TiO2-SiO2 및 H2SO4으로 개질된 TiO2-SiO2의 촉매특성과 산 성질

손종락; 장향자

Journal of the Korean Industrial and Engineering Chemistry, Vol.1, No.1, 35-43, October, 1990

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TiO₂-SiO₂ 및 H₂SO₄으로 개질된 TiO₂-SiO₂의 촉매특성과 산 성질

Catalytic and Acidic Properties of TiO₂ -SiO₂ Unmodified and Modified with H₂SO₄

손종락, 장향자

초록

일련의 TiO₂ - SiO₂촉매를 TiCl₄와 NaSiO₃혼합용액을 공침전시켜 제조하였으며 이중 일부의 촉매는 1N H₂SO₄로 처리하여 촉매표면을 개질하였다. 개질된 촉매의 촉매활성은 개질 안된 촉매보다 높은 촉매활성을 나타내었으며 cumene dealkylation 반응에서 보다 2 - propanol dehydration 반응에서 더욱 효과가 크게 나타났다. 개질 안된 촉매의 상기 두 반응에 대한 촉매활성은 산의 양과 관계가 있었다. TiO₂ - SiO₂촉매는 비교적 많은 양의 약한 산자리와 작은 양의 강한 산자리를 가졌기 때문에 cumene dealkylation 반응에서 보다 2- propanol dealkylation 반응에 더 높은 촉매활성을 나타내었다. 촉매활성에 미치는 H₂SO₄의 개질효과는TiO₂ 함량에 비례 하였으며 92-TiO₂-SiO₂/SO₄²가 2- propanol dealkylation 반응에 가장 큰 촉매활성의 증가를 나타내었다.

A series of TiO₂-SiO₂ catalysts were prepared by coprecipitation from the mixed solution of titanium tetrachloride and sodium silicate. Some of the samples were treated with 1N H₂SO₄ and used as modified catalysts. The catalytic activities of modified catalysts were higher than those of unmodified catalysts, and the effect of modification on the catalytic activity was higher for 2 - propanol dehydration than for cumene dealkylation. The catalytic activity of unmodified catalysts was correlated with their acid amount for the above two reactions. As TiO₂-SiO₂ catalysts had relatively large amount of weak acid sites and small amount of strong acid sites, the catalytic activity for 2 - propanol dehydration was higher than that for cumene dealkylation. The effect of modification on catalytic activity increased with increasing TiO₂ content of the catalysts. Actually, 92-TiO₂-SiO₂/SO₄² had the highest increment in catalytic activity and 10-TiO₂-SiO₂/SO₄² had the lowest increment for the 2 - propanol dehydration.

[References]

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[Referenced By]

[1] Damon JP, Delmn B, Bonnier JM, J. Chem. Soc.-Faraday Trans., 11, 372 (1976)

[2] Scokort PO, Declerck FD, Sempels RE, J. Chem. Soc.-Faraday Trans., 10, 359 (1976)

[3] Lercher JA, Nollar H, J. Catal., 77, 152 (1982)

[4] Holm VCF, Bailey GC, Clark A, J. Phys. Chem., 63, 129 (1959)

[5] Murayama H, Meguro K, Bull. Chem. Soc. Jpn., 43, 2386 (1970)

[6] Shibata K, Kiyoura T, Kitagawa J, Sumiyashi T, Tanabe K, Bull. Chem. Soc. Jpn., 46, 2985 (1973)

[7] Tanabe K, Ito M, Sato M, Chem. Commun., 676 (1973)

[8] Dziko VA, "Binary Oxide Catalysts Based on Silica," Academic Press, New York, p. 422 - 432 (1970)

[9] Ito M, Hattori H, Tanabe K, J. Catal., 35, 225 (1974)

[10] Kaneko S, Tsukamoto K, Chem. Lett., 1425 (1983)

[11] Morrison C, Kiwi J, J. Chem. Soc.-Faraday Trans., 85, 1043 (1989)

[12] Tamele MW, Discuss. Faraday Soc., 8, 270 (1950)

[13] Johnson O, J. Phys. Chem., 59, 827 (1955)

[14] Tanabe K, Seiyama T, hueki K, "Metal Oxide and Mixed Oxides," Kodansa Tokyo (1978)

[15] Kurosaki A, Okajaki S, Nippon Kagaku Kaishi, 1816 (1976)

[16] Hino M, Arata K, Chem. Lett., 477 (1976)

[17] Hino M, Arata K, J. Chem. Soc.-Chem. Commun., 851 (1980)

[18] Hino M, Kobayashi S, Arata K, J. Am. Chem. Soc., 101, 6439 (1979)

[19] Hino M, Arata K, J. Chem. Soc.-Chem. Commun., 1148 (1979)

[20] Hino M, Arata K, Chem. Lett., 1259 (1979)

[21] Hino M, Arata K, Chem. Lett., 1483 (1985)

[22] Hino M, Arata K, J. Chem. Soc.-Chem. Commun., 112 (1985)

[23] Wang GW, Hattori H, Tanabe K, Chem. Lett., 277 (1983)

[24] Sohn JR, Kim HJ, J. Catal., 101, 428 (1986)

[25] Sohn JR, Kim HW, Kim JT, J. Mol. Catal., 41, 375 (1987)

[26] Sohn JR, Kim NW, Kim JT, Korean J. Chem. Eng., 4(1), 1 (1987)

[27] Sohn JR, Kim HW, J. Mol. Catal., 52, 361 (1989)

[28] Nakamoto K, "Infrared and Raman Spectra of Inorganic and Coordination Compounds," 3rd Edn., Wiley, New York (1964)

[29] Okamoto Y, Ohhara M, Maezawa A, Imanaka T, Teranishi S, J. Phys. Chem., 90, 2396 (1986)

[30] Hammett LP, Deyrup AJ, J. Am. Chem. Soc., 54, 272 (1932)

[31] Miura M, Kubota Y, Iwaki T, Takimoto K, Muraoka Y, Bull. Chem. Soc. Jpn., 42, 1476 (1969)

[32] Parry EP, J. Catal., 2, 371 (1963)

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