Hydrogen production from methane in a dielectric barrier discharge

using oxide zinc and chromium as catalyst

Shortened title: H2 production from CH4 in a DBD with Zn-Cr oxide catalyst

Antonius Indarto1,*

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

PO Box 131, Cheongryang, Seoul, Korea

1
Address: Plasma-Catalyst Process Laboratory, Korea Institute of Science & Technology,
P.O. Box 131, Cheongryang, Seoul 130-650, Korea
Phone: +82-10-2296-3748
Email: indarto_antonius@yahoo.com

2
Abstract- The hydrogen fuel cell is a promising option for as a future energy
resource,; but however, the nature of the gas is such that the conversion process of
other fuels to hydrogen on board process is necessary. Among other the raw fuel
resources, methane could be the best candidate as the amounts are numerousit is
plentiful. In this experiment, the possibility to of produce producing hydrogen with
less carbon formation from methane by a dielectric barrier discharge (DBD) was
investigated. Without the addition of a catalyst, the formation of hydrogen reached
between 30% and 35% at methane residence time of 0.22 min and supplied powers at
in the range of 60W to 130W. The hydrogen selectivity increased at higher supplied
power, but the process efficiency, defined as a ratio of the produced hydrogen to the
supplied power, decreased slightly decreased. In order to boost the hydrogen
production with less carbon formation, a mixed oxide catalyst of zinc and chromium
was added to the reactor. It showed was shown that the production of hydrogen was
ca. 40% higher than the non catalytic plasma process.

Keywords: Plasma, dielectric barrier discharge, methane, hydrogen production

3
1. Introduction
The development of fuel-efficient engines that produces less fewer pollutants
has been a major objective for many years. Regulatory requirements have been and
will be a of major importance in defining the standards (Cooper, 1994). Increasingly
stringent legislation directs the attention at factors to that reduce the pollutioning
emissions, such as a cold-start process and lowering sulfur levels in fuel (Matsumoto,
2000). Among many selective compound candidates, hydrogen and methanol have
been considered as green fuels starting materials. Compared to a hydrogen-based
process, the kinetics of methanol conversion was was relatively slower and catalyst
deactivation occurred simultaneously. As the a result, hydrogen is preferred
(Cameron, 1999; Ralph and Hards, 1998; Hoogers and Thompsett, 1999), but this
situation turns to the presentpresents obvious problems with generation, storage, and
distribution of the gas. Pressurized vessels or metal hydrides of hydrogen in a vehicle
are relatively dangerous because hydrogen is categorized as a highly and flammable
material.
Currently, the attention has been focused on the design and operation of
compact and efficient devices designed to generate hydrogen on board a vehicle.
Jamal and Wyszynski (1994) reviewed many possible onboard hydrogen generators
and the alternative fuels for spark ignition engines. Hydrogen production from
methane (CH4) and methanol has attracted the consideration of many experts to think
about. Although methanol has more advantages than methane, e.g. in the case of
easier storage and safety, the side productionalong with the by-product of carbon
monoxide was being annoying for both environmental and human health (Velu et al.,
1999; Liu et al., 2004). On the other hand, nowadays, methane for fuel is getting
populargaining popularity and widely usedwidespread use, especially in the
transportation sector.
In order to produce hydrogen from methane, a methane cracking process is
necessary. However, the conventional thermal method requires a high temperature
condition to achieve high methane conversion (Indarto et al., 2006a) and can be very
costly for the onboard process. In particular, decomposition of methane using plasma
could be a candidate for this purpose as the existence of high-energy electrons were
able to decompose methane conversion at lower temperature. Yao et al. (2001)
investigated the methane conversion using non-thermal plasma and showed that the
methane conversion could be dramatically improved by through this method.
As high hydrogen production is the goal of the process, the process
modification, e.g. by the addition of a catalyst, is necessary to change the nature of the
product distribution. In thermal-based processes, the catalytic conversion of methane
to hydrogen is usually carried out by the catalyst of Ni or Pt (Peña et al., 1996; Twigg,

4
1989; Rostrup -Nielsen, 1984). Our previous research using Pt/γ-Al2O3 catalyst to
convert CH4 in a DBD showed a negative effect on the production of hydrogen, as
higher hydrocarbons transformation was the more dominant phenomena (Kim et al.,
2004). Better results by employing Ru and Rh catalysts were obtained in a catalytic
thermal process (Rostrup-Nielsen and Hanses, 1993). That result was supported by
our investigation that Ru and Rh were also active metal catalysts for converting
methane to hydrogen in a non-thermal plasma (Indarto et. al., 2007), but, as the price
in the market is relatively expensive, this material was has been rarely used in the
industry.
Bridger et al. (1970) has developed a relatively cheaper mixture catalyst
based on Zn and Cr oxide metal for hydrogen production. Using a mixture of CH4 and
CO2 as the reactants, the production of hydrogen yielded 35% at a relatively low
temperature (ca. 100oC). Davis et al. (1976) thoroughly has investigated thoroughly
on the activity of Zn catalyst for H2 production. Recent experiments by Liu et atl.
(2004) showed that the existence of ZnO-based catalyst has increased the production
of hydrogen from methanol. The activity of ZnO-Cr2O3 catalyst at low temperature
condition has been investigated by Ohta et al. (2004) for the dehydrogenation of
isobutane. However, no- publication was found for the use of mixed oxide of Zn-Cr
catalyst for methane conversion to produce hydrogen both by thermal and plasma
methods.
In this research, the direct methane conversion to hydrogen was investigated
using a dielectric barrier discharge (DBD). DBD is a widely used plasma technique
for many applications because it is was an easy-installationeasily installed and
cheaplow-cost of operation instrument. In concordance accordance with the above
discussion, a catalyst -based on Zn and Cr oxide metal was made and employed in
order to boost the production of hydrogen. In order to increase the lifetime of the
catalyst, the research would like to suppress the production of carbon. The deposition
of carbon by covering the surface of catalyst is a major reason of the catalyst
deactivation (Venugopal et al., 2007).

2. Experimental setup

Figure 1

The schematic diagram of the experimental setup is shown in Fig. 1. The

reactor was a quartz tube with an inside diameter of 6 mm and length of 20 cm. A thin
silver film, works asserving as the outer electrode, was coated on the outer wall of the
reactor wall. The inner electrode was two stainless- wires (∅ = 0.2 mm) located in the
center of the reactor. The plasma was generated by a high-voltage alternating current

5
(AC) generator (Auto electric, model A1831) that has maximum voltage of 10.0 kV
and maximum frequency of 20 kHz. In this experiment, the power frequency was
maintained fixed at 20 kHz, while the output supplied power to the reactor was
manipulated by varying the voltages and currents. The measurement of applied power
was done by a watt-meter (Metex, model M-3860M).
All experiments were carried out in under atmospheric pressure and ambient
temperature. The flow rates of methane gas were controlled by a mass flow controller.
The output of the reactor was connected to a gas chromatograph (YoungLin model
M600D, column: 30 ft of Hayesep D) equipped by with two detectors (thermal
conductivity and flame ionized detector). Considering the volume expansion and/or
compression of the product stream, the flow difference between the input and output
line was measured by a bubble flow meter (Hewlett Packard) refers referring to the
condition before and after plasma reaction. The formulation of methane conversion
and product selectivity follows:
moles of CH 4 converted
Conversion of CH 4 = × 100 (1)
moles of initial CH 4
n moles of C m H n produced
Selectivity of C m H n = × × 100 (2)
2 moles of CH 4 converted
The atom balance of carbon and hydrogen were was calculated in each experiment to
know gain the quantitative satisfaction detection of products by our analysis
instruments.
In order to increase the production of hydrogen, a mixed oxide catalyst of
zinc (Zn) and chromium (Cr) was added on the plasma system. The catalyst was made
by liquid mixing of Zn(NO3)2.6H2O and Cr(NO3)3.9H2O precursor with distillated
water. The Ddetailed procedure of the catalyst preparation was described clearly in
the patent paper of Bridger et al. (1970). Before it was used, the dried gel catalyst was
crushed and sieved until it reached uniform size of ca. 60-90 mesh. The fresh catalyst
was then calcined at 300oC for 2hr in atmospheric air. The XRD spectrum of the
catalyst after the calcinations is presented in Fig. 2, which shows the dominant ZnO
and ZnCr2O4 crystal phase. Simard et al. (1995) mentioned that those two phases were
more active compared to single ZnC2O4 or Cr2O3 for the transformation of synthesis
synthetic gas. Those crystal phases could be active for the case of H2 production from
methane. Only 0.5 gram of catalyst was added in the reactor and put at the ~1.5-2 cm
before the end of the plasma zone in order to avoid the products’s decomposition by
plasma. In this experiment, the catalyst treatments, e.g. calcinations and regeneration,
were used as the variable to investigate the activity of the catalyst and its durability.

3. Results and discussion

6
3.1. Non-catalytic plasma reaction
The conversion of methane using non-thermal plasma devices, especially
dielectric barrier discharge (DBD), has been commonly used. Numerous reports and
papers were have been published with different differing results and conclusions as
many aspects and variables were existed in a DBD (Yao et al., 2001; Yang, 2003; Kim
et al., 2004; Indarto et al., 2005; 2006a; 2006b). Although plasma reaction is known
as one of the most difficult reactions to determine the kinetics, the tendency to follow
a certain pattern could be studied (Indarto et al., 2007a). The pathway pattern can
easily change at under different conditions as the reactions are very sensitive to the
population of active species, ions, and electrons. This is the reason why the
optimization of the parameters is necessary to obtain the optimum conditions for the
best results.
Figure 3

Supplied power from an electrical generator to the reactor is one of the most
important parameters in the plasma chemical reaction to activate or decompose the
methane molecule. The magnitude of the external supplied power is related to the
intensity of the internal electric field inside the reactor. The An increase of power
could produce more energy to activate molecules to the higher energy levels and
results in more energetic electrons. In this condition, the possibility of breaking the C-
H bond in the molecule of methane could be initiated. Figure 3 shows the effect of
supplied powers variation on the methane conversion and products selectivity at the
fixed input flow rate of 15 ml/min or residence time of 0.6 min. Methane conversion
was raising raised from 30% to 45% when the power was increased from 60 W to 130
W. It can be deduced, trivially, that supplying more energy will increase the
molecules’ instability inside the reactor and affectcause to the more conversion of
methane. Increasing energy will also increase the density of electron and radical
species inside the plasma zone.
The gaseous products of non-catalytic plasma of methane conversion were
dominated by H2, C2 (mostly C2H6), C3, and small amount of C4H10. Liquid product
was not detected in all ranges of experiment, and a small amount of solid carbon was
found deposited on the reactor wall and the surface of inner electrodes. The
production of hydrogen was relatively stable in the range between 30% and 35%.
Figure 3b shows that the maximum production of C3 hydrocarbons was occurred at a
supplied power of 90 W or at the minimum C4 hydrocarbons production. On the other
hand, production of C4 reached the highest value at higher supplied power (130 W)
and suppressed the production of C3. Similar to the trend of H2, the production of C2
compounds was not affected much by supplied powers variation. A Pprevious paper
by Kim et al. (2004) reported the similar situations when methane was treated by a

7
DBD.

Figure 4

The effect of the residence time of methane in the reactor was also examined.
Figure 4 shows the results on methane conversion (Fig. 4a) and the selectivity of
products (Fig. 4b) vs. residence time variation at a fixed supplied power of 80W.
Different from the previous parameter, the effect of residence time gives more clear
results in terms of product distribution. Methane conversion was significantly
increased with increasing an increase in residence time, as shown in Fig. 4a. Longer
periods of methane inside the reactor will create more chances opportunities for
methane molecules to collide with other energetic species, e.g. electrons or radicals.
Figure 4b shows that the production of H2 was clearly increased when the
residence time was increased. As the production of H2 increased, it reduced the
selectivity of other products contained containing an H atom in their molecules. Our
previous research on gliding arc plasma also produced the similar results (Indarto et
al., 2005; 2006b). At a longer residence time, produced higher hydrocarbon (CxHy)
from adduct reactions will be easily decomposed in the present presence of a single
atom of hydrogen and transform to theinto hydrogen molecules (H2) other molecules
(CxHy-1) and other molecules (CxHy-1) hydrogen molecule (H2) by a dehydrogenation
reaction. Ab-initio1 calculation of Gibbs energy different (ΔGT=298K) shows the
products of dehydrogenation reactions are more stable than the reactants, which
means that H2 production is more preferable. Fig.ure 5 shows the Gibbs energy
diagram of dehydrogenation reactions sequence occurred occurring in C2
hydrocarbons. Although, at longer residence times, the selectivity of hydrogen
reaches the highest value, the power efficiency to H2 production (calculated as ratio of
H2 production to the total supplied power) decreasedwas decreasing. In this condition,
the process could be said to be not very efficient and rather costly to be appliedy.
The maximum selectivity of C2 and C3 hydrocarbons were was 35% and 20%
respectively, both occurred occurring at the a residence time of 0.22 min. At Under
similar conditions, the production of C4 was also reached maximum ~15% of the total
selectivity. At a very short residence time, it showed that the probability of higher
hydrocarbons formation was greater and that the dehydrogenation reactions could be
avoided. Eliasson et al. (2000) reported that methane chain reaction could be
occurredoccur following:
•CH3 + •CH3 → C2H6 (3)
C2H6 + e → •C2H5 + •H + e (4)
•C2H5 + •C2H5 → C4H10 (5)
1 Ab-inito calculation was done by using Gaussian 03 software (Frisch et al., 2004) with DFT
(UB3LYP) method and basis set of 6-31G(d).

8
As all of the above reactions have almost zero reaction energy barriers (~0 kcal/mol),
a longer residence time is not necessary to form higher hydrocarbons. Moreover, the
longer the higher hydrocarbons stays in the plasma zone, the greater the probability to
beof being attacked by hydrogen or electrons is getting higher.

3.2. Plasma with oxide of Zn and Cr catalyst

Figure 6
The use of a catalyst is necessary in order to control the chemical reactions of
plasma and increase the products yield. Some papers have reported some results
related to the use of catalysts (usually metal oxide catalyst) for hydrogen production.
Most authors preferred Pt, Ru, and Rh catalysts, owing to their good activity and
stability. Meanwhile, Ni-based catalysts are commercially more interesting but suffer
the disadvantage of a high rate of deactivation. Moreover, exploration to find the best
catalyst is still challenging, especially in as far as the perspective of reasonable price
and good availability. In this experiment, a catalyst based on Zn and Cr oxide will be
used combined with plasma to convert methane and produce H2 as the product. Low
production of carbon is also necessary to prevent the catalyst from fast deactivation.
In order to find the best region in where the catalyst was able to show the
activity significantly, we did a set of ‘screening’ experiments. As the reaction
temperature was relatively low (ca. room temperature), some catalysts did not show
any activities activity (Indarto et al., 2007b). In this case, increasing the supplied
power to increase the density of active species could be a way to of activateing the
surface property of the catalyst.
At relatively low supplied powers or higher input flow rates, the product
distribution was not much different compared to the one ofdistribution from the non-
catalytic plasma process. The existence of radicals and/or ions from methane
fragmentation was low due to the low conversion of methane. The optimum optimal
point of hydrogen production was occurred at a flow rate of 30 ml/min and power of
80 Watt.
Before the catalyst was used, we treated it with two different activation
methods. The first catalyst was calcined at 300oC using atmospheric air for 2 h, noted
as 1a, and the second one was not calcined, noted as 3a. After around 2 hours and 40
minutes operation, all catalysts were taken out from of the reactor and dried for one
night long to remove the any possible moisture (probably liquid hydrocarbons)
attached on to the surface of the catalyst. The dried catalysts were then re-used for the
similar experiment. It wasThey were noted as 1b (for the catalyst comes coming from
1a) and 3b (for the dried catalyst coming from 3a). However, a haft half portion of the
dried catalyst from 1b was reactivated by calcination at 300oC for 2 h, noted as 2a.

9
After 2a was used in the experiment for around 2 hr and 40 mins, the catalyst was
then dried for one night long and used again for the similar plasma reaction, and noted
as 2b. This method is proposed to know the effect of the calcinations to the catalyst
activity and to investigate the durability of the catalyst, i.e. whether whether or not it
is re-useable or not.
As shown in Fig.ures 6a-b, the existence of the catalyst, especially the
calcined catalyst, increased the conversion of methane. The methane conversion of the
catalytic plasma process was higher ~50% than non-catalytic plasma process at the
beginning of the operation but decreased slightly as the operation operating time
increased (1a). We found that the catalyst was began losing its activity after around
8hr of operation. After that time, the H2 selectivity and methane conversion were
similar to the non -catalytic plasma process. From Fig.ure 6a, it shows that the activity
the catalyst could not be regenerated by only by drying the catalyst, as the conversion
of methane was similar to the non-catalytic plasma process but it could slightly
recover the activity to theof H2 selectivity. It This means that the moisture or liquids
which possibly existed on the surface was were not affecting the catalyst activity or
that the moisture or liquid did was not present during the process. However, the
catalytic activity significantly reappeared when the used catalyst was recalcined. The
activity of 2a catalyst was nearly similar to the activity of the 1a catalyst for both
methane conversion and H2 selectivity. It is good news that the catalyst can be re-used
with almost similar activity by re-calcination. It is necessary to calcine the catalyst to
oxidize the adsorbed carbon by oxygen. Moreover, in another point of view, the
calcination could be an important factor, shows as shown by the different trend of 1a
(catalyst with calcinations) and 3a (catalyst without calcinations). The activity of
uncalcined catalyst showed was shown to be very low as compared to the calcined
catalyst, and it this could refer to the crystal phases present in the catalyst. The effect
of re-calcination on the activity of converting methane is still being studied further by
analyzing the XRD, TEM, and SEM picture.
The above phenomenon was also occurred for the H2 selectivity. The addition
of the catalyst has increased the H2 selectivity ~40% at for the first time operation of
the catalyst. Different from the catalyst activity to in the methane conversion, the
selectivity of H2 production was relatively stable both for 1a and 2a catalyst. For the
3a catalyst, the H2 selectivity was also stable but in lower values (ca. 30%). After the
first 1 hour of operation of the “b” catalyst (both 1b and 2b), the production of H2 was
slightly lower than a the “a” catalyst (i.e. 1a and 2a), and decreasing the production
decreased rapidly after 2h operation with the “b” catalyst. The interesting point,
similar to the case of methane conversion, is the catalyst activity can be regenerated
by calcination.

10
 It One can concludes that the catalytic plasma process is more efficient as
compared to the non-catalytic process for H2 production as the catalytic plasma
process produces higher H2 when compared to the non-catalytic process at similar
supplied power to the reactor. However, Ohta et al. (2004) and Venugopal et al.
(2007) mentioned the problem of the ZnO-Cr2O3 catalyst was being easily
deactivation deactivated by coke deposition. In the plasma process, nano-sized carbon
can be formed in non-thermal plasma by methane fragmentation (Indarto, 2006c).
Calcination of the catalyst using air could remove the carbon by oxidizing it with
oxygen to form CO or CO2.
Other hydrocarbon products selectivity is shown in Fig. 6c. The phenomenon
is similar to the case of residence time effect in non-catalytic experiments. When the
H2 selectivity rose, it sacrificed the other hydrocarbon products by suppressing their
selectivity. It is proposed that the existence of a catalyst will ease the H2 production
reactions, by adsorbing hydrogen produced from dehydrogenation on of hydrocarbons
(shown in Fig. 5). Although it is not clear and is still ambiguous, the existence of Cr
on the surface of catalyst was seemed able to affect the kinetics of the H2 reaction
(Kato et al., 2006). This found finding also mentioned that Cr could adsorb more
hydrogen atoms than Co and Ni and possibly performed H2 formation on the surface
of the catalyst. Higher distributed Cr, acted acting as active site, would increase the
production of H2, and ZnO could disperse the Cr during the catalyst formation
(Thomas and Thomas, 2006).

4. Conclusions

The production of hydrogen from methane by a dielectric barrier discharge

with mixed oxide catalyst of zinc and chromium was investigated. Non -catalytic
plasma reactions resulted in hydrogen with selectivity of ca. 30-35%. The selectivity
of hydrogen increased with increasing the supplied power supplied to the reactor. The
addition of calcined mixed Zn-Cr oxide catalyst increased the hydrogen production,
40% higher than the non -catalytic reaction. The existence of a catalyst also increased
the methane conversion, but the conversion decreased slightly at over a longer
operation time. However, the cCarbon deposition could be proposed as the main
reason for the catalyst deactivation, but it can be catalyst activity can be regenerated
by catalyst recalcination.

Acknowledgments
The first author thanks to the Korea Institute of Science and Technology (KIST) and
the Korea University (KU) for the financial of the study. The first author also would

11
like to express his appreciation to the Università degli studi di Torino for the support
during study period in Turin, Italy.

12
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15
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16
M e th a n e AC
M FC g e n e ra to r

p la s m a
zone
B u b b le flo w
m e te r
c a ta ly s t

R e a c to r G as
C h ro m a to g ra p h y

Figure 1. Experimental setup

17
 ZnO
Z n C r2O 4
C r2O 3

Figure 2. XRD spectra of calcined catalyst

18
 70

60

50
Conversion (%)
40

30

20

10

0
60 80 100 120 140
S u p p lie d p o w e r ( W )
(a)

1.0

0.8 unkno w n
n - C 4H 10
Selectivity

0.6 i- C 4 H 1 0
C3
0.4 C 2H 6
C 2H 2 + C 2H 2
0.2 H2

0.0
60 70 80 90 100 110 120 130
S u p p lie d p o w e r ( W )

(b)

Figure 3. Effects of supplied power variation on

(a) methane conversion and (b) products distribution

19
 100

80

Conversion (%)
60

40

20

0
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

R e s id e n c e t im e ( m in )

(a)

1 .0

0 .8
Selectivity

0 .6
unknow n
0 .4 C4
C3
0 .2
C 2
H 2

0 .0
0 .3 0 .5 0 .7 0 .9 1 .1 1 .3 1 .5 1 .7 1 .9

R e s id e n c e t im e ( m in )

(b)

Figure 4. Effects of methane residence time on

(a) methane conversion and (b) products distribution

20
 20
C 2H 6
+ H --> C 2H 5
+ H 2
0

∆G (kcal/mol) - 20
C 2H 5 + H --> C 2H 4 + H 2
- 40

- 60 C 2H 4 + H --> C 2H 3 + H 2

- 80

- 100 C 2H 3 + H --> C 2H 2 + H 2

- 120

- 140

Figure 5. The Gibbs energy different (ΔG) profile of dehydrogenation of

C2 hydrocarbons in the present of hydrogen atom

21
 60

50
H2 selectivity (%)
40

b la n k
30

1a
20 1b
2a
2b
10 3a
3b

0
20 40 60 80 100 120 140 160 180
S a m p lin g tim e ( m in .)

(a)

60

50
CH4 conversion (%)

40

30 b la n k

1a
20 1b
2a
2b
10 3a
3b

0
0 20 40 60 80 100 120 140 160 180
S a m p l in g t im e ( m in . )

(b)

22
 30

25

Selectivity (%)
20 C 2H 6

15
C 3
C 2H 2
+ C 2H 4
10

5
i- C 4 H 10
+ n -C 4H 10
0
0 20 40 60 80 100 120 140
S a m p l in g t im e ( m in . )

(c)

Figure 6. Effect of the catalyst on (a) methane conversion, (b) hydrogen selectivity,
and (c) hydrocarbons selectivity. Data was obtained at gas flow rate of 30ml/min and
supplied power of 80W.

23