실리카 담지 12-몰리브도인산 촉매상에서의 아산화질소에 의한 메탄의 부분산화반응

홍성수; 우희철; 주창식; 이근대; Moffat JB

Journal of the Korean Industrial and Engineering Chemistry, Vol.5, No.1, 139-148, February, 1994

Export Citation

실리카 담지 12-몰리브도인산 촉매상에서의 아산화질소에 의한 메탄의 부분산화반응

The Partial Oxidation of Methane by Nitrous Oxide over Silica-Supported 12-Molybdophosphoric Acid

홍성수, 우희철, 주창식, 이근대, Moffat JB

초록

실리카에 담지된 헤테로폴리산 촉매에서 아산화질소에 의한 메탄의 부분산화반응을 연구하였다. 여러 가지의 반응조건, 즉 반응온도, 반응물의 분압, 접촉시간, 촉매의 담지량 및 전처리온도 등이 전환율이나 생성물의 선택도 및 속도론에 미치는 영향이 연구되었다. 20 wt%로 담지된 촉매가 전환율과 포름알데히드의 수율에 있어서 가장 높은 값을 보여 주었다. 메탄은 전환반응에서의 속도식을 구한 결과, 메탄에 대해서는 1차식을 보여 주었고, 아산화질소에 대한 반응차수는 약 0.4였다. 또한 전체반응의 겉보기 활성화에너지는 30.78 kcal/mole 이었다. 반응물 중에 첨가된 소량의 사염화탄소는 메탄의 산화반응에서 실리카 담지 HPMo 촉매의 활성을 증가시키는 반면에, 반응물에 첨가된 물은 오히려 활성을 감소시키는 것을 볼 수 있었다.

The partial oxidation of methane with nitrous oxide on silica-supported metal-oxygen cluster compounds, known as heteropoly acids, has been studied. The effects of several variables such as reaction temperature, partial pressure of reactants, residence time, loading of the catalysts, and pretreatment temperature, on the conversion and product distribution were observed. The kinetics also has been studied. The conversion and yield of formaledehyde show maximum values at a loading of 20 wt%. The apparent reaction order of methane conversion is ca. 1.0 with respect to CH₄ and ca. 0.4 with respect to N₂O. In addition, the apparent activation energy is 30.78 kcal/mole. The addition of small quantities methane whereas water introduced to the reactant decreased the activity of catalyst under present study.

[References]

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Kasztelan S, Moffat JB, J. Catal., 106, 512 (1987)
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Ahmed S, Moffat JB, J. Catal., 118, 281 (1989)
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Khan MM, Somorjai GA, J. Catal., 91, 263 (1985)
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Hodnett BK, Moffat JB, J. Catal., 88, 253 (1984)
Hodnett BK, Moffat JB, J. Catal., 91, 93 (1985)
Highfield JG, Moffat JB, J. Catal., 95, 108 (1985)
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Moffat JB, J. Mol. Catal. A-Chem., 26, 385 (1986)
Hayashi H, Moffat JB, J. Catal., 77, 473 (1982)
Hayashi H, Moffat JB, J. Catal., 81, 61 (1983)
Misono N, Watanabe T, Misono M, J. Phys. Chem., 89, 80 (1985)
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Cullis CF, Keene DE, Trimm DL, J. Catal., 19, 378 (1970)
Hong SS, Moffat JB, Appl. Catal., in press
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Kasztelan S, Payen E, Moffat JB, J. Catal., 128, 479 (1991)
Hong SS, Ph.D. Dissertation, Seoul National Univ., Seoul, Korea (1989)
Payen E, Kasztelan S, Moffat JB, J. Chem. Soc.-Faraday Trans., 88, 2263 (1992)
Mendelovici L, Lunsford JH, J. Catal., 94, 37 (1985)
ErdoHelyi A, Mate F, Solymosi F, J. Catal., 135, 563 (1992)
ErdoHelyi A, Solymosi F, J. Catal., 129, 497 (1991)

[Referenced By]

[1] Parkyns ND, Chem. Br., 26, 841 (1990)

[2] Blair EW, Wheeler TS, J. Soc. Chem. Ind., 41, 303 (1922)

[3] Kasztelan S, Moffat JB, J. Catal., 106, 512 (1987)

[4] Kasztelan S, Moffat JB, J. Chem. Soc.-Chem. Commun., 1663 (1987)

[5] Kasztelan S, Moffat JB, Appl. Catal., 40, 101 (1988)

[6] Ahmed S, Moffat JB, J. Catal., 112, 54 (1988)

[7] Ahmed S, Moffat JB, J. Catal., 118, 281 (1989)

[8] Pitchai R, Klier K, Catal. Rev.-Sci. Eng., 28, 13 (1986)

[9] Foster NR, Appl. Catal., 19, 1 (1985)

[10] Sofranko JA, Leonard JJ, Jones CA, J. Catal., 103, 302 (1987)

[11] Liu HF, Liu RS, Liew KY, Johnson RE, Lunsford JH, J. Am. Chem. Soc., 106, 4117 (1984)

[12] Khan MM, Somorjai GA, J. Catal., 91, 263 (1985)

[13] Zhen KJ, Khan MM, Mak CH, Lewis KB, Somorjai GA, J. Catal., 94, 501 (1985)

[14] Hodnett BK, Moffat JB, J. Catal., 88, 253 (1984)

[15] Hodnett BK, Moffat JB, J. Catal., 91, 93 (1985)

[16] Highfield JG, Moffat JB, J. Catal., 95, 108 (1985)

[17] Highfield JG, Moffat JB, J. Catal., 98, 245 (1986)

[18] Moffat JB, J. Mol. Catal. A-Chem., 26, 385 (1986)

[19] Hayashi H, Moffat JB, J. Catal., 77, 473 (1982)

[20] Hayashi H, Moffat JB, J. Catal., 81, 61 (1983)

[21] Misono N, Watanabe T, Misono M, J. Phys. Chem., 89, 80 (1985)

[22] Tan SA, Grant RB, Lambert RM, J. Catal., 100, 383 (1986)

[23] Cullis CF, Keene DE, Trimm DL, J. Catal., 19, 378 (1970)

[24] Hong SS, Moffat JB, Appl. Catal., in press

[25] Kasztelan S, Payen E, Moffat JB, J. Catal., 125, 45 (1990)

[26] Kasztelan S, Payen E, Moffat JB, J. Catal., 128, 479 (1991)

[27] Hong SS, Ph.D. Dissertation, Seoul National Univ., Seoul, Korea (1989)

[28] Payen E, Kasztelan S, Moffat JB, J. Chem. Soc.-Faraday Trans., 88, 2263 (1992)

[29] Mendelovici L, Lunsford JH, J. Catal., 94, 37 (1985)

[30] ErdoHelyi A, Mate F, Solymosi F, J. Catal., 135, 563 (1992)

[31] ErdoHelyi A, Solymosi F, J. Catal., 129, 497 (1991)