이산화탄소와 메탄을 이용한 함성개스 제조에 있어서 Ni/Y-zeolite 촉매의 특성

김건중; 김광호; 고완석; 조동수; 김종호

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.2, 200-212, April, 1995

Export Citation

이산화탄소와 메탄을 이용한 함성개스 제조에 있어서 Ni/Y-zeolite 촉매의 특성

Catalytic Properties of Ni/Y-zeolites for the CO₂+CH₄ Reaction into Synthesis Gas

김건중, 김광호, 고완석, 조동수, 김종호

초록

이산화탄소와 메탄으로부터 합성개스를 직접 제조하는 반응을 니켈, 팔라듐 및 백금이 담지된 촉매상에서 수행하였다. NaY상에 담지된 니켈은 메탄의 탈수소 및 이산화탄소의 수소화반응에 대하여 높은 활성을 보였다. 이 촉매 상에서 이산화탄소의 전환율은 84%에 이르렀다. 소성한 NiO와 PtO도 역시 메탄의 탈수소반응에 대하여 활성을 나타내었다. 촉매활성은 NaY상에 도입된 니켈 함량에 크게 의존하였으며, 니켈 담지량이 3.3wt%인 경우에 가장 높은 이산화탄소 및 메탄 전환율이 얻어졌다. 촉매의 특성은 Y-제올라이트 중에 존재하는 양이온의 종류에 의해 영향을 받았다. 높은 이산화탄소 전환율은 산성이 아닌 제올라이트 상에 니켈을 담지하였을 때 얻어졌다. 제올라이트 담체의 정전기장이 증가할수록 이산화탄소의 전환율은 감소하였다. 또한 이산화탄소가 순수한 제올라이트 담체나 니켈이 담지된 촉매로부터 탈착되는 현상을 승온탈착법으로 관찰하였다.

Synthesis gas formation by the direct reaction of CO₂ with CH₄has been studied on Ni, Pd and Pt suppored catalysts. Ni supported on NaY zeolite showed a high catalytic activity for the dehydrogenation of methane and the hydrogenation of carbon dioxide. The conversion of CO₂ over this catalyst reached up to 84%. The calcined NiO and PtO also showed the dehydrogenation activity of methane. The activity strongly depended on the nickel amount over NaY, and the maximum conversion of CO₂ and CH₄ was obtained with 3.3wt% Ni loading. The catalytic properties were influenced by the cations in Y-zeolite. The higher CO₂ conversion was obtained over Ni supported on non-acidic zeolites. As the electrostatic field of zeolite increased, the CO₂ conversion decreased. In addition, the measurement of CO₂ desorbed from pure zeolites or Ni/support was carried out by the temperature programmed desorption method.

[References]

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[1] Rostrup-Nielsen JR, "CATALYSIS," ed. J.R. Anderson and M. Boudart, 5, 1, Springer-Verlag, Berlin (1984)

[2] Trimm DL, "Methane Conversion," ed. D.M. Bibby, C.D. Chang, R.F. Howe, and S. Yurchak, 39, Elsevier Science, Amsterdam (1988)

[3] Rose F, Stahl Eisen, 95, 1012 (1975)

[4] Manley J, Metals Bull., Dec., 49 (1981)

[5] Asami K, Shikada T, Fujimoto K, Bull. Chem. Soc. Jpn., 74, 266 (1991)

[6] Rostrup-Nielsen JR, "Methane Conversion," ed. D.M. Bibby, C.D. Chang, R.F. Howe, and S. Yurchak, 73, Elsevier Science, Amsterdam (1988)

[7] Nakamura J, Umeda S, Kubushiro K, Ohashi T, Kunimori K, Uchijima T, Catalyst, 33, 99 (1991)

[8] Kim GJ, Cho BR, J. Korean Ind. Eng. Chem., 4(2), 432 (1993)

[9] Kim GJ, Jung SJ, Kim TJ, Kwon LM, HWAHAK KONGHAK, 25(5), 477 (1987)

[10] Turlier P, Pereira EB, Martin GA, Proc. of Int. Conf. on CO₂ Utilization, 119 (1993)

[11] Satterfield CN, "Heterogeneous Catalysis in Practice," 280, McGraw-Hill, New York (1980)

[12] Martin GA, Primet M, Dalmon JA, J. Catal., 53, 321 (1978)

[13] Dalmon JA, Martin GA, J. Chem. Soc.-Faraday Trans., 10, 11 (1979)

[14] Fujita S, Terunuma H, Nakamura M, Takezawa N, Ind. Eng. Chem. Res., 30, 146 (1991)

[15] Kneale B, Ross JRH, Faraday Trans. I, 79, 157 (1983)

[16] McCarty JG, Wise H, J. Catal., 57, 406 (1979)

[17] Davis SM, Zaera F, Somorjai G, J. Catal., 77, 439 (1982)

[18] Falconer JL, Zagli AE, J. Catal., 62, 280 (1980)

[19] Figueiredo JL, Trimm DL, J. Catal., 40, 154 (1975)

[20] Bernardo CA, Trimm DL, Carbon, 17, 115 (1979)

[21] Minachev KM, Isakov YI, "Zeolite Chemistry and Catalysis (ACS Mono. 171)" ed. J.A. Rabo, Amer. Chem. Soc. Washington D.C., 552 (1976)

[22] Iizuka T, Tanaka Y, Tanabe K, J. Catal., 76, 1 (1982)

[23] Chutoransky P, Krannich WL, J. Catal., 21, 1 (1971)

[24] Vannice MA, J. Catal., 44, 152 (1976)

[25] Richardson JT, J. Catal., 21, 122 (1971)

[26] Huang CP, Richardson JT, J. Catal., 51, 1 (1978)

[27] DellaBetta RA, Boudart M, Proceedings of the 5th International Congress on Catal, 1329, Elsevier, Amsterdam (1973)

[28] Ward JW, "Zeolite Chemistry and Catalysis (ACS Mono. 171)," ed. J.A. Rabo, 118, Amer. Chem. Soc. Washington D.C. (1976)

[29] Ward JW, J. Catal., 10, 34 (1968)

[30] Baba T, Kim GJ, Ono Y, J. Chem. Soc.-Faraday Trans., 88, 891 (1992)

[31] Tauster SJ, Fung SC, Garten RL, J. Am. Chem. Soc., 4, 170 (1978)

[32] Park DS, Lee JR, Kim JT, HWAHAK KONGHAK, 27(5), 723 (1989)

[33] Sauvion GN, Guillex MF, Tempere JF, Delafosse D, "Metal Microstructure in Zeolite (Studies in Surface Science and Catalysis 12)," ed. P.A. Jacobs, N.I. Jaeger, P. Jiru and G. Schulz-Ekloff, 229, Elsevier, Amsterdam (1982)