Beruflich Dokumente
Kultur Dokumente
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
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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
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.
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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 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
is economically interesting, but also very difficult to achieve as a result of the high
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
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
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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
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
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
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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-
(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
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
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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
(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
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.
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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
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
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.
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
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
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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
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.,
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.
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.
Table 2
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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
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
From table 2, it shows that the addition of Pt increases the selectivity of CO2 and
remaining products, e.g. C2. It concludes that oxidation of CO to CO2 was occurred and
CO CO(surf) (6)
O O(surf) (7)
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CO(surf) + O(surf) CO2(surf) (8)
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
Insertion reaction of single atom oxygen to methane was rarely occurred because
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
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.
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YSZ has oxygen vacancy sites which are able to adsorb O- to the surface of the catalyst,
O2 + e O2- (14)
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
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
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
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
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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
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
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
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-
amount of methanol production was around 23% occurred when 3% nickel metal was
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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
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CH4
MFC
He AC power
MFC supply
O2
MFC
blow heater
Plasma
Reactor
GC
heating tape
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
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.
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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.
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.
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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
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