~T~

! ELSEVIER Applied Catalysis A: General 128 (1995) 61-77

AP PLIED CATALYSIS A: GENERAL

The use of carbon catalysts and of nitrous oxide in promoting the conversion of methane
Martin Bajus a, Margaret H. Back b,.
Slovak Technical UniversiO,, Facul~ of Chemical Technology 81237 Bratislava, Slovakia b University of Ottawa Department of Chemistr 3' Ottawa, Ontario KIN 6N5, Canada

Received 16 September 1994; revised 14 February 1995; accepted 14 February 1995

Abstract
This paper reports on the coupling of methane to C 2 and higher hydrocarbons over a carbon catalyst in the absence and presence of nitrous oxide and a lithium-promoted carbon catalyst in the absence and presence of nitrous oxide. The kinetics of the methane conversion were studied in a flow system over the temperature range 700-1100C. At 850C the conversion of methane was increased by a factor of about 800 in the presence of the carbon catalyst. The selectivity to C2 hydrocarbons was, however, low and the main products were hydrogen and carbon. The Li/carbon catalyst was similarly effective and led to a better selectivity for C~ hydrocarbons. Nitrous oxide had a strong promoting effect on the homogeneous coupling of methane but a less noticeable effect in the presence of the catalysts. Nitrous oxide improved the selectivity to C2 hydrocarbons. Under the conditions of the present experiments the carbon-lithium oxide catalyst is able to facilitate the oxidative coupling of methane to give 36% conversion with selectivity to C2 hydrocarbons over 70%.
Keywords." Carbon catalyst; Methane conversion; Methane coupling; Methane pyrolysis; Nitrous oxide

1. Introduction In the search for an efficient technology for conversion of natural gas into liquid fuels and petrochemicals, catalytic processes have dominated the efforts of research workers. The oxidative coupling of methane process, using a variety of alkalialkaline earth oxides and rare earth oxides, has received the most attention and the characteristics of the reaction are now reasonably well understood [ 1-4]. Still, a serious disadvantage of this process is the relatively low selectivity because of the large proportion of methane that is converted into carbon monoxide and carbon
* Corresponding author. Tel. ( + 1-613) 562-5800-6076, fax. ( + 1-613) 5625170. 0926-860X/95/$09.50 1995 Elsevier Science B.V. All rights reserved SSDI O926-860 X ( 95 ) 0 0 0 5 0 - X

62

M. Bajus, M.H. Back~Applied Catalysis A: General 128 (1995)61-77

dioxide. The high reactivity of oxygen not only induces dissociation of methane but drives the oxidation further to carbon monoxide and carbon dioxide. It is useful therefore to explore other catalysts [5]. One such catalyst is carbon. Active carbon and carbon fibers derived from coal, either alone or doped with active metals, catalyze many industrially important chemical reactions. Carbon is thus readily available and inexpensive. Carbon catalysts are usually relatively inert compared to an active metal, but compared to a surface without metal, quartz, for example, carbon may be, under some conditions, highly reactive. Although both the accelerating effect [ 6,7 ] and the inhibiting effect [8,9] of carbon catalysts on the rate of the thermal reactions of hydrocarbons have been reported many times the mechanism of this interaction with carbon is not understood. A recent study from Japan [ 10] described the effect of carbon fibers on the reactivity of methane, where a substantial accelerating effect was observed. The purpose of the present study was first to explore the effect of activated carbon on the rate of coupling of methane, which is the first step in the conversion of natural gas into higher molecular weight products. In the absence of oxidizing agents no oxidative products will be formed and the only products will be hydrocarbons. Secondly, the effect of nitrous oxide on the coupling of methane was investigated, both in the presence and absence of the carbon catalyst. Thirdly, the effect of the incorporation of lithium as a metal oxide into the carbon catalyst was studied.

2. Experimental
2.1. Apparatus
The pyrolysis apparatus was a typical flow system. It had provision for the introduction of three reactants, a tubular quartz reactor, diameter 10 ram, maintained at constant temperature in a Lindberg three-zone furnace model #54957, a condenser, traps and a sample collector for analysis of products. The temperature in the pyrolysis oven was regulated by a control console, Lindberg model #597744A. The movable NiCr-Ni thermocouple was placed in thermotubes by the side of the reaction vessel. The flow-rates of the reactants were controlled by flow controllers, measured on rotameters, and calibrated by a soap bubble flowmeter. The reactant gases were pre-mixed before entering the reactor. Nitrogen was used as the diluent. Equimolar mixtures of methane and nitrogen were fed to the reactor with a total pressure of 101.2 kPa. Flow-rates varied from 4.7 to 255 cm 3 rain 1.

2.2. Analysis
Products were analyzed by gas chromatography a using Hewlett-Packard instrument 5710A with FID detector and 5750A with TC detector. The gaseous products

M, Bajus, M.H. Back~Applied Catalysis A: General 128 (1995) 61-77

63

from the pyrolysis of methane consisted of ethane, ethylene, propane, propene and acetylene. Separation was achieved on a column of n-octane on Porasil C, 5.5 m of 1/4 in. + 2 m of 3/8 in., maintained at 60C. An FID detector was used. The products H2, CO, CO2 and N20 were analyzed using a column of carbosieve 511, 10 ft. 1/8 in. maintained at 100C and using a thermal conductivity detector. The liquid fraction of the pyrolysis products consisted mainly of benzene and naphthalene. Analysis was done using a column of OV-17, programmed in stages from room temperature up to 280C.

2.3. Materials
Instrument grade methane (99.7%) and nitrous oxide (U.H.P. 99.99%) were obtained from Matheson Gas Products Canada and used without further purification. Other reactants and their sources were as follows: activated carbon, Darco, 20-40 mesh, granular, surface area 1500 m 2 g - l , pore volume 1.5 cm 3 g 1, Aldrich Chemical Company, Inc., [7440-44-0]; lithium hydroxide ( L i O H . H 2 0 ; monohydrate), P406-04, Baker Analyzed, J.T. Baker Inc., Phillipsburg, N.J. 08865, USA.

2.4. Preparation and treatment of the carbon catalyst

The carbon catalyst was heated in a flow of nitrogen at 900C for several hours before experiments were commenced. The Li-promoted carbon catalyst was prepared by adding activated carbon and LiOH. H20 to deionized water and evaporating the water, while stirring, until only a thick paste remained. The paste was dried at 140C for more than 5 h. The LiOH. H20/carbon thus obtained was then converted to the lithium-promoted carbon by heating in the reactor at 465C for one hour under an oxygen flow of 0.83 cm 3 s i. The catalyst comprised 7% by weight lithium.

2.5. Treatment ofresul~

The effective reactor volume was calculated from the temperature profile in the reactor as described by Hougen and Watson [ 11]. All data were related to a reference temperature TR 'the temperature of the pyrolysis'. The equivalent reactor volume VR is the volume which gives at the temperature TR the same conversion as the real reactor with its temperature profile and may be expressed as
v

VR=exp(_ ) f (- dv
1 exp E o where E is the measured activation energy of the reaction.

64

M. Bajus, M.H. B a c k / A p p l i e d Catalysis A." General 128 (1995) 6 1 - 7 7

The temperature was measured at intervals of 5 cm. In the presence of catalyst, the equivalent volume was replaced by the volume of the catalyst, VK. The residence time of the mixture in the reactor is given as follows

:r=v.
v~
where VR is the volume of the reactor and VF is the volume flow-rate of methane. The results show that under the conditions of the experiments the conversion of methane is a reaction of the first order. For a stationary reactor with plug flow, where an irreversible reaction of the first order proceeds, Levenspiel [ 12] derived the following equation: k. 7 = ( 1 + 6.)In 1 1-X - 6..X

where 6. represents the relative change of the volume in the system when passing from zero to complete conversion
6--

V xl - V x
Vx- o

and X represents the fractional conversion of methane. Selectivity of a product was based on methane reacted, and was calculated from the yield (tool-%) and conversion of methane: Si (Yield); X

3. Results

3.1. Pyrolysis of methane without catalyst Pyrolysis of methane alone

The pyrolysis of methane without catalyst was studied over the temperature range 800-1100C, at eight temperatures. Measurements of the rate of conversion as a function of residence time showed that the reaction was first order at conversions less than about 3%. Typical results are shown in Fig. 1. First-order rate constants were calculated and were in good agreement with values reported by others [ 1316]. The activation energy was 384+ 17 kJ tool 1. The main products analyzed were ethane, ethylene, acetylene and hydrogen. Some representative results of the reaction at 850C under a variety of conditions are summarized in Table 1. Yields of propane and propene are not included since they were usually negligible and never more than 0.05 mol-%. The yield of carbon

M. Bajus, M.H. Back/Applied Catalysis A: General 128 (1995) 61-77

0.0L.

65

0.03

0.02

001

20

40

60

80

I00

RESIDENCE TIME,s Fig. 1. Graphic representation of the first-order rate equation for the thermal decomposition of methane. () 850C, ((]I) 875C. (ID) 900C.

was obtained from the stoichiometric balance between the hydrogen and the hydrocarbon products. Higher molecular weight products were negligible at short reaction times and at low temperatures where conversion was low. The major products were ethane and hydrogen. At the same time the balance between the yield of hydrogen and ethane showed the formation of carbon. At each temperature the selectivity of ethane decreased with time and ethylene increased, as a secondary product. Also, acetylene appeared at 850C and its selectivity followed that of ethane at all temperatures. As the residence time was increased the yields of C2 products rapidly achieved a maximum value and then decreased whereas the yields of hydrogen and carbon increased but approached a plateau value. The maximum yield of ethane and acetylene appeared at shorter times as the temperature increased. The maximum yield of C2 products was at 1000C. At higher temperatures and longer residence time, where the severity of pyrolysis was high, liquid product was observed in the condenser and the first cold trap. Three samples of this liquid were collected for analysis by gas chromatography. Sample 1 was collected during several experiments at 1000C and samples 2 and 3 were collected at 1050C. Sample 2 was collected at short reaction times and sample 3 at longer reaction times. The analysis is shown in Table 2. Many polyaromatic hydrocarbons, from benzene to anthracene were present. At 1000C naphthalene and its derivatives were the most abundant but at 1050C benzene was the major constituent. Pyrolysis of methane in the presence of nitrous oxide Experiments were made at three temperatures, 800, 850 and 900C. At 850C the effect on the rate of increasing concentration of nitrous oxide from 0.5 to 20% was measured with residence time of 2 s. Some results at 850C are given in Table

66

M. Bc(jus, M.H. Back~Applied Catalysis A: General 128 (1995) 61-77

d d ~ d ~ d d

E~

N d o 2 ododo d od ~ d

e~J ~ ~

r~

ee~ TM

~"

r "~-

r)

eq

ee'~ ~ f

"d
E
c

7
,.2:

e~

~z
Z r.) > ,v r...)

ZZ

,.9

M. Bajus, M.H. Back/Applied Catalysis A: General 128 (1995)61-77

Table 2 Composition of the liquid product mixture (mass-%) from the pyrolysis of methane
Sample Temperature ( C ) I 1000 1.50 0.56 0.16 40.2 3.47 6.81 12.7 1.00 4.31 15.7 2.77 10.8 2 1050 62.1 3.84 3.52 2,23 15,7 0,28 1,55 2,48 1,23 0.24 3.90 0.30 2.58 3 1050

67

Benzene Toluene Styrene lndene Naphthalene Methylnaphthalene Biphenyl Dimethylnaphthalene Acenaphthene Fluorene Phenanthrene Anthracene Other (non-ident.)

75.7 0.58 0.82 13.5 1.32 1.32 2.18 0.54 1.21 1.47 1.31

1. Fig. 2 shows the relative conversion of methane as a function of the content of nitrous oxide. Fig. 3 shows the effect of increasing concentration of nitrous oxide on the selectivity of the products ethane, ethylene and carbon monoxide. The selectivity of ethane decreased as the concentration of nitrous oxide increased, but the selectivity of ethylene increased and approached a plateau. The maximum selectivity of carbon monoxide was about 16%. Using a mixture of 5% N20 the effect of reaction time on the rate was measured at 800C. In Fig. 4 is shown the graphic representation of the first-order rate equation for decomposition of methane. At 800C the reaction was first-order in the range of reaction times shown and the rate constant was 5.3.10 3 s ~. At the same temperature the first-order rate constant for decomposition of methane was
400

300
c 0 11) L_

c 200 o (.3

o [1:
0

100

1 L L 10 15 20 KI20 c o n t e n t in the f e e d (% r o t )

Fig. 2. The ratio of the conversion of methane in the presence and absence of nitrous oxide at 850C in the absence of catalyst as a function of the content of nitrous oxide in the feed. Residence time 2 s.

68

M. Bajus, M.H. Back/Applied Catalysis A." General 128 (1995) 61-77

80t
60
g
40

B G~
G) o3 20
A

O
~ v ,h-""
0

I
10

I
20

N20 content in the feed (% vol)

Residence time

Fig. 3. Effectof the contentof nitrous oxide on the selectivity of the products at 850Cin the absence of catalyst. 2 s. (O) Ethane, ( ~ ) ethylene, (@) carbonmonoxide

3.5.10 -5 s i. The ratio of rate constants for the rate of decomposition in the presence and absence of 5% NzO was therefore 150, as illustrated in Fig. 2. The maximum value of this ratio was 320 at a nitrous oxide content of 20%. These ratios are not immediately evident from Table 1 because the experiments listed are not necessarily directly comparable in all variables. Even though nitrous oxide is a reactant, the rate of decomposition of methane remains first order with respect to
x 0.10

0.08

006

0.0/,

O /

0 02

~-

12

16 20 RESIDENCETIHE,s 800C

Fig. 4. Graphic representation of the first-order rate equation in the presence of 5% by volume nitrous oxide.

for the thermal decomposition of methane at

M. Bajus, M.H. Back/Applied Catalysis A: General 128 (I995) 61-77

69

o~ ~oo

~-J

80

60

z,O

2O

10

12

1~.

16

18

20

22

24

26

CONTENT OF N20 IN THE FEED (%VOL) Fig. 5. Effect of content of nitrous oxide on the selectivity of the products over the carbon catalyst at 850C. Residence time 0.33 s, (O) Hydrogen, ( 0 ) carbon, (tD) carbon monoxide, ( ~ ) carbon dioxide, ( ~ ) ethane.

the concentration of methane. To compare rates in the presence and absence of nitrous oxide it is convenient to compare the values of the first-order rate constants since these provide the best average representation of the rate.

3.2. Pyrolysis of methane with catalysts Pyrolysis of methane over carbon catalyst
Pyrolysis of methane was studied with the carbon catalyst in the absence and in the presence of nitrous oxide at temperatures of 700, 750, 800 and 850C. Some results at 850C are given in Table 1. The first experiments were performed using 32 cm 3 of catalyst. In the absence of nitrous oxide the products were mainly hydrogen and carbon with very low yields of C2 hydrocarbons. The rate of decomposition was greatly increased by the carbon catalyst. The ratio of the rates of decomposition in the presence and absence of the carbon catalyst was 750 at 800C and 800 at 850C. Again, the ratios were calculated from the first-order rate constants for decomposition of methane both with and without the catalyst. Although the rate constant for decomposition of methane on the carbon surface should, for completeness, include a term for the reactivity of the carbon surface, for the purpose of comparison with the homogeneous reaction the apparent first-order rate constant is suitable. The question arises whether the carbon catalyst or the carbon deposited during a reaction may act as a reactant and become incorporated into the products. If the

70

M. Bajus, M,H. Back~Applied Catalysis A." General 128 (1995) 61 77

12-

8 u)
o
c O

(D > (D (3.)

__

10

15

20

N20 content in the feed (% vol)

Fig. 6. The relative conversion of methane over the Li/carbon catalyst in the presence and absence of nitrous oxide as a function of the content of nitrous oxide in the feed at 850C. Residence time 0.06 s.

carbon catalyst undergoes reaction there should be a deficit of hydrogen in the products. In fact a large excess of hydrogen was produced in experiments with the carbon catalyst. With the Li/C catalyst a deficit was observed only in the presence of large amounts of nitrous oxide where water may be a product. The fact that the activity of the catalysts, both the carbon and the Li/C, remained constant for several hours of use suggests that deposited carbon does not influence the rate of the reaction. The activity of the carbon catalyst, 32 cm 3, had not changed after 19 h of use. The 1 cm 3 sample of the carbon catalyst was unchanged after 7 h of experiments and two samples of the Li/C catalyst remained unchanged after 23 and 27 h of use.
100

80

o~ 6 o

.~: 4 0
<9 (2)

-6 60 2O

10 N20 content in the feed ( % v o l )

20

Fig. 7. Effect of nitrous oxide on the selectivity of the products in the presence of the Li/carbon catalyst at 850C. Residence time 0.06 s. ( O ) Ethane, ( 0 ) ethylene, (@) hydrogen.

M. Bajus, M.H. Back/Applied Catalysis A: General 128 (1995) 61-77

71

12

_J

>-

10

0t,

08

1,2

1.6

RESIDENCE TIME,s Fig. 8. Effect of residence time on the yields of products at 900C in the presence of Li/carbon catalyst in the presence of 5% by volume nitrous oxide. (O) Ethane, ( 0 ) ethylene, (tD) carbon monoxide.

This constant activity also suggests that the carbon from the catalyst was not removed during the reaction. The addition of nitrous oxide had very little effect on the rate of decomposition. Hydrogen and carbon were again the main products but carbon monoxide (up to 10%) and minor amounts of carbon dioxide were also formed. The reactivity of nitrous oxide with the carbon catalyst was tested by experiments in the absence of methane. Under conditions of high temperature and long reaction time a small amount of reaction occurred, producing carbon monoxide and carbon dioxide. The extent of reaction was reduced considerably by the presence of the inert diluent, nitrogen. For example, at 850C with nitrous oxide alone with reaction times between 2 and 20 s, the formation of carbon monoxide and carbon dioxide varied between 0.1 and 1 mol-%, but in the presence of 50% nitrogen with similar reaction times the formation of carbon monoxide and carbon dioxide was not more than 0.1 mol-%. The volume of the catalyst was then reduced to 5 cm 3 and further experiments were done at 850C. Again only a small increase in rate was observed by increasing the percentage nitrous oxide from zero to 25%. With increasing concentration of

72

M. Bajus, M.H. Back/Applied Catalysis A." General 128 (1995) 61-77

>80

II
60

~0

,020

0
)-

o~
~0
_J

ta.I >..

30

20

10

0 0 & 8 12 16 20 2&

N,~O CONTENT (% VOL) JN THE FEED

Fig. 9. Influence of nitrous on conversion, selectivity and yields of C2 hydrocarbons in the presence of Li/carbon catalyst at 900C. () Conversion, (@) selectivity, ( ~ ) percent yield ethylene, (ID) percent yield ethane.

nitrous oxide the selectivity of hydrogen and carbon decreased and the selectivity of carbon monoxide and carbon dioxide increased. C2 hydrocarbons were observed with larger amounts of nitrous oxide but the selectivity was not more than 3%. These results are shown in Fig. 5.

M. Bajus, M.H. Back~Applied Catalysis A: General 128 (1995) 61 77

73

~6

V-

12

ID
8

0 700 750 803 850 900 TEMPERATURE,C Fig. 10. Effect of temperature on the yields of C2 hydrocarbons over Li/carbon catalyst in the presence of 8% by volume nitrous oxide. (ID) Ethane, ((1t) ethylene.

Pyrolysis of methane over Li/carbon catalyst

Methane was pyrolyzed over the Li/carbon catalyst at the temperatures 700, 750, 800, 850 and 900C, alone and in the presence of nitrous oxide or oxygen. Table 1 includes some results at 850C. The main effect of the addition of lithium to the carbon catalyst was a reduction in the percent conversion of methane by a factor between 20 and 50, depending on the amount of catalyst and the temperature. At the same time the products showed a major increase in the selectivity of ethane. At 900C the selectivity of ethane was 90% at a reaction time of 0.05 s, but it decreased with increasing reaction time. Over the same time range the selectivity of hydrogen increased in a corresponding fashion. At 850C the addition of nitrous oxide or oxygen to the methane increased the conversion substantially, as illustrated in Fig. 6. At residence times shorter than O. 1 s the selectivity of ethane remained high (ca. 90%) in the presence of nitrous oxide and ethylene was a significant product. The results are shown in Fig. 7. At residence times greater than 0.3 s increasing the content of nitrous oxide decreased the selectivity of ethane but increased the selectivity of ethylene. At 850C and short residence times ethane was the major product but at longer residence time and with greater content of nitrous oxide ethylene became the major product, reaching a yield of 23% with 15% nitrous oxide. At 900C the effect of residence time on the yields of products in the presence of 5% nitrous oxide is shown in Fig. 8. Ethylene is clearly formed from ethane. Carbon monoxide is now a measurable product. At 900C the effects of increasing content of nitrous oxide on conversion, selectivity and yields is shown in Fig. 9. Conversion increased with content of the additive but selectivity for C2 hydrocar-

74

M. Bajus, M.H. Back~Applied Catalysis A: General 128 (1995) 61-77

bons (ethane, ethylene and acetylene) passed through a maximum and decreased. In the presence of nitrous oxide the yields of C2 hydrocarbons reached 44% by mass. Under the same conditions the yields of carbon monoxide were 5%, carbon dioxide 2% and carbon was negligible. The yields of ethane and ethylene in the presence of 8% nitrous oxide are shown as a function of temperature in Fig. 10.

4. Discussion The most important result of the present study is the demonstration of the effectiveness of carbon as a catalyst for the decomposition of methane. The ratio of the rates of conversion of methane at 850C in the presence and absence of the carbon catalyst was approximately 800. The ratio may in fact be greater than this because the conversion, although measured at the same temperature, was represented by a different product distribution in the two cases. Decomposition over the carbon catalyst, at the temperatures of these experiments gave almost completely hydrogen and carbon, whereas the homogeneous decomposition gave mainly ethane and ethylene. The absence of the C2 hydrocarbons from the reaction over the carbon catalyst suggests the reaction progressed beyond the initial stages and at these temperatures the intermediate or final hydrocarbon products were rapidly and efficiently converted to carbon. Whether this occurs entirely on the surface before the products desorb into the gas phase or whether secondary decomposition takes place after the gaseous products have been formed cannot be ascertained from the present results. An important question concerning the role of the carbon catalyst is whether the catalyst itself may react to form carbon monoxide or carbon dioxide or whether these products come directly from methane. Also involved in this question is the possibility of differences in reactivity or in catalytic activity of the carbon deposited during the reaction and the carbon used as the catalyst. These questions cannot be decisively answered from the present results but their significance lies more in the unravelling of the mechanism than in the search for an efficient coupling of methane. From the point of view of the production of fuels from methane any carbon monoxide or carbon dioxide formed, from whatever source, represents a loss and hence an inefficiency. Whether this inefficiency arises from loss of methane or loss of carbon is less important than the demonstration of the effectiveness of the carbon surface in the coupling process. Nitrous oxide was an important oxidizing agent for the coupling of methane, particularly in the homogeneous reaction in the absence of the catalyst. Increasing content of nitrous oxide in the reactant led to a high percentage conversion of methane, but the selectivity of the C2 hydrocarbons fell and carbon monoxide became an important product. In the presence of the carbon catalyst nitrous oxide had little effect on the conversion. Again it led to the formation of carbon monoxide which reduced the selectivity of the C2 hydrocarbons.

M. Bajus, M.H. Back/Applied Catalysis A: General 128 (1995) 61-77

75

In terms of the rate of conversion of methane the Li/C catalyst was no more effective than the carbon catalyst itself. The important effect of this catalyst, however, was in promoting the selectivity of ethane. Its selectivity approached 100% at very short reaction times, but fell rapidly at longer times. With the Li/C catalyst nitrous oxide had a significant promoting effect on the conversion and at short reaction times the selectivity to the C2 hydrocarbons remained high even for 20% nitrous oxide content. As the proportion of nitrous oxide increased, ethylene became the major C2 hydrocarbon product and the yield of ethane was reduced. The maximum selectivity for C2 hydrocarbons was achieved before the maximum conversion of methane, as shown in Fig. 9. Although carbon monoxide was also formed, it remained a minor product. Although nitrous oxide is an effective oxidant for the conversion of methane, the rate of incorporation of oxygen into the lattice and the regeneration of the active centers is slower than with oxygen [ 17 ]. The results using the two oxidants are compared in Table 2. The fact that the effect of nitrous oxide was significant in the homogeneous reaction and negligible or minor in the presence of the catalysts suggests that nitrous oxide reacts directly with methane in the gas phase rather than on the surface. In the presence of the catalysts, where the rate of decomposition of methane is accelerated on the surface, the homogeneous reaction with nitrous oxide is relatively less important. The reaction mechanism of the oxidative coupling of methane comprises many elementary reactions including those at the catalyst surface and those taking place in the gas phase. The role of the catalyst in the oxidative coupling of methane is the formation of methyl radicals by the reaction of methane with an active oxygen species on the catalyst surface. The form of the active oxygen is not clear. It may be adsorbed oxygen (molecular or atomic) or lattice oxygen. Presumably, that part of lithium which is incorporated into the carbon structure, or adsorbed on the surface, forming Li+O sites, is of essential importance for the activation of the methane molecule. This process is very efficient on the lithium-promoted catalyst because the surface area of the catalyst based on carbon is much higher (up to 1500 m 2 g 1) than that of the catalyst based on MgO (up to 200 m 2 g I and frequently lower). The number of active sites for methane oxidative coupling is low as compared to the total oxygen content on the surface. The overall process proceeds by a mechanism of surface reduction and reoxidation. Ethane is formed by recombination of methyl radicals in the gas phase. The probability of this reaction on the surface is low. Ethane can be converted into ethylene by oxidative dehydrogenation of ethane and the ethyl radical by their interaction with the surface oxygen or in the gas phase. The reaction is faster than the interaction between methane and the surface oxygen. Complete oxidation to carbon monoxide and carbon dioxide occurs either in the gas phase through CH302 and its further oxidation or on the surface by interaction with alkyl radicals and mobile oxygen atoms.

76

M. Bajus, M.H. Back~Applied Catalysis A: General 128 (1995) 61-77

The main advantage of the Li/C catalyst over the carbon catalyst was the higher selectivity for ethane, although this was achieved only at low conversion. Both carbon catalysts are so reactive that the hydrocarbon product was rapidly converted to carbon. This result raises a question concerning the nature of the active sites on the catalytic surface. Is the effective catalytic material the freshly deposited carbon, which is clearly formed during the reaction? There have been suggestions that this type of carbon is highly reactive [ 18] and may easily catalyze the decomposition of methane. In a flow system such as used in these experiments carbon will accumulate and even with short reaction times will quickly form a reactive layer. Nevertheless, because the activity of the catalysts remained constant for such long periods of time it appears that the deposited carbon is not very different from the catalyst itself in its ability to activate methane.

5. Conclusion
The present results demonstrate the effectiveness of carbon, combined with lithium oxide, as a catalyst in the conversion of methane. Addition of nitrous oxide to the reactants increased the effectiveness of the conversion to ethane, particularly at short reaction times. Loss to carbon monoxide and carbon dioxide was minor. The system appears promising for further development.

Acknowledgements
The authors thank the Department of Energy Mines and Resources, Canada, for financial support of this work and Dr. E. Furimsky of the same Department for helpful advice and encouragement.

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M. Bajus, M.H. Back/Applied Catalysis A: General 128 (1995) 61-77

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77