical

Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand
2 National Metal and Materials Technology Center (MTEC), Pathumthani 12120, Thailand
3 Faculty of Industrial Education and Technology, King Mongkut’s University of Technology Thonburi,
Bangkok, 10140, Thailand
*E-mail: [email protected]

Abstract. The oxidative coupling of methane (OCM) over a 5%Na2WO4-2%Mn on YSZ,

has been investigated in a fixed bed reactor (FBR) and a solid oxide fuel cell reactor
(SOFC). A 60% C2 selectivity and a 26% CH4 conversion have been obtained in a FBR at
800oC and CH4/O2 of 4:1. Importantly, an addition of Na2WO4-Mn to YSZ support can
significantly enhance the performance of the catalyst especially C2 hydrocarbons selectivity
and CH4 conversion. A maximum power density of 7.8 mW cm−2 was achieved at 800°C
with CH4 in the SOFC reactor having a 50 μm thick YSZ electrolyte. The CH4 conversion
and C2 selectivity at 800°C were 1.1% and 85.2%, respectively.

Keywords: C2 hydrocarbons, OCM, YSZ, Na2WO4-Mn.

ENGINEERING JOURNAL Volume 19 Issue 1

Received 11 April 2014
Accepted 22 September 2014
Published 30 January 2015
Online at http://www.engj.org/
DOI:10.4186/ej.2015.19.1.13
DOI:10.4186/ej.2015.19.1.13

1. Introduction

Oxidative coupling of methane (OCM) to C2-hydrocarbons has attracted much attention during the past
three decades as it is a potential route in utilizing methane, a major component of natural gas and a
byproduct of oil refining and chemical processing. Since the pioneering work of Keller and Bhasin [1], there
have been many research efforts on a production of C2 hydrocarbons from OCM reaction. A wide variety
of catalysts have been studied. However, the yield of C2 hydrocarbons achieved in a fixed-bed reactor
(FBR) was limited to about 25% due to the presence of undesired partial or complete oxidation in gas
phase and on catalyst surface [2–4]. To overcome this limiting problem, selective catalysts for the methane
coupling reaction and some reactors have been designed to inhibit the side reactions. A Solid Oxide Fuel
Cell (SOFC) reactor is one of the most attractive reactors. It simultaneously co-generates electricity as by
product and C2 hydrocarbons through OCM reaction. Solid oxide membranes were used to control the
necessary oxygen for the OCM process. Therefore, an SOFC reactor is potentially more interesting than
other conventional reactors due to the achievement of high selectivity and possible use of generated
electricity. Many electrochemical studies of OCM reaction over metallic catalyst-electrodes have been
reported but the yield of C2 hydrocarbons was low ( 10%). Therefore, the development of anode
catalysts for OCM in SOFC becomes an important goal to improve the conversion, selectivity and yield of
C2 hydrocarbons.
Among several catalysts, 5wt%Na2WO4-2wt%Mn/SiO2 offers a good performance in OCM with 20%
of methane conversion and 80% of C2+ selectivity [3, 5–7]]. Lunsford and co-workers [8-9] reported that
Na-O-Mn species were responsible for an activation of methane, in which Mn was an active component,
Na provided selectivity, and W was required to stabilize the catalyst.Afterwards, Lapeña-Rey et al.
investigated OCM in SOFC using YSZ as a solid electrolyte, 5wt%Na2WO4-2wt%Mn/SiO2 was used as an
anode catalyst. Very high C2 hydrocarbon selectivity was obtained while the methane conversion was low.
However, the SiO2 support had low electrical conductivity, thus it was required to be mixed with a
conductive component such as silver to increase the electrical conductivity [10]. In addition, the
performance-limiting factor in solid oxide fuel cells (SOFC) is often the electrode impedance [11–13] which
can be avoided by using low-temperature, infiltration procedures to synthesize the electrodes [14–17]. This
procedure involves a preparation of porous YSZ (dense YSZ is the electrolyte) scaffold together with the
electrolyte layer, then infiltrating the required precursor salts to form the particle within the scaffold.
Because the procedure allows a formation of a long three-phase boundary (TPB), the initial performance of
these electrodes can be good.
The main objective of this research was to investigate the new anode catalysts in SOFC. In the present
work, 5wt%Na2WO4-2wt%Mn/YSZ catalysts were examined. The catalysts were characterized by BET,
XRD and XPS. The catalytic activity of catalysts for OCM was evaluated using a continuous-flow fixed bed
reactor and a solid oxide fuel cell reactor.

2. Experimental

2.1. Catalyst Preparation and Characterization

5 wt%Na2WO4–2 wt%Mn/YSZ catalyst (denoted by Na-W–Mn/YSZ) was prepared by a two-step

incipient wetness impregnation method. In the first stage, manganese was impregnated onto YSZ support
(8 mol% Yttria-Stabilized Zirconia, TZ-8Y, Tosoh, Japan) with Mn(NO2)3.6H2O (Aldrich) dissolved in
deionized water. Then the sample was dried at 110°C overnight. In the second stage, 2% wt of Na2WO4 was
added to the support sample using Na2WO4.4H2O (Aldrich) solution. The impregnated particles were dried
again and calcined in air at 850°C for 5 h. For comparison, the 5 wt%Na2WO4–2 wt%Mn/SiO2 catalyst
(denoted by Na-W–Mn/SiO2) was prepared using the same method. Herein, SiO2 commercial (40-60 mesh,
250 m /g, Sigma Aldrich) were selected as a support.
2

The synthesized catalysts were determined by various techniques for their physical properties. Surface
area and pore size were determined using BET method. The crystalline phases of prepared samples were
identified using x-ray diffraction technique with Cu-Kα radiation. The x-ray diffractograms were recorded
in the range of 10° to 90° (2Ɵ). A scanning electron microscope (SEM) was used to study the morphology.

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 DOI:10.4186/ej.2015.19.1.13

2.2. Catalytic Activity Testing in Fixed Bed Reactor

The reaction was carried out in a tubular quartz reactor filled with 200 mg of selected sample and small
amount of quartz wool. The reactor was vertically mounted inside a furnace. Gas mixture between methane
and oxygen diluted in helium were allowed to continually flow into the reaction zone. The catalytic activity
was tested at atmospheric pressure and within a temperature range of 700-900°C in a conventional fixed-
bed micro-reactor made of quartz (i.d. 6 mm). The reactants, CH4 (99.9%) and O2 (99.9%) without any
diluents, were co-fed into the reactor with suitable CH4/O2 ratios and gas hourly space velocity (GHSV) at
STP of 15000 ml·g−1·h−1. A cold trap was used to remove water from the exit gas stream at the reactor
outlet. The products were analyzed with an on-line GC equipped with a TCD, using a Porapak Q column
and a (5A˚) molecular sieve column, every 30 min until reaching the steady state condition.

2.3. Single Cell Fabrication and Fuel Cell Performance Testing

The cell fabrication of a porous-dense-porous YSZ wafer was carried out using a tape-casting method. As
described elsewhere [18] the dense electrolyte layers were approximately 50 µm thick and 2 cm in diameter,
while the two porous layers were each 150 µm thick. After synthesizing the three-layer YSZ, La0.8Sr0.2FeO3
(LSF) was added to the cathode porous layers using aqueous nitrate solutions until the loading of LSF was
45 wt.% as described by Vohs and Gorte [18]. For the anode side, Mn-Na2WO4 was added after the final
850°C calcination used to produce the LSF. Ag paste and Ag wire were used to make electrical connections
to both electrodes. In the cell testing, both electrodes were exposed to either humidified (3% H2O) H2 or
CH4. Impedance spectra were measured at open circuit in the galvanostatic mode using a Solartron
potentiostat. Products from the anode side were analyzed with an equipped on-line GC.

3. Results and Discussion

3.1. Catalyst Characteristics

The BET surface area, volume and pore size of all catalysts prepared in this work are summarized in Table
1. After the active phase was loaded with Na2WO4 and Mn precursor, the surface areas, volume and pore
sizes of the YSZ and SiO2 decreased due to a packing effect during the drying and calcination processes.
For Na-W-Mn/SiO2 catalyst, calcinations of the amorphous silica in the presence of an alkali salt like
sodium tungstate as a mineralizing agent caused the complete conversion of the silica to the low surface
area crystalline phase [19].

Table 1. Surface area, average pore size and pore volume.

surface Total pore Mean pore
Catalysts area volume diameter
(m g )
2 -1 (cm3 g-1) (nm)
SiO2 255.0 0.878 10.5
YSZ 14.2 0.0964 26.4
Na-W-Mn/SiO2 3.50 0.0043 6.50
Na-W-Mn/YSZ 7.90 0.0405 18.5

The SEM images in Fig. 1 clearly show a congregation of many particles. The Mn distribution
determined by EDX spectroscopy (shown in Figs. 1(a-d)) also qualitatively confirm that Mn elements were
well dispersed on the YSZ and SiO2 supports. Malekzadeh et al. [19] have reported that manganese oxide
(MnOx) promoted catalyst can decrease the band gap of the catalyst. The conductivity of the catalyst
depends on the band gap of the metal oxide constituent of the catalyst. MnOx shows the high electrical
conductivity, which could improve a performance in OCM reaction.
X-ray powder diffraction (XRD) was used to identify bulk phase composition in the catalysts. The
XRD patterns of YSZ, Na-W-Mn/SiO2 and Na-W-Mn/YSZ are displayed in Figs. 2(a-c). For Na-W-
Mn/SiO2 catalyst, the main phase is Na2WO4, Mn2O3 and α-cristobalite [7]. For the XRD spectra of Na-W-

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Mn/YSZ, the formation of the Na2WO4 and Mn2O3 phase were not detected. However, Na2WO4 and
Mn2O3 phases on YSZ support were confirmed by using an X-ray photoelectron spectroscopy (XPS).

Fig. 1. SEM images and Mn elemental mappings of (a) SEM of Na-W-Mn/YSZ , (b) Mn mapping of Na-
W-Mn/YSZ (c) SEM of Na-W-Mn/SiO2, (d) Mn mapping of Na-W-Mn/ SiO2.

Fig. 2. XRD patterns of (a) Na-W-Mn/SiO2, (b) YSZ and (c) Na-W-Mn/YSZ, ( ) Na2WO4, ( ) Mn2O3.

Table 2. Surface composition (at%) of the components of fresh catalysts.

Catalysts Na(1s) W(4f) Mn(2p) O(1s) O(1s)(MOx) Y(3d) Zr(3d)

Na-W-Mn/YSZ 12.3 7.2 3.1 24.8 17.8 3.8 31

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Table 2 shows the observed elemental concentrations near the surface of the fresh catalysts by XPS
characterization. These catalysts show that the surface atomic concentrations of Na, W and Mn are close to
those of the bulk compositions, indicating that Na, W and Mn are enriched on the catalysts surface.
Moreover, two kinds of surface oxygen on the catalysts were found. Na(1s), W(4f) and Mn(2p) are clearly
present on the catalyst surface. This confirms that YSZ surface have the Na2WO4 and Mn2O3 active species
on the catalyst surface.

3.2. Catalytic Performance of Catalysts

Table 3 summarizes the catalytic performances of different catalysts after 90 min of reaction at steady state
under GHSV of 15000 ml g-1 h-1, 800°C and a molar ratio of CH4/O2 of 4:1 [6, 20]. For Na-W-Mn/SiO2
catalyst, 12.0% CO selectivity, 12.9% CO2 selectivity and 69.0% C2 selectivity at 28.5% CH4 conversion are
obtained, which are in agreement with several reports [21-24]. In a comparison among different supports,
YSZ shows greater selectivity to partial oxidation than the complete combustion, as the selectivity to CO is
much greater than that to CO2. When Na2WO4 and Mn are added on YSZ, the promoting effects on CH4
conversion from 10.6 to 26.9% and C2 selectivity from 18.9 to 60.6% are obviously observed. It is really
interesting to note that the promotion of tri- metallic oxide (Na, W, and Mn) can significantly improve the
catalytic performance of YSZ for the selective OCM reaction.

Table 3. Catalytic performance of catalystsa.

Conversion (%) Selectivity (%) Yield (%)
Catalyst
CH4 H2 CO CO2 C2H4 C2H6 C2 C2
YSZ 10.6 48.5 54.0 27.3 0 18.9 18.9 2.0
Na-W-Mn/SiO2 28.5 4.1 12.0 12.9 21.2 47.8 69.0 19.7
Na-W-Mn/YSZ 26.9 2.6 9.9 25.2 22.9 37.7 60.6 16.3
a
Reaction condition: T=1073 K; CH4/O2=4; WHSV=15000 mlg-1h-1; 0.2 g catalyst.

Fig. 3. Catalytic performance of Na-W-Mn/SiO2 and Na-W-Mn/YSZ catalysts as related to operating

temperatures at GHSV of 15000 mlg-1h-1 and CH4/O2 of 4. (a) Na-W-Mn/SiO2, (b) Na-W-
Mn/YSZ. ( ) conversion of CH4, ( ) C2 selectivity, ( ) C2 yield.

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Effect of temperature for OCM reaction over Na-W-Mn/SiO2 and Na-W-Mn/YSZ catalysts is shown
in Fig. 3. Trends of CH4 conversion over three catalysts showed a slight increase with rising operating
temperature. However, decreases in C2 selectivity and C2 hydrocarbons yield are observed in the
temperature range of 800-900°C because of kinetic limitations. The upper limit of OCM yield under the
conventional fixed bed is considered to be dominated by the enthalpies of hydrogen severance from
methane and oxygen dissociative adsorption [20]. The optimum temperature for three catalysts appears to
be at 800°C, where C2 hydrocarbon yields are 19.7% and 16.3% for Na-W-Mn/SiO2 and Na-W-Mn/YSZ,
respectively in which these results are not significantly different while higher C2 selectivity (61%) is
observed over Na-W-Mn/YSZ. Therefore, Na-W-Mn/YSZ is an attractive catalyst for use in an SOFC
reactor.

3.3. OCM in SOFC Reactor for C2H4 Hydrocarbon and Electricity Co-Generation

After being tested in a fixed bed reactor, the Na-W-Mn/YSZ was tested in an SOFC reactor to investigate
the fuel cell performance and performance to produce C2 hydrocarbons and electric current. Figure 4
shows voltage, current, and power density properties for three tape-cast SOFC cells fabricated by
impregnation of Na2WO4 and Mn2O3 with Ag current collectors. The measurements of these cells at 800°C
in wet H2 and wet CH4 are shown in Figs. 4a and 4b, respectively. For H2 fuel, their open circuit voltage
(OCV) values were 1.07 V, which were very close to the theoretical value calculated from Nernst equation.
Such high OCV values indicate that a dense structure is well-formed in the YSZ electrolyte and leakage of
the gas is negligible for each sample. As seen in Figs. 4a and 4b, the power density was 13.2 and 7.8
mW.cm-2, respectively. The power density of the specimen measured in H2 was nearly double of that
measured in CH4. From the experiments at 800°C under load of 0.3 V, the methane conversion was around
2.1% and 85.2% for C2 hydrocarbons selectivity observed with a significant C2 hydrocarbons production.

Fig. 4. Voltage current and power density versus current density plots for the cells with each of the four
anode compositions at 800°C, under (a) wet H2 and (b) wet CH4.

Conclusions

Na-W catalysts supported YSZ catalyst was synthesized, characterized and explored as anode catalyst
materials for the OCM reaction. The presence of Mn3+ and W6+ on YSZ were confirmed while they
significantly improve the catalytic activity and C2 selectivity despite of a very low surface area YSZ.
Additionally, using YSZ as a support has reduced the distance and thickness of interface layer between
anode and cathode, resulting in a good diffusion and catalytic reaction. Therefore, Na-W-Mn/YSZ is
potentially a promising anode catalyst for use in an SOFC reactor for C2 hydrocarbons production via
OCM reaction.

Acknowledgements

W.A. and S.A. would like to thank the Royal Golden Jubilee Ph.D. program (contact no. PhD 0317/2551)
from Thailand Research Fund and Chulalongkorn University, and the authors gratefully acknowledge the
Thailand Research Fund, Higher Education Commission, Chulalongkorn university and King Mongkut's

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 DOI:10.4186/ej.2015.19.1.13

University of Technology Thonburi for financial support, as well as Professor Piyasan Praserthdam and
Professor John Irvine for supporting some facilities.

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