산화크롬-질코니아 촉매의 산화-환원거동

손종락; 류삼곤

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.4, 663-669, December, 1992

Export Citation

산화크롬-질코니아 촉매의 산화-환원거동

Redox Behavior of Chromium Oxide-Zirconia Catalyst

손종락, 류삼곤

초록

분말의 Zr(OH)₄를 (NH₄)₂CrO₄ 수용액에 함침시킨 후 공기중에 소성하여 질코니아에 담지된 산화크롬 촉매를 제조하였다. 제조된 CrO_x/ZrO₂ 촉매상에 cumene을 반응시켜 산화-환원 거동을 연구한 결과 크롬의 산화상태가 +6인 chromate형태로 질코니아 표면에 존재할 때는 강한 산점이 생성되어 cumene의 탈알킬화 반응에 촉매활성을 나타내었다. 그러나 많은 양의 Cr⁶⁺종은 반응중에 탈수소로 생성된 H₂에 의하여 환원되어 Cr³⁺종으로 변환되었으며 Cr³⁺종은 cumene 을 탈수소화시켜 α-methyl styrene을 생성하는 반응에 활성점으로 작용하였다. 환원된 C³⁺종은 O₂로 처리하면 다시 Cr⁶⁺종으로 되고 따라서 산화된 촉매는 cumene의 탈알킬화 반응에 활성을 나타내었다.

Chromium oxide/zirconia catalysts were prepared by dry impregnation of Zr(OH)₄ powder with aqueous solution of (NH₄)₂CrO₄ followed by calcining in air. The redox behavior of prepared catalysts were investigated by reacting cumene as test material over catalysts. As a result it was found that Cr⁶⁺ species(as chromate) on the surface of catalyst was responsible for the formation of strong acid site and the catalytic activity for the dealkylation of cumene. How ever, much of the Cr⁶⁺ species was reduced to Cr³⁺ species by H₂ formed during the catalytic reaction of cumene and the reduced Cr³⁺ species was an active site for dehydrogenation of cumene to form α-methyl styrene. The reduced Cr³⁺ species was also reoxidized to a Cr⁶⁺ species after treatment with O₂ and consequently the deoxidized catalyst exhibited catalytic activity for the dealkylation reaction of cumene.

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[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. Catal., 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. A-Chem., 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)

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[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)

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[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., in press (1992)

[29] Sohn JR, Ryu SG, Langmuir, submitted for publication (1992)

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[31] Decanio SJ, Sohn JR, Fritz PP, 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, Ohimann G, J. Catal., 123, 147 (1990)

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

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