자일렌 산화반응 촉매의 산특성과 반응성에 관한 연구

김택중; 김영호; 이호인

Journal of the Korean Industrial and Engineering Chemistry, Vol.2, No.4, 330-339, December, 1991

Export Citation

자일렌 산화반응 촉매의 산특성과 반응성에 관한 연구

A Study on the Acid Property and the Activity of Xylene Oxidation Catalyst

김택중, 김영호, 이호인

초록

V₂O₅-TiO₂/SiO₂ 촉매를 제조하여 그 산특성을 조사하였고, 동 촉매상에서 o-자일렌의 무수프탈산으로의 부분산화반응에 대한 활성측정을 병행하여 촉매의 산특성과 반응성과의 연관성을 알아보았다. V₂ O₅ 촉매는 V=O로 추정되는 약산점과 V-O-V로 추정되는 강산점을 가지고 있었으며, 소성온도가 높아질수록 약산점의 양이 감소하였다. V₂O₅-TiO₂/SiO₂ 촉매의 경우 약산점이 크게 나타났으며, 그 양은 SiO₂의 담지량이 20 mole% 일 때 최대치를 보였고 그 이상에서 일정하였다. 한편, o-자일렌 부분산화반응에서 V₂O₅-TiO₂/SiO₂ 는 V₂O₅/SiO₂ 에 비해 전체 전환율 및 무수프탈산으로의 선택도를 크게 증가시켰으며, V₂ O₅-TiO₂/SiO₂에서 TiO₂의 양이 증가할 경우 전체 전환율은 증가하였으나 무수프탈산으로의 선택도는 크게 변하지 않았다. V=O로 추정되는 약산점은 o-자일렌을 약하게 흡착함으로써 무수프탈산으로의 부분산화반응을, V-O-V로 추정되는 강산점은 o-자일렌을 보다 강하게 흡착하여 C₁으로의 완전산화반응을 각각 유도함을 알 수 있었다.

The acid properties of V₂O₅-TiO₂/SiO₂ catalysts and the partial oxidation of o-xylene into phthalic anhydride had been investigated in order to relate the acid property of catalyst to the catalytic activity. V₂O₅ had both weak (V=O) and strong (V-O-V) acid sites which gave pyridine desorption peaks at 230℃ and 300 ℃, respectively, and the amount of weak acid sites at 230 ℃ decreased with the increase of calcination temperature. On the other hand, the amount of weak acid sites increased considerably by increasing the amount of TiO₂ to the V₂O₅-TiO₂/SiO₂, and the maximum value was shown at 20 and higher mole % of TiO₂ with respect to SiO₂. In the oxidation of o-xylene, V₂O₅-TiO₂/SiO₂ enhandced more the total conversion and the selectivity to phthalic anhydride than V₂O₅/SiO₂, and the higher TiO₂ ratio to V₂O₅ increased the total conversion but could not change the selectivity to phthalic anhydride. Weak acid sites (V=O) led o-xylene to partial oxidation producing phthalic anhydride by adsorbing o-xylene weakly, while acid sites (V-O-V) led it to total oxidation producing CO and CO₂ by adsorbing it strongly.

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[9] Takagikawai M, Soma M, Onishi T, Tamaru K, Can. J. Chem., 58, 2132 (1980)

[10] Miyata H, Nakagawa Y, Ono T, Kubokawa Y, Chem. Lett., 8, 1141 (1983)

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[12] Centi G, Trifiro F, Poli G, Appl. Catal., 19, 225 (1985)

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[19] Boag IF, Bacon DW, Downie J, J. Catal., 5, 125 (1966)

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[23] Saleh RH, Wachs IE, Appl. Catal., 31, 87 (1987)