Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Effect of Composition of γ-Al2O3/SiO2 Mixed Support on Fischer-Tropsch Synthesis with Iron Catalyst

철 기반 촉매의 Fischer-Tropsch 합성에서 γ-Al2O3/SiO2 혼합 지지체 조성의 영향

  • Min, Seon Ki (Department of Energy, Materials & Chemical Engineering, Korea University of Technology & Education) ;
  • No, Seong-Rae (Department of Energy, Materials & Chemical Engineering, Korea University of Technology & Education) ;
  • You, Seong-sik (Department of Energy, Materials & Chemical Engineering, Korea University of Technology & Education)
  • 민선기 (한국기술교육대학교 에너지.신소재.화학공학부) ;
  • 노성래 (한국기술교육대학교 에너지.신소재.화학공학부) ;
  • 유성식 (한국기술교육대학교 에너지.신소재.화학공학부)
  • Received : 2017.02.28
  • Accepted : 2017.03.21
  • Published : 2017.06.01
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Abstract

Fischer-Tropsch synthesis is the technology of converting a syngas (CO+$H_2$) derived from such as coal, natural gas and biomass into a hydrocarbon using a catalyst. The catalyst used in the Fischer-Tropsch synthesis consists of active metal, promoter and support. The types of these components and composition affect the reaction activity and product selectivity. In this study, we manufactured an iron catalyst using ${\gamma}-Al_2O_3/SiO_2$ mixed support (100/0 wt%, 75/25 wt%, 50/50 wt%, 25/75 wt%, 0/100 wt%) by an impregnation method to investigate how the composition of ${\gamma}-Al_2O_3/SiO_2$ mixed support effects on the reaction activity and product selectivity. The physical properties of catalyst were analyzed by $N_2$ physical adsorption and X-Ray diffraction method. The Fischer-Tropsch synthesis was conducted at $300^{\circ}C$, 20bar in a fixed bed reactor for 60h. According to the results of the $N_2$ physical adsorption analysis, the BET surface area decreases as the composition of ${\gamma}-Al_2O_3$ decreases, and the pore volume and pore average diameter increase as the composition of ${\gamma}-Al_2O_3$ decreases except for the composition of ${\gamma}-Al_2O_3/SiO_2$ of 50/50 wt%. By the results of the X-Ray diffraction analysis, the particle size of ${\alpha}-Fe_2O_3$ decreases as the composition of ${\gamma}-Al_2O_3$ decreases. As a result of the Fischer-Tropsch synthesis, the CO conversion decreases as the composition of ${\gamma}-Al_2O_3$ decreases, and the selectivity of C1-C4 decreases until the composition of ${\gamma}-Al_2O_3$ was 25 wt%. In contrast, the selectivity of C5+ increases until the composition of ${\gamma}-Al_2O_3$ is 25 wt%.

Fischer-Tropsch 합성(F-T 합성)은 석탄, 바이오매스, 천연가스 등을 개질하여 얻은 합성 가스(CO, $H_2$)를 촉매를 이용하여 탄화수소로 전환 하는 기술이다. Fischer-Tropsch 합성에 이용되는 촉매는 활성 금속, 조촉매, 지지체로 구성되는데 이들의 종류와 조성은 반응의 활성 및 생성물 선택도에 영향을 미친다. 본 연구에서는 ${\gamma}-Al_2O_3$와 $SiO_2$ 혼합 지지체의 조성이 Fiscsher-Tropsch 반응의 활성과 생성물 선택도에 미치는 영향을 알아 보기위해, ${\gamma}-Al_2O_3/SiO_2$ 혼합 지지체를(100/0 wt%, 75/25 wt%, 50/50 wt%, 25/75 wt%, 0/100 wt%) 이용하여 함침(impregnation)법으로 철 촉매를 제조하였다. 촉매의 물리적 특성은 질소 물리 흡착 법과 X-선 회절 분석법을 통해 분석 하였고, 고정층 반응기에서 Fischer-Trosch 반응을 $300^{\circ}C$, 20bar에서, 60시간 동안 수행 하였다. 촉매의 물리적 특성 분석 결과 촉매의 BET 표면적은 ${\gamma}-Al_2O_3$의 조성이 감소함에 따라 감소하였으며, 촉매 기공의 부피 및 평균 크기는 지지체 조성이 ${\gamma}-Al_2O_3/SiO_2$ (50/50 wt%)인 경우를 제외 하고 증가하는 경향을 보였다. 또한, X-선 회절 분석법을 통해 ${\alpha}-Fe_2O_3$의 입자 크기를 계산한 결과 ${\gamma}-Al_2O_3$의 조성이 감소함에 따라 입자 크기가 감소 하였다. Fischer-Tropsch 합성 결과 ${\gamma}-Al_2O_3$의 조성이 감소함에 따라 CO 전환율은 감소 하였으며, C1-C4의 선택도는 ${\gamma}-Al_2O_3$의 조성이 25 wt%일 때 까지 감소하였으며 이와 반대로, C5+의 선택도는 ${\gamma}-Al_2O_3$의 조성이 25 wt%일 때 까지 증가 하였다.

Keywords

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