Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Effects of Acid Treatment of SAPO-34 on the Catalytic Lifetime and Light Olefin Selectivity during DTO Reaction

DTO 반응에서 촉매수명과 경질 올레핀 선택도에 미치는 SAPO-34의 산 처리 효과

  • Choi, Ki-Hwan (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University) ;
  • Lee, Dong-Hee (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University) ;
  • Kim, Hyo-Sub (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University) ;
  • Park, Chu-Sik (Hydrogen and fuel cell department, Korea Institute of Energy Research) ;
  • Kim, Young-Ho (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University)
  • 최기환 (충남대학교 정밀응용화학과) ;
  • 이동희 (충남대학교 정밀응용화학과) ;
  • 김효섭 (충남대학교 정밀응용화학과) ;
  • 박주식 (한국에너지기술연구원 수소연료전지연구단) ;
  • 김영호 (충남대학교 정밀응용화학과)
  • Received : 2015.02.11
  • Accepted : 2015.03.10
  • Published : 2015.04.10
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Abstract

Effects of the post-acid treatment of SAPO-34 sample by hydrochloric acid were investigated to enhance the catalytic performance in DTO reaction. Uniformly sized SAPO-34 samples with cubic-like morphology were prepared by hydrothermal method using TEAOH and DEA as the structure directing agents. It was modified in terms of the HCl concentration and treating time. As a result, the total surface area and micropore volume for the well modified samples increased and the total acid site was somewhat decreased along with the erosion of the external surface. Especially, the catalytic lifetime and light olefins selectivity for acid treated SAPO-0.2 M (3 h) samples were considerably enhanced compared with those of untreated SAPO-34 samples. It indicates that the deactivation by coke formation proceeds mainly at the pore entrance on the external surface. Therefore, the acid treatment was confirmed to be a simple method which can significantly improve the catalytic performance by modifying the external surface of SAPO-34 catalyst.

DTO (dimethyl ether to olefin) 반응에서 촉매 성능을 향상하기 위하여 염산에 의한 SAPO-34 시료의 산 처리 영향을 연구했다. 먼저 TEAOH (tetraethylammonium hydroxide)와 DEA (diethylamine)를 구조유도제로 사용하여 정육면체 형태를 갖는 균일한 크기의 SAPO-34 시료를 수열 합성했다. 제조된 촉매는 염산의 농도 및 처리 시간을 변수로 하여 개조되었다. 그 결과, 우수하게 개조된 시료는 외부 표면의 침식과 함께 총 비표면적 및 마이크로 세공부피가 증가하였으며, 산점량이 다소 감소하는 것으로 나타났다. 특히, 개조된 SAPO-0.2 M (3 h) 시료 상에서의 DTO 반응에서 촉매 수명과 경질 올레핀 선택성은 모체 SAPO-34 시료와 비교하여 크게 향상되었다. 이것은 코크 형성에 의한 비활성화가 주로 결정 외부 표면의 기공 입구에서 상대적으로 빠르게 진행된다는 것을 의미한다. 따라서 산 처리는 SAPO-34 촉매의 외부 표면을 개조함으로써 촉매의 성능을 향상할 수 있는 단순한 방법임을 확인했다.

Keywords

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  1. DTO 반응에 미치는 SAPO-34 촉매의 식각 처리 효과 vol.32, pp.1, 2015, https://doi.org/10.14478/ace.2020.1091