Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Effect of Metal Addition and Silica/Alumina Ratio of Zeolite on the Ethanol-to-Aromatics by Using Metal Supported ZSM-5 Catalyst

금속담지 ZSM-5 촉매를 사용한 에탄올로부터 방향족 화합물 제조에 관한 제올라이트의 금속성분 및 실리카/알루미나 비의 영향

  • Kim, Han-Gyu (Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology) ;
  • Yang, Yoon-Cheol (Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology) ;
  • Jeong, Kwang-Eun (Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology) ;
  • Kim, Tae-Wan (Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology) ;
  • Jeong, Soon-Yong (Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology) ;
  • Kim, Chul-Ung (Research Center for Green Catalysis, Division of Green Chemistry and Engineering Research, Korea Research Institute of Chemical Technology) ;
  • Jhung, Sung Hwa (Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University) ;
  • Lee, Kwan-Young (Department of Chemical and Biological Engineering, Korea University)
  • 김한규 (한국화학연구원 그린화학연구단) ;
  • 양윤철 (한국화학연구원 그린화학연구단) ;
  • 정광은 (한국화학연구원 그린화학연구단) ;
  • 김태완 (한국화학연구원 그린화학연구단) ;
  • 정순용 (한국화학연구원 그린화학연구단) ;
  • 김철웅 (한국화학연구원 그린화학연구단) ;
  • 정성화 (경북대학교 화학과) ;
  • 이관영 (고려대학교 화학공학과)
  • Received : 2013.04.01
  • Accepted : 2013.05.01
  • Published : 2013.08.01
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Abstract

The catalytic conversion of ethanol to aromatic compounds ETA was studied over ZSM-5 heterogeneous catalysts. The effect of reaction temperature, weight hourly space velocity (WHSV), and addition of water and methanol, which are the potential impurities of bio-ethanol, on the catalytic performance was investigated in a fixed bed reactor. Commercial ZSM-5 catalysts having different Si/$Al_2$ ratios of 23 to 280 and modified ZSM-5 catalysts by addition of metal (Zn, La, Cu, and Ga) were used for the activity and stability tests in ETA reaction. The catalysts were characterized with ammonia temperature programmed desorption ($NH_3$-TPD) and nitrogen adsorption-desorption techniques. The results of catalytic performance revealed that the optimal Si/$Al_2$ ratio of ZSM-5 is about 50~80 and the selectivity to aromatic compounds decreases in the order of Zn/La > Zn > La > Cu > Ga for the modified ZSM-5 catalysts. Among these catalysts from the ETA reaction, Zn-La/ZSM-5 showed the best catalytic performance for the ETA reaction. The selectivity to aromatic compounds was 72% initially and 56% after 30 h over the catalysts at reaction temperature of $437^{\circ}C$ and WHSV of $0.8h^{-1}$.

고정층 반응기를 사용하여 상압에서 에탄올로부터 방향족화합물 제조에 관한 ZSM-5 제올라이트의 금속성분 및 실리카/알루미나 비의 영향을 고찰하였으며, 반응온도, 중량공간속도(WHSV), 반응물인 에탄올에 물 및 메탄올 첨가 영향도 검토하였다. 촉매로는 Si/$Al_2$ 비율이 23~280 범위의 상용 ZSM-5에 Zn, La, Cu, Ga 성분을 함침시켜 촉매 활성 및 안전성 테스트에 사용하였다. 촉매의 특성분석을 위해 암모니아 승온탈착 실험($NH_3$-TPD)과 질소 흡-탈착실험을 수행하였다. 실험결과, 방향족화합물의 선택도에 관한 ZSM-5에 함침한 금속성분과 ZSM-5의 Si/$Al_2$비에 크게 영향을 받았는데, 함침금속은 Zn-La > Zn > La > Cu > Ga 순으로 감소하였으며, ZSM-5의 적절한 산점을 가진 Si/$Al_2$=50, 80에서 가장 우수하였다. 최적 반응온도($437^{\circ}C$)와 공간속도($0.8h^{-1}$)에서 방향족화합물의 선택도는 초기 72%에서 30시간 이후 56%로 서서히 감소하는 경향을 나타내었다.

Keywords

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