• Applied Chemistry for Engineering
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• v.3 no.2
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• pp.256-265
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• 1992

The kinetics for the oxidative coupling of methane over NaCl(30wt%)/ZnO(60wt%)/${\alpha}-Al_2O_3$ catalyst was investigated, and then the active oxygen species were discussed. The conversion rate of methane was measured at the atmospheric pressure with various combinations of partial pressure of methane and oxygen at temperature range of $650^{\circ}C{\sim}750^{\circ}C$, at conversions less than with 10%. These rate data were then used to verify the proposed Langmuir-Hinshelwood kinetic equation. The rate limiting step appeared to be the formation of the methyl radicals by the reactin of the adsorbed methane and the adsorbed oxygen, which were adsorbed on the different active sites of the catalyst. The activation energy of the methyl radical formation was estimated to be ca. 39 kcal/mol. From the kinetic studies, the oxygen species respolsible for the formation of methyl radicals was proposed to be diatomic oxygen such as $O{_2}{^{2-}}$ or $O_2{^-}$ on the surface.

• Journal of the Korean Applied Science and Technology
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• v.13 no.1
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• pp.67-74
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• 1996

This study was conducted to find a catalyst system which has high conversion and selectivity for the oxidative coupling of methane to produce ethane and ethylene. Various catalysts were tested in a fixed bed reactor ar $750^{\circ}C$, 1 atm, and the feed ratio($CH_4/O_2$) of 2/1. Under the reaction condition, 10wt%$PbSO_4/MgO$ catalyst showed the highest catalytic activity : methane conversion, $C_2$ selectivity and yield were 50, 40 and 20%, respectively. Catalysts containing sulfate compounds, 10wt%$PbSO_4/MgO$, 10wt%$MgSO_4/MgO$ and $Na_2SO_4/MgO$ revealed a moderate methane conversions such as 38, 50 and 50%, respectively and low $C_2$ selectivities such as 18, 5 and 9%, respectively. Catalysts containing carbonate compounds, 10wt%$PbCO_3/MgO$, 10wt%$Li_2CO_3/MgO$ and $NaCO_3/MgO$, also showed a moderate methane conversions such as 64, 44 and 51%, respectively and low $C_2$ selectivities such as 5, 6 and 2%, respectively. With the existence of chlorine and mercury, $C_2$ selectivity was decreased.

• Bulletin of the Korean Chemical Society
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• v.28 no.6
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• pp.1049-1052
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• 2007

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.147-156
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• 1992

Supported lead oxide catalysts were prepared by using ${\alpha}-,{\beta}-{\gamma}$-alumina, and MgO as a support. Among the supported lead oxide catalysts, MgO-supported catalyst showed the highest $C_2^+$ hydrocarbon selectivity for the methane conversion into $C_2^+$ hydrocarbons, but ${\gamma}$-alumina-supported PbO catalyst gave the highest $CO_2$ selectivity. And ${\alpha}$-alumina-supported catlyst showed the midium activity, whereas ${\beta}$-alumina-supported catalyst gave little activity. These reaction characteristics seemed to be largely dependent on the acticity of lattice oxygens in supported catalysts, which would be influnto be largely dependent on the activity of lattice oxygens in supported catalysts, which would be influenced in the interaction between the supports and lead oxides and the properties of supports. Especially, much higher ration of (002)/(111) peak intensities for PbO phase on MgO support than on the other supports in X-ray diffraction analysis was considered to be ab evidence that methane oxidative coupling of methane might be so-called structure-sensitive reaction, and this seemed to be an example of surface oxide-support interaction (SOSI) in the oxidative coupling reaction.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.807-813
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• 1993

Oxidative coupling of methane(OCM), one of the methods of direct methane conversion, was performed. Metal oxide catalysts used were Li/MgO and Pb/MgO. To investigate the reactivity of the catalysts with temperature, the reaction was carried out at 600, 700 and $800^{\circ}C$; and to investigate the effect of the feed ratio of the reactants($CH_4:O_2$) on reactivity, conversion, and selectivity the reaction was performed at $700^{\circ}C$ with the feed ratio of 2:1 and 1:1. The results indicate that 7wt% Li/MgO catalyst is a good catalyst for OCM reaction with 20% conversion and 65% selectivity at $700^{\circ}C$ with the feed ratio of 2:1. As feed ratio was 1:1, methane conversion was increased to 30% while $C_2$ selectivity decreased to 45% at $700^{\circ}C$ with 7wt% Li/MgO catalyst. The Pb/MgO catalyst showed less selectivity(25%) than Li/MgO did.

• Applied Chemistry for Engineering
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• v.5 no.4
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• pp.580-587
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• 1994

The oxidative coupling of methane was studied kinetically using $Na^+(50wt%)/MgO$ catalyst at 710, 730, 750, 770 and $790^{\circ}C$ in a fixed bed flow reactor at the atmospheric pressure under differential conversion conditions. Through curve fitting, it was found that the Langmuir-Hinshelwood type mechanism was fitted to this reaction rather than Rideal-Redox type or Eley-Rideal type mechanism. Therefore, it was proposed that the $O_2{^-}$ or $O_2{^{2-}}$ species on the surface was related to the production of $CH_3{\cdot}$. The estimated activation energy of $CH_3{\cdot}$ production was about 39.3kcal/mol. Moreover, as the result of curve fitting, the stoichiometric coefficient of $O_2$ for the production of $CH_3{\cdot}$ to produce $CO_x$was approximately 1.5. Accordingly, it could be concluded that the $CH_3O_2{\cdot}*$ was prouduced through the partial oxidation of $CH_3{\cdot}$ with the surface oxygen.

• Bulletin of the Korean Chemical Society
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• v.15 no.12
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• pp.1058-1064
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• 1994

Mn/In$_2O_3$ systems with a variety of Mn mol${\%}$ were prepared to investigate the effect of Mn-addition on the catalytic activity of Mn/In$_2O_3$ in the oxidative coupling of methane. The oxidative coupling of methane was examined on pure In$_2O_3$ and Mn/In$_2O_3$ catalysts by cofeeding gaseous methane and oxygen under atmospheric pressure between 650 and 830 $^{\circ}C$. Although pure In$_2O_3$ showed no C$_2$ selectivity, both the C$_2$ yield and the C$_2$ selectivity were increased by Mn-doping. The 5.1 mol${\%}$ Mn-doped In$_2O_3$ catalyst showed the best C$_2$ yield of 2.6${\%}$ with a selectivity of 19.1${\%}$. The electrical conductivities of pure and Mn-doped In$_2O_3$ systems were measured in the temperature range of 25 to 100 $^{\circ}C$ at PO$_2$'S of 1 ${\times}$ 10$^{-7}$ to 1 ${\times}$ 10 $^{-1}$ atm. The electrical conductivities were decreased with increasing Mn mol${\%}$ and PO$_2$, indicating the specimens to be n-type semiconductors. Electrons serve as the carriers and manganese can act as an electron acceptor in the specimens. Manganese ions doped in In$_2O_3$ inhibit the ionization of neutral interstitial indium or the transfer of lattice indium to interstitial sites and increase the formation of oxygen vacancy, giving rise to the increase of the concentration of active oxygen ion on the surface. It is suggested that the active oxygen species adsorbed on oxygen vacancies are responsible for the activation of methane.

• Bulletin of the Korean Chemical Society
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• v.30 no.6
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• pp.1368-1372
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• 2009

• Advances in Energy Research
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• v.5 no.1
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• pp.13-29
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• 2017

The roles of Na, Mn, W and silica, and the synergistic effects between each metal in the $MnNa_2WO_4/SiO_2$ catalyst have been investigated for oxidative coupling of methane (OCM). The crystallisation of amorphous silica during calcination at $900^{\circ}C$ was promoted primarily by Na, but Mn and W also facilitated this process. The interaction between Na and Mn tended to increase the extent of conversion of $Mn_3O_4$ to $Mn_2O_3$. The formation of $Na_2WO_4$ was dependent on the order in which Na and W were introduced to the catalyst. The impregnation of W before Na resulted in the formation of $Na_2WO_4$, but this did not occur when the impregnation order was reversed. $MnWO_4$ formed in all cases where Mn and W were introduced into the silica support, regardless of the impregnation order; however, the formation of $MnWO_4$ was inhibited in the presence of Na. Of the prepared samples in which a single metal oxide was introduced to silica, only $Mn/SiO_2$ showed OCM activity with significant oxygen conversion, thus demonstrating the important role that Mn plays in promoting oxygen transfer in the reaction. The impregnation order of W and Na is critical for catalyst performance. The active site, which involves a combination of Na-Si-W-O, can be formed in situ when distorted $WO_4^{2-}$ interacts with silica during the crystallisation process facilitated by Na. This can only occur if the impregnation of W occurs before Na addition, or if the two components are introduced simultaneously.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2457-2460
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• 2011