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Y-제올라이트계 촉매를 이용한 나프탈렌류의 이소프로필화 반응
Isopropylation of Naphthalenes over Y-zeolite Catalyst
HWAHAK KONGHAK, June 1996, 34(3), 395-400(6), NONE
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Abstract
2-methylnaphthalene의 6-위치에 선택적으로 이소프로필기를 도입하기 위한 반응에서 Y-제올라이트계 촉매의 특성을 연구하였다. 촉매에 흡착된 암모니아 승온탈착실험과 반응 후 촉매에 생성된 코크의 승온산화실험에 의하여 촉매의 특성화를 하였다. 알킬화제로 프로필렌을 사용하였고, 이온교환법에 의하여 제조된 촉매를 사용하여 연속흐름식 미세반응기 및 상압에서 실험을 하였다. NaY-제올라이트는 반응 활성이 거의 없었으며, HY-제올라이트는 반응초기 90% 정도의 전환율을 보였으나 반응시간에 따라 급격한 비활성화를 나타냈다. Zn12+, Co2+, Ca2+ 및 Mg2+ 금속이온이 90% 이상 이온교환된 촉매(Zn/NaY, Co/NaY, Ca/NaY 및 Mg/NaY)는 HY 촉매에 비하여 비활성화가 크게 개선되었다. 이것은 반응 후 촉매에 형성된 코크의 TPO분석 결과에서 Zn/NaY에 생성된 코크의 양이 현저히 감소한 결과로 잘 설명할 수 있었다. Zn/Nay 촉매에 소량(1wt% 이하)의 tetraethyl orthosilicate(TEOS)를 증착시키거나 함침시킨 촉매도 비활성화가 약간 개선되었다. 그러나 Zn 등의 양이온 교환이나 TEOS가 처리된 촉매에서 2,6-체로의 선택도 개선은 없었다.
Selective catalytic isopropylation of 2-methylnaphthalene(2-MN) to obtain 2,6-dialky- lnaphthalene over Y-zeolite catalyst was studied in a continuous flow micro reactor under atmospheric pressure. NaY, HY and cation-exchanged Y-zeolite catylysts were characterized by temperature programmed desorption(TPD) with NH3 and the used catalysts by temperature programmed oxidation(TPO) of coke. HY-zeolite showed intially a high activity(about 90% conversion) and then was deactivated rapidly with time on stream. The catalysts ion-exchanged by Zn2+, Co2+, Ca2+ and Mg2+(Zn/NaY, Co/NaY, Ca/NaY and Mg/NaY) offered a remarkably improved stability, whcih was attribute to less amount of coke formed during reaction as shown in TPO results. The stability of Zn/NaY treated by chemical vapor deposition or impregnation of tetraethyl orthosilicate(TEOS) against deactivation was slightly enhanced. However, the selectivity to 2,6-dialkylnaphthalene was not improved by cation-exchange and TEOS treatment of Y-zeolite.
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