EFFECT OF MANGANESE ON Cu/SiO<SUB>2</SUB> CATALYSTS FOR THE DEHYDROGENATION OF CYCLOHEXANOL TO CYCLOHEXANONE

Jeon GS; Chung JS

Korean Journal of Chemical Engineering, Vol.14, No.2, 79-87, March, 1997

EFFECT OF MANGANESE ON Cu/SiO₂ CATALYSTS FOR THE DEHYDROGENATION OF CYCLOHEXANOL TO CYCLOHEXANONE

The effect of the addition of manganese to Cu/SiO₂ catalysts for cyclohexanol dehydrogenation reaction was investigated. At reaction temperature of 250℃, the conversion and the selectivity to cyclohexanone were both increased with the addition of manganeses to Cu/SiO₂ catalyst. However, as the reaction temperature was further increased, higher loading of manganese in Cu/SiO₂ catalyst led to a decrease in the conversion of cyclohexanol. Manganese in Cu/SiO₂ catalyst decreased the reduction temperature of copper oxide, increased the dispersion of copper metal, and decreased the selectivity to cyclohexene. It was found that the dehydration of cyclohexanol to cyclohexene occurred on the intermediated acid sites of catalyst. At high Mn loading, catalyst surface was more enriched with manganese in used catalyst compared to that in freshly calcined or reduced catalyst, which may account for the sharp decrease of the conversion at high temperature of 390℃. Upon reduction, copper manganate on silica was decomposed into fine particles of copper metal and manganese oxide （Mn₃O₄）.

Keywords:Cu/Mn/SiO₂;Cyclohexanol Dehydrogenation;Hydrogen TPR;XRD;N₂O Titration;Ammonia TPD;XPS

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[2] Bartley GJJ, Burch R, Chappel RJ, Appl. Catal., 43, 91 (1988)

[3] Busca G, J. Mol. Catal., 43, 225 (1987)

[4] Castro VD, Furlani C, Gargano M, Rossi M, Appl. Surf. Sci., 28, 270 (1987)

[5] Chen WS, Lee MD, Lee JF, Appl. Catal. A: Gen., 83, 201 (1992)

[6] Chinchen GC, Hay CM, Vandervell HD, Waugh KC, J. Catal., 103, 79 (1987)

[7] Cocke DL, Veprek S, Solid State Commun., 57, 745 (1986)

[8] Cubberley AH, Mueller MB, J. Am. Chem. Soc., June, 1535 (1947)

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[10] Fridman VZ, Bedina LN, Petrov IY, Kinet. Katal., 29, 621 (1988)

[11] Guczi L, Solymosi F, Tetenyi P, "New Frontiers in Catalysis: B," Budapest (1992)

[12] Hino M, Arata K, Chem. Lett., 1737 (1990)

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[17] Jeon GS, "The Dehydrogenation of Cyclohexanol over Silica-Supported Copper Catalysts," Pohang University of Science and Technology (1995)

[18] Klier K, Adv. Catal., 31, 243 (1982)

[19] Komarov VS, Bel'skaya RI, Skruko OF, Taborissakaya EA, "Catalyst for Dehydrogenation of Cyclohexanol to Cyclohexanone," U.S.S.R. Patent, 411 888 (1974)

[20] Leith IR, Howden MG, Appl. Catal., 37, 75 (1988)

[21] Lin YM, Wang I, Yeh CT, Appl. Catal., 41, 53 (1988)

[22] Lockwood WH, Frazer JCW, J. Phys. Chem., 38, 735 (1934)

[23] Parris GE, Klier K, J. Catal., 97, 374 (1986)

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[27] Sermon PA, Bond GC, Catal. Rev.-Sci. Eng., 8, 211 (1974)

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[29] Sivaraj CSivaraj C, Reddy BM, Rao PK, Appl. Catal., 45, L11 (1988)

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[31] Takezawa N, Kobayashi H, Kamegai Y, Shimokawabe M, Appl. Catal., 3, 381 (1982)

[32] Uemichi Y, Sakai T, Kanazuka T, Chem. Lett., 777 (1989)

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[34] Veprek S, Cocke DL, Kehl S, Oswald HR, J. Catal., 100, 250 (1986)

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[36] Wang I, Lin YM, "Method of Producing Cyclohexanone from Cyclohexanol through Oxidative Dehydrogenation," U.S. Patent, 4,198,239 (1990)

[37] Wollner A, Lange F, Knozinger H, Appl. Catal. A: Gen., 94, 181 (1993)

[38] Yang BL, Chan SF, Chang WS, Chen YZ, J. Catal., 130, 52 (1991)

[39] Yoon C, Cocke DL, Appl. Surf. Sci., 31, 118 (1988)

[40] Yoon C, Cocke DL, J. Catal., 113, 267 (1988)