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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,*

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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

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Abstract- The hydrogen fuel cell is a promising option for future energy resource, but

the nature of the gas is such that the conversion of other fuels to hydrogen on board

process is necessary. Among other raw fuel resources, methane could be the best

candidate as the amounts are numerous. In this experiment, the possibility to produce

hydrogen with less carbon formation from methane by a dielectric barrier discharge

(DBD) was investigated. Without the addition of catalyst, the formation of hydrogen

reached between 30% and 35% at methane residence time of 0.22 min and supplied

powers at range of 60W to 130W. The hydrogen selectivity increased at higher

supplied power but the process efficiency, defined as a ratio of the produce hydrogen

to the supplied power, 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 that the production of hydrogen was ca. 40% higher than non

catalytic plasma process.

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

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1. Introduction

The development of fuel-efficient engines that produces less pollutant has been a

major objective for many years. Regulatory requirements have been and will be a

major importance in defining the standards (Cooper, 1994). Increasingly stringent

legislation directs the attention at factors to reduce the pollution emissions, such as

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 material. Compared to hydrogen-based process, the kinetic of

methanol conversion was relatively slower and catalyst deactivation occurred

simultaneously. As the result, hydrogen is preferred (Cameron, 1999; Ralph and

Hards, 1998; Hoogers and Thompsett, 1999), but this situation turns to the present

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 many experts to think about. Although methanol has more

advantages than methane, e.g. in the case of easier storage and safety, the side

production of carbon monoxide was 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 popular and widely used especially in the transportation sector.

In order to produce hydrogen from methane, methane cracking process is necessary.

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However, conventional thermal method requires 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 this method.

As high hydrogen production is the goal of the process, the process modification, e.g.

by addition of catalyst, is necessary to change the nature of the product distribution. In

thermal-based process, the catalytic conversion of methane to hydrogen is usually

carried out by the catalyst of Ni or Pt (Peña et al., 1996; Twigg, 1989; Rostrup Nilsen,

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 catalyst were obtained in catalytic thermal process (Rostrup-

Nilsen and Hanses, 1993). That result was supported by our investigation that Ru and

Rh were also active metal catalyst 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 rarely used in the industry.

Bridger et al. (1970) has developed relatively cheaper mixture catalyst based on Zn

and Cr oxide metal for hydrogen production. Using mixture of CH4 and CO2 as the

reactants, the production of hydrogen yielded 35% at relatively low temperature (ca.

100oC). Davis et al. (1976) has investigated thoroughly on the activity of Zn catalyst

for H2 production. Recent experiment by Liu et at. (2004) showed that the existence of

ZnO-based catalyst has increased the production of hydrogen from methanol. The

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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 method.

In this research, the direct methane conversion to hydrogen was investigated using a

dielectric barrier discharge (DBD). DBD is widely used plasma technique for many

applications because it was easy-installation and cheap-cost operation instrument. In

concordance with 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 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 inside diameter of 6 mm and length of 20 cm. A thin silver film,

works as outer electrode, was coated on the outer 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 (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

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voltages and currents. The measurement of applied power was done by a watt-meter

(Metex, model M-3860M).

All experiments were carried out in 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 two detectors (thermal conductivity and

flame ionized detector). Considering the volume expansion and/or compression of the

product stream, the flow difference between input and output line was measured by a

bubble flow meter (Hewlett Packard) refers 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 calculated in each experiment to

know the quantitative satisfaction detection of products by our analysis instruments.

In order to increase the production of hydrogen, 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. Detail

procedure of 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 then calcined at 300oC for

2h 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

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single ZnC2O4 or Cr2O3 for the transformation of synthesis 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 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

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 published with different 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

reaction to determine the kinetic, the tendency to follow a certain pattern could be

studied (Indarto et al., 2007a). The pathway pattern can easily change at 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 condition for the best result.

Figure 3

Supplied power from electrical generator to the reactor is one of the most important

parameter 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 increase of power could produce more

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energy to activate molecules to the higher energy levels and results more energetic

electrons. In this condition, 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 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 affect 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 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 supplied power of

90 W or at 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. Previous paper by Kim et al. (2004)

reported the similar situations when methane was treated by a 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

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previous parameter, the effect of residence time gives more clear result in term of

product distribution. Methane conversion was significantly increased with increasing

residence time as shown in Fig. 4a. Longer period of methane inside the reactor will

create more chances for methane molecules to collide with other energetic species,

e.g. electron or radical.

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 H atom in their molecules. Our previous research on gliding

arc plasma also produced the similar results (Indarto et al., 2005; 2006b). At longer

residence time, produced higher hydrocarbon (CxHy) from adduct reactions will be

easily decomposed in the present of single atom hydrogen and transform to the other

molecules (CxHy-1) and hydrogen molecule (H2) by dehydrogenation reaction. Ab-

initio1 calculation of Gibbs energy different (ΔGT=298K) shows the products of

dehydrogenation reactions are more stable than the reactants means that H 2 production

is more preferable. Fig. 5 shows the Gibbs energy diagram of dehydrogenation

reactions sequence occurred in C2 hydrocarbons. Although at longer residence times

the selectivity of hydrogen reaches the highest, the power efficiency to H2 production

(calculated as ratio of H2 production to the total supplied power) was decreasing. In

this condition, the process could be said not very efficient and rather costly to be

applied.

The maximum selectivity of C2 and C3 hydrocarbons were 35% and 20% respectively,

both occurred at the residence time of 0.22 min. At similar condition, the production

of C4 was also reached maximum ~15% of the total selectivity. At very short

residence time, it showed that the probability of higher hydrocarbons formation was

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).

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greater and the dehydrogenation reactions could be avoided. Eliasson et al. (2000)

reported that methane chain reaction could be occurred following:

•CH3 + •CH3 → C2H6 (3)

C2H6 + e → •C2H5 + •H + e (4)

•C2H5 + •C2H5 → C4H10 (5)

As all above reactions have almost zero reaction energy barriers (~0 kcal/mol), longer

residence time is not necessary to form higher hydrocarbons. Moreover, the longer

higher hydrocarbons stays in the plasma zone, the probability to be attacked by

hydrogen or electron is getting higher.

3.2. Plasma with oxide of Zn and Cr catalyst

Figure 6

The use of catalyst is necessary in order to control the chemical reactions of plasma

and increase the products yield. Some papers 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 the perspective of reasonable price and good

availability. In this experiment, catalyst based on Zn and Cr oxide will be used

combined with plasma to convert methane and produce H2 as the product. Low

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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

(Indarto et al., 2007b). In this case, increasing the supplied power to increase the

density of active species could be a way to activate 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 of 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 point of hydrogen production was occurred at

flow rate of 30 ml/min and power of 80 Watt.

Before the catalyst was used, we treated 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 mins

operation, all catalysts were taken out from the reactor and dried for one night long to

remove the possible moisture (probably liquid hydrocarbons) attached on the surface

of the catalyst. The dried catalysts were then re-used for the similar experiment. It was

noted as 1b for the catalyst comes from 1a and 3b for the dried catalyst from 3a.

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However, a haft portion of the dried catalyst from 1b was reactivated by calcination at

300oC for 2 h, noted as 2a. After 2a was used in the experiment for around 2 and 40

mins, the catalyst was then dried for one night long and used again for the similar

plasma reaction, 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

whether it is re-useable or not.

As shown in Fig. 6a-b, the existence of the catalyst, especially the calcined catalyst,

increased the conversion of methane. The methane conversion of catalytic plasma

process was higher ~50% than non-catalytic plasma process at the beginning of the

operation but decreased slightly as the operation time increased (1a). We found that

the catalyst was losing its activity after around 8h operation. After that time, the H 2

selectivity and methane conversion were similar to non catalytic plasma process.

From Fig. 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 non-catalytic

plasma process but it could slightly recover the activity to the H2 selectivity. It means

that the moisture or liquids which possibly existed on the surface was not affecting the

catalyst activity or the moisture or liquid did 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 by the different trend of 1a (catalyst

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with calcinations) and 3a (catalyst without calcinations). The activity of uncalcined

catalyst showed very low compared to the calcined catalyst and it 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

catalyst has increased the H2 selectivity ~40% at the first time operation of the

catalyst. Different from the catalyst activity to 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

operation of the b catalyst (both 1b and 2b), the production of H 2 was slightly lower

than a catalyst (i.e. 1a and 2a) and decreasing rapidly after 2h operation. The

interesting point, similar to the case of methane conversion, is the catalyst activity can

be regenerated by calcination.

It concludes that the catalytic plasma process is more efficient compare to non-

catalytic process for H2 production as catalytic plasma process produce higher H2

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 easily deactivation by coke deposition. In 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

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selectivity. It is proposed that the existence of 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 still ambiguous, the existence of Cr on

the surface of catalyst was able to affect the kinetic of H2 reaction (Kato et al., 2006).

This found also mentioned that Cr could adsorb more hydrogen atom than Co and Ni

and possibly performed H2 formation on the surface of the catalyst. Higher distributed

Cr, acted 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

reaction resulted hydrogen with selectivity of ca. 30-35%. The selectivity of hydrogen

increased with increasing supplied power to the reactor. The addition of calcined

mixed Zn-Cr oxide catalyst increased the hydrogen production, 40% higher than non

catalytic reaction. The existence of catalyst also increased the methane conversion but

the conversion decreased slightly at longer operation time. However, the carbon

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

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the Korea University (KU) for the financial of the study. The first author also would

like to express his appreciation to the Università degli studi di Torino for the support

during study period in Turin, Italy.

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