n-Hexane반응에 대한 Zirconia에 담지된 산화크롬의 촉매성질

손종락; 류삼곤; 배영일

HWAHAK KONGHAK, Vol.30, No.6, 725-730, December, 1992

Export Citation

n-Hexane반응에 대한 Zirconia에 담지된 산화크롬의 촉매성질

Catalytic Properties of Chromium Oxide Supported on Zirconia for n-Hexane Reaction

손종락, 류삼곤, 배영일

초록

분말의 Zr(OH)₄를 (NH₄)₂CrO₄수용액에 함침시킨 후 공기 중에 소성하여 지르코니아에 담지된 산호크롬 촉매를 제조하였다. 제조된 CrO_x/ZrO₂ 촉매상에 n-hexane을 반응시켜 촉매성질을 연구한 결과 크롬의 산화상태가 +6인 chromate 형태로 지르코니아 표면에 존재할 때는 강한 산점이 생성되어 n-hexane의 cracking 반응에 촉매활성을 나타내었다. 그러나 많은 양의 Cr⁺⁶ 종은 반응중에 n-hexane에 의하여 환원되어 Cr³⁺종으로 변화되었으며 Cr³⁺종은 n-hexane을 탈수소 고리화시켜 benzene을 생성하는 반응에 활성점으로 작용하였다. 환원된 Cr³⁺종은 O₂로 처리하면 다시 Cr⁶⁺종으로 되고 따라서 산회된 촉매는 cracking반응에 활성을 나타내었다.

Chromium oxide/zirconia catalysts were prepared by dry impregnation of powdered Zr(OH)₄ with aqueous solution of (NH₄)₂CrO₄ followed by calcining in air. The catalytic properties of prepared catalysts were investigated by reacting n-hexane as test material over catalysts. As a consequence it was found that Cr⁶⁺ species(as chromate) existing on the surface of catalyst was responsible for the formation of strong acid site and the cracking catalytic activity of n-hexane. However, the Cr⁶⁺ species was reduced to Cr³⁺ species during the catalytic reaction of n-hexane and the reduced Cr³⁺ species was acitive for the benzene formation due to the dehydrocylization of n-hexane. The reduced Cr³⁺species was reoxidized by treatment with O₂ and consequently the reoxidized catlyst exhibited catalytic activity for the cracking reaction of n-hexane.

[References]

Hogan JP, J. Polym. Sci., 8, 2637 (1970)
Holm VCF, Clark A, J. Catal., 11, 305 (1968)
Clark A, Catal. Rev.-Sci. Eng., 3, 145 (1969)
McDaniel MD, Adv. Catal., 33, 47 (1985)
Shelef M, Otto K, Gandhi H, J. Catal., 12, 361 (1968)
Kazansky VB, Boreskov GK, Kinet. Katal., 5, 434 (1964)
Myers DL, Lunsford JH, J. Catal., 99, 140 (1986)
Sohn JR, Han YH, HWAHAK KONGHAK, 26(4), 445 (1988)
Beck DD, Lunsford JH, J. Catal., 68, 121 (1981)
Eley DD, Rochester CH, Scurrell MS, J. Chem. Soc.-Faraday Trans., 69, 660 (1973)
Matsunaga Y, Bull. Chem. Soc. Jpn., 30, 868 (1957)
Rasko J, Solymosi F, J. Mol. Catal., 3, 305 (1977)
Iwasawa Y, Chiba T, Ito N, J. Catal., 99, 95 (1986)
Damyanov D, Vlaev L, Bull. Chem. Soc. Jpn., 56, 1841 (1983)
Peri JB, J. Phys. Chem., 78, 588 (1974)
Poole P, Kehl WL, MacIver DS, J. Catal., 1, 407 (1962)
Cimino A, Cordisch D, Febbraro S, Gazzoli D, Indovina V, Occhiuzzi D, Indovina V, Occhiuzzi M, Valigi M, J. Mol. Catal., 55, 23 (1989)
Ghiotti G, Chiorino A, Boccuzzi F, Surf. Sci., 251-252, 1110 (1991)
Hino M, Arata K, J. Chem. Soc.-Chem. Commun., 1356 (1987)
Livage J, Doi K, Mazieres C, J. Am. Ceram. Soc., 51, 349 (1968)
Lee BY, Inoue Y, Yasumori I, Bull. Chem. Soc. Jpn., 54, 13 (1981)
Hertl W, Langmuir, 5, 96 (1989)
Tseng SC, Jackson NJ, Ekerdt JG, J. Catal., 109, 284 (1988)
Abe H, Maruya K, Domen K, Onishi T, Chem. Lett., 1875 (1984)
He MY, Ekerdt JG, J. Catal., 90, 17 (1984)
Jackson NB, Ekerdt HG, J. Catal., 101, 90 (1986)
Onishi T, Abe H, Maruya K, Domen K, J. Chem. Soc.-Chem. Commun., 617 (1985)
Sohn Jr, Ryu SG, Park MY, Pae YI, Bull. Korean Chem. Soc., 13, 605 (1992)
Sohn JR, Ryu SG, Langmuir, in press (1992)
Sohn JR, Ryu SG, Pae YI, HWAHAK KONGHAK, 30(5), 586 (1992)
Decanio SJ, Sohn JR, Fritz PO, Lunsford JH, J. Catal., 101, 132 (1986)
Sohn JR, Decanio SJ, Fritz PO, Lunsford JH, J. Phys. Chem., 90, 4847 (1986)
Grunert W, Saffert W, Feldhaus R, Anders K, J. Catal., 99, 149 (1986)
Merryfield M, McDaniel M, Parks G, J. Catal., 77, 348 (1982)
Welch MB, McDaniel MP, J. Catal., 82, 110 (1983)
Hill W, Ohlmann G, J. Catal., 123, 147 (1990)
Leonard MB, Carrick WL, J. Org. Chem., 33, 616 (1968)
Hammett LP, Deyrup AJ, J. Am. Chem. Soc., 54, 2721 (1932)

[1] Hogan JP, J. Polym. Sci., 8, 2637 (1970)

[2] Holm VCF, Clark A, J. Catal., 11, 305 (1968)

[3] Clark A, Catal. Rev.-Sci. Eng., 3, 145 (1969)

[4] McDaniel MD, Adv. Catal., 33, 47 (1985)

[5] Shelef M, Otto K, Gandhi H, J. Catal., 12, 361 (1968)

[6] Kazansky VB, Boreskov GK, Kinet. Katal., 5, 434 (1964)

[7] Myers DL, Lunsford JH, J. Catal., 99, 140 (1986)

[8] Sohn JR, Han YH, HWAHAK KONGHAK, 26(4), 445 (1988)

[9] Beck DD, Lunsford JH, J. Catal., 68, 121 (1981)

[10] Eley DD, Rochester CH, Scurrell MS, J. Chem. Soc.-Faraday Trans., 69, 660 (1973)

[11] Matsunaga Y, Bull. Chem. Soc. Jpn., 30, 868 (1957)

[12] Rasko J, Solymosi F, J. Mol. Catal., 3, 305 (1977)

[13] Iwasawa Y, Chiba T, Ito N, J. Catal., 99, 95 (1986)

[14] Damyanov D, Vlaev L, Bull. Chem. Soc. Jpn., 56, 1841 (1983)

[15] Peri JB, J. Phys. Chem., 78, 588 (1974)

[16] Poole P, Kehl WL, MacIver DS, J. Catal., 1, 407 (1962)

[17] Cimino A, Cordisch D, Febbraro S, Gazzoli D, Indovina V, Occhiuzzi D, Indovina V, Occhiuzzi M, Valigi M, J. Mol. Catal., 55, 23 (1989)

[18] Ghiotti G, Chiorino A, Boccuzzi F, Surf. Sci., 251-252, 1110 (1991)

[19] Hino M, Arata K, J. Chem. Soc.-Chem. Commun., 1356 (1987)

[20] Livage J, Doi K, Mazieres C, J. Am. Ceram. Soc., 51, 349 (1968)

[21] Lee BY, Inoue Y, Yasumori I, Bull. Chem. Soc. Jpn., 54, 13 (1981)

[22] Hertl W, Langmuir, 5, 96 (1989)

[23] Tseng SC, Jackson NJ, Ekerdt JG, J. Catal., 109, 284 (1988)

[24] Abe H, Maruya K, Domen K, Onishi T, Chem. Lett., 1875 (1984)

[25] He MY, Ekerdt JG, J. Catal., 90, 17 (1984)

[26] Jackson NB, Ekerdt HG, J. Catal., 101, 90 (1986)

[27] Onishi T, Abe H, Maruya K, Domen K, J. Chem. Soc.-Chem. Commun., 617 (1985)

[28] Sohn Jr, Ryu SG, Park MY, Pae YI, Bull. Korean Chem. Soc., 13, 605 (1992)

[29] Sohn JR, Ryu SG, Langmuir, in press (1992)

[30] Sohn JR, Ryu SG, Pae YI, HWAHAK KONGHAK, 30(5), 586 (1992)

[31] Decanio SJ, Sohn JR, Fritz PO, Lunsford JH, J. Catal., 101, 132 (1986)

[32] Sohn JR, Decanio SJ, Fritz PO, Lunsford JH, J. Phys. Chem., 90, 4847 (1986)

[33] Grunert W, Saffert W, Feldhaus R, Anders K, J. Catal., 99, 149 (1986)

[34] Merryfield M, McDaniel M, Parks G, J. Catal., 77, 348 (1982)

[35] Welch MB, McDaniel MP, J. Catal., 82, 110 (1983)

[36] Hill W, Ohlmann G, J. Catal., 123, 147 (1990)

[37] Leonard MB, Carrick WL, J. Org. Chem., 33, 616 (1968)

[38] Hammett LP, Deyrup AJ, J. Am. Chem. Soc., 54, 2721 (1932)