Zirconia에 담지된 산화텅스텐 촉매의 산 성질과 산 촉매활성

손종락; 박만영

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.2, 247-251, April, 1999

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Zirconia에 담지된 산화텅스텐 촉매의 산 성질과 산 촉매활성

Acidic Properties of Tungsten Oxide Supported on Zirconia and Catalytic Activities for Acid Catalysisp

손종락, 박만영

초록

분말 Zr(OH)₄를 ammonium metatungstate수용액에 넣어서 증발 건조시킨 후 공기중 높은 온도에서 소성하여 zirconiz에 담지된 WO₃촉매를 제조하였다. ZrO₂에 소량 (1 wt%)의 WO₃를 첨가하면 촉매의 산의 양과 세기가 급격하게 증가하였으며 촉매는 Lewis산과 Bronsted산 모두를 가지고 있었다. 이와 같은 WO₃/ZrO₂촉매의 큰 산의 세기와 많은 산의 양은 WO₃와 ZrO₂의 상호작용으로 생성된 W=O결합의 성질에 기인하였다. 2-propanol의 탈수반응에서는 WO₃함량이 20 wt%이고 973K에 소성한 촉매가 최대의 촉매활성을 보였으며 cumene의 탈알킬화 반응에서는 WO₃함량이 15wt%이고 1023 K에서 소성한 촉매가 최대 촉매활성을 나타내었다. 2-propanol의 탈수반응에서 촉매활성의 변화는 대략적으로 촉매의 산의 양의 변화와 상호 관련되었다.

Tungsten oxide supported on zirconia was prepared by drying powdered Zr(OH)₄ with ammonium metatungstate aqueous solution, followed by calcining in air at high temperature. Upon the addition of only small amount of tungsten oxide (1 wt% WO₃) to ZrO₂, both the acidity and acid strength of catalyst increased remarkably, showing the presence of Bronsted and Lewis acid sites on the surface of WO₃/ZrO₂. The high acid strength and large amount of acid sites on WO₃/ZrO₂ were due to the presence of the W=O bond nature of complex formed by the interaction between WO₃ and ZrO₂. The catalyst containing 20 wt % WO₃, calcined at 973 K, showed the highest catalytic activity for the 2-propanol dehydration, while the catalyst containing 15 wt % WO₃, calcined at 1023 K, exhibited the highest catalytic activity for the cumene dealkylation. For the 2-propanol dehydration the catalytic activities of WO₃/ZrO₂ catalysts were roughly correlated with their acidities.

Keywords:Tungsten Oxide;Acidic Properties;Zirconia;2-propanol dehydration;Cumene dealkylation

[References]

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Lange FC, Cheung TK, Gates BC, Catal. Lett., 41(1-2), 95 (1996)
Zarkalis AS, Hsu CY, Gates BC, Catal. Lett., 29(1-2), 235 (1994)
Hosoi T, Shimadzu T, Ito S, Baba S, Takaoka H, Imai T, Yokoyama N, Prepr. Symp. Div. Petr. Chem. American Chemical Society, Los Angeles, 562 (1988)
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Sohn JR, Cho SG, Pae YI, Hayashi S, J. Catal., 159(1), 170 (1996)
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Olah FGA, Prakash GKS, Sommer J, Science, 206, 13 (1979)
Sohn JR, Kim HJ, J. Catal., 101, 428 (1986)
Parry EP, J. Catal., 2, 371 (1963)
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[Referenced By]

[1] Cheung TK, Ditri JL, Lange FC, Gates BC, Catal. Lett., 31(2-3), 153 (1995)

[2] Tanabe K, Misono M, Ono Y, Hattori H, "New Solid Acids and Bases," Elsevier Science, Amsterdam (1989)

[3] Arata K, Adv. Catal., 37, 165 (1990)

[4] Ward DA, Ko EI, J. Catal., 150(1), 18 (1994)

[5] Kustov LM, Kazansky VB, Figueras F, Tichit D, J. Catal., 150(1), 143 (1994)

[6] Hsu CY, Heimbuch CR, Armes CT, Gates BC, J. Chem. Soc.-Chem. Commun., 1645 (1992)

[7] Lange FC, Cheung TK, Gates BC, Catal. Lett., 41(1-2), 95 (1996)

[8] Zarkalis AS, Hsu CY, Gates BC, Catal. Lett., 29(1-2), 235 (1994)

[9] Hosoi T, Shimadzu T, Ito S, Baba S, Takaoka H, Imai T, Yokoyama N, Prepr. Symp. Div. Petr. Chem. American Chemical Society, Los Angeles, 562 (1988)

[10] Ebitani K, Konishi J, Hattori H, J. Catal., 130, 257 (1991)

[11] Hino M, Arata K, J. Chem. Soc.-Chem. Commun., 1259 (1987)

[12] Larsen G, Lotero E, Parra RD, "Proc. 11th Int. Conger. Catal," 533 (1996)

[13] Basrur AG, Patwardham SR, Vyas SN, J. Catal., 127, 86 (1991)

[14] Murrell LL, Grenoble DC, Baker RTK, Prestridge EB, Fung SC, Hianelli RR, Cramer SP, J. Catal., 79, 207 (1983)

[15] Roosnaiern AJ, Koster D, Moi JC, J. Phys. Chem., 84, 3075 (1980)

[16] Karakonstantis L, Bourikas K, Lycourghiotis A, J. Catal., 162(2), 295 (1996)

[17] Grunert W, Shpiro ES, Feldhaus R, Anders K, Antoshin GV, Minachev KM, J. Catal., 107, 522 (1987)

[18] Sohn JR, Park MY, J. Ind. Eng. Chem., 4(2), 84 (1998)

[19] Sohn JR, Ryu SG, Langmuir, 9, 126 (1993)

[20] Sohn JR, Cho SG, Pae YI, Hayashi S, J. Catal., 159(1), 170 (1996)

[21] Sohn JR, Lee SY, Appl. Catal. A: Gen., 164(1-2), 127 (1997)

[22] Olah FGA, Prakash GKS, Sommer J, Science, 206, 13 (1979)

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

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

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

[26] Sohn JR, Jang HJ, Park MY, Park EH, Park SE, J. Mol. Catal., 93, 149 (1994)