Issue
Korean Journal of Chemical Engineering,
Vol.14, No.2, 79-87, 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).
[References]
  1. Anderson JR, "Structure of Metallic Catalysts," Academic Press, London, 1975
  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
  9. Emelyanov NP, Belskaya RI, Semyachko RY, "Catalyst for Dehydrogenation of Cyclohexanol to Cyclohexanone," U.S. Patent, 3,652,460, 1972
  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
  13. Jeon GS, Chung JS, Korean J. Chem. Eng., 12(1), 132, 1995
  14. Jeon GS, Chung JS, Appl. Catal. A: Gen., 115(1), 29, 1994
  15. Jeon GS, Seo G, Chung JS, Korean J. Chem. Eng., 13(4), 412, 1996
  16. Jeon GS, Seo G, Chung JS, HWAHAK KONGHAK, 34(5), 605, 1996
  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
  24. Robertson SD, McNicol BD, deBaas JH, Kloet SC, Jenkins JW, J. Catal., 37, 424, 1975
  25. Schon G, Surf. Sci., 35, 96, 1973
  26. Schwab GM, Kanungo SB, J. Phys. Chem., 107, 109, 1977
  27. Sermon PA, Bond GC, Catal. Rev.-Sci. Eng., 8, 211, 1974
  28. Sinha APB, Sanjana NR, Biswas AB, J. Phys. Chem., 62, 191, 1958
  29. Sivaraj CSivaraj C, Reddy BM, Rao PK, Appl. Catal., 45, L11, 1988
  30. Sivaraj C, Srinvas ST, Rao VN, Rao PK, J. Mol. Catal., 60, L23, 1990
  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
  33. Vandenberghe RE, Phys. Stat. Sol., 50, K85, 1978
  34. Veprek S, Cocke DL, Kehl S, Oswald HR, J. Catal., 100, 250, 1986
  35. Wagner CD, Riggs WH, Davis LE, Mullenberg GE, "Handbook of X-ray Photoelectron Spectroscopy," Perkin-Elmer Co., Minnesota, 1979
  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