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12-헤테폴리산 동염 촉매의 특성과 Methanol의 산화반응에 대한 활성

Properties of Cupric Salt Catalysts of 12-Heteropoly Acids and Catalytic Activity for the Oxidation of Methanol

HWAHAK KONGHAK, December 1986, 24(6), 485-493(9), NONE
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Abstract

고정층 상압 유통식 반응 장치와 12-헤테로폴리산 동염 촉매를 이용하여, methanol의 산화반응을 조사하였다. 열분석, IR에 의한 조사, 전처리 gas의 영향, NH3의 흡착 및 H2에 의한 환원반응 등을 통하여 촉매의 특성을 검토하였다. 조제하여 사용한 촉매들은 모두 Keggin구조를 이루고 있었으며, 폴리원자와 Cu2+의 함유도에 따라 촉매의 산성도와 산화능은 영향을 받았다. 폴리원자가 Mo인 촉매는 W인 촉매에 비하여 산성도는 작지만 산화능은 크며, Cu2+의 함유도가 증가함에 따라 촉매의 산성도는 감소하고 산화능은 증가하는 경향을 보였다. 상대적으로 산성도가 약하고 산화능이 강한 촉매에서는, methanol의 전화율은 낮지만 산화 생성물인 formaldehyde의 선택률이 매우 우수하였다. 한편 산성도가 강하고 산화능이 약한 촉매의 경우, methanol의 전화률은 높지만 강한 산점에 의한 탈수반응이 진행되므로 formaldehyde의 선택률은 낮고 dimethylether의 선택률이 매우 높았다.
The vapor phase oxidation of methanol over cupric salt catalysts of 12-heteropoly acids was studied in a fixed bed flow reactor at atmospheric pressure. The catalysts prepared were characterized by thermal analysis. IR absorption, ammonia adsorption, H2 reduction, and by pretreating with various gases. Both acidity and oxidation ability of catalysts were affected by polyatom and the content of Cu2+ cation. The conversion of methanol over the catalysts with Mo as polyatom was much lower than that over the catalysts with W as polyatom, but the selectivity of formaldehyde was much higher; methanol was mainly dehydrated to dimethylether by strong acidic sites over the catalysts with W as polyatom. Increasing the content of Cu2+ cation in CuxH3-2xPMo catalysts, the conversion of methanol was decreased, but the selectivity of formaldehyde was increased.

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