전이금속 이온교환 제올라이트의 산촉매 반응에 대한 수소촉진효과

김재승; 박남국; 서성규

HWAHAK KONGHAK, Vol.30, No.4, 440-449, August, 1992

Export Citation

전이금속 이온교환 제올라이트의 산촉매 반응에 대한 수소촉진효과

Enhancing Effect of Hydrogen on Acid-Catalyzed Reactions over Transition Metal Ion Exchanged Zeolites

김재승, 박남국, 서성규

초록

Ag⁺이온교환 제올라이트 촉매상에서 관찰되는 산촉매 반응에 대한 수소촉진효과를 다른 전이금속(Cu²⁺, Ni²⁺) 이온교환 제올라이트 촉매에 대하여 연구하였다. 대표적 산촉매 반응으로 1-buten의 이성질화 반응, o-xylene의 transformation과 ethanol의 탈수반응을 택하였다. 산촉매 활성에 대한 수소촉진효과, 환원 및 반응온도, 수소분압, 수소촉진효과의 가역성, 이온교환 금 속의 종류, 제올라이트의 형태 및 이온교환율의 영향 등을 조사하였다. 수소로 환원된 Ag⁺ 및 Cu²⁺ 이온교환 제올라이트 촉매는 반응계 내의 수소 공존여부에 따라 산촉매 반응에 대한 수소촉진효과가 가역적으로 관찰되었다. 이는 촉매상에 수소가 가역적으로 화학흡착되며, 흡착된 수소가 proton의 형태로 존재함을 의미한다. 한편, 수소로 환원된 Ni²⁺ 이온교환 제올라이트 촉매의 경우는 공존하는 수소에 의한 선택적인 수소화 반응이 촉진되었다. 또한 제올라이트의 형태에 따라 1-butene의 이성질화반응에 대한 생성물의 형상선택성이 관찰되었다.

As an acid-catalyzed reactions, the isomerization of 1-butene, the transformation of o-xylene and the dehydration of ethanol over the transition metal ion(Cu²⁺, Ni²⁺) exchanged zeolites were carried out to compare with Ag⁺ ion exchanged zeolite. Hydrogen enhancing effect and its reversibility, the effect of reduction and reaction temperature, partial pressure of hydrogen, the type of metal ion, the type of zeolite, ion exchange ratio were studied to the catalytic activity. The reversible hydrogen enhancing effect on the catalytic activity was observed over the hydrogen reduced Ag⁺ and Cu²⁺ ion exchanged zeolites by the presence or absence of hydrogen in the reaction system. This means that hydrogen was reversibly chemisorb-ed and retained as an acidic protons on those zeolites. But, the selective hydrogenation of 1-butene was occurred over the hydrogen reduced Ni²⁺ ion exchanged zeolite by the presence of 1-butene was occurred over the hydrogen reduced Ni²⁺ ion exchanged zeolite by the presence of hydrogen. Also, the shape-selectivity of product in the 1-butene isomerization was observed with the type of zeolite.

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[1] Breck DW, "Zeolite Molecular Sieves," John Wiley and Sons, New York (1974)

[2] Jacobs PA, Uytterhoeven JB, Beyer HK, J. Chem. Soc.-Faraday Trans., 73, 1755 (1977)

[3] Baba T, Seo SG, Ono Y, Grobet PJ, "Innovation in Zeolite Materials Science," Elsevier, Amsterdam, 443 (1988)

[4] Ono Y, Baba T, Kanae K, Seo SG, Nippon Kagaku Kaishi, 985 (1988)

[5] Kim JS, Seo SG, Korean J. Chem. Eng., 6(2), 138 (1989)

[6] Baba T, Seo SG, Ono Y, MRS Int'l Mtg. Adv. Mats., 2, 173 (1989)

[7] Kim JS, Park NC, Seo SG, HWAHAK KONGHAK, 29(4), 440 (1991)

[8] Seo SG, Ph.D. Dissertation, Chonnam National University, Kwangju, Korea (1989)

[9] Kim JS, Park NC, Seo SG, HWAHAK KONGHAK, 26(6), 664 (1988)

[10] Iwamoto M, Nagano H, Furukawa H, Kagawa S, Chem. Lett., 471 (1983)

[11] Barrer RM, Villiger H, Z. Krist., 128, 352 (1969)

[12] Angell CL, Schaffer PC, J. Phys. Chem., 70, 1413 (1966)

[13] Herman RG, Lunsford JH, J. Phys. Chem., 79, 2388 (1975)

[14] Kim JS, Seo SG, HWAHAK KONGHAK, 24(6), 485 (1986)

[15] Knor Z, Anderson JR, Boudart M, "Catalysis," Springer-Verlag, Berlin, 3, 231 (1982)

[16] Beyer H, Jacobs PA, Uytterhoeven JB, J. Chem. Soc.-Faraday Trans., 72, 674 (1976)

[17] Kim Y, Seff K, J. Phys. Chem., 91, 668 (1987)