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Received September 1, 2011
Accepted September 22, 2011
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수열특성 및 기계적 안정성의 개선으로 슬러리상 CSTR에 적합한 P 첨가 알루미나 기반의 Fischer-Tropsch 합성용 코발트 촉매
Phosphorus Modified Co/Al2O3 Fischer-Tropsch Catalyst for a Slurry Phase CSTR with Enhanced Hydrothermal and Mechanical Stability
Gyu-In Jung1 2
Kyoung-Su Ha1†
Seon-Ju Park1
Du-Eil Kim1
Min-Hee Woo1
Ki-Won Jun1
Jong-Wook Bae3
Yong Kang2†
1한국화학연구원 그린화학촉매연구센터, 305-600 대전광역시 유성구 신성로 19 2충남대학교 화학공학과, 305-764 대전시 유성구 궁동 220 3성균관대학교 화학공학과, 440-746, 경기도 수원시 장안구 천천동 300
1Research Center for Green Catalysis, Korea Research Institute of Chemical Technology, 19 Sinseong-ro, Yuseong-gu, Daejeon 305-600, Korea 2School of Chemical Engineering, Chungnam National University, 220 Gung-dong, Yuseong-gu, Daejeon 305-764, Korea 3Department of Chemical Engineering, Sungkyunkwan University, 300 Chunchun-dong, Jangan-gu, Suwon-si, Gyeonggi-do 440-746, Korea
filoseus@krict.re.kr
Korean Chemical Engineering Research, April 2012, 50(2), 229-237(9), NONE Epub 30 March 2012
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Abstract
Fischer-Tropsch 합성용 Co/Al2O3 촉매에서 알루미나 지지체에 인산 용액으로 알루미나 표면을 개질하여 촉매적 활성은 물론이고, 기계적 강도와 수열 안정성을 개선하였다. FT-IR과 같은 촉매 표면 분석법을 통하여 P 첨가로 알루미나 표면에 AlPO4 상이 생성되어 촉매인 코발트와 지지체인 알루미나 사이의 상호작용이 약화되어 촉매의 환원도가 높아졌음을 보였다. 이에 따른 촉매성능을 평가하기 위하여 C5+ productivity와 turnover frequency를 계산하였다. 또한, 2 wt.%P 첨가 알루미나를 대상으로 지지체의 소성온도가 촉매활성에 미치는 영향도 살펴보았다. 한편, 고온 가압 하에서 물을 이용하여 P 첨가 알루미나(P-알루미나)를 지지체로 한 촉매의 수열 특성을 살펴보았으며, 실험 전후의 XRD 패턴을 분석함으로써 P 첨가 알루미나 기반 촉매가 수열 안정성이 우수하다는 것을 증명하였다. 뿐만 아니라, 촉매의 기계적 강도를 측정하기 위하여 유동화 반응기를 직접 제작하여 P-알루미나 기반 촉매의 P 함량이 증가할수록 마모도가 감소함을 확인하였다. 촉매 활성, 수열 안정성, 그리고 기계적 강도를 모두 고려하면, 알루미나에 첨가된 P의 함량이 1~2 wt.% 이고, 지지체를 500 ℃에서 소성하여 제조한 촉매가 가장 좋은 성능을 보였다.
Phosphorus was incorporated into Co/Al2O3 catalyst for FTS by impregnating an acidic precursor, phosphoric acid, in γ-Al2O3 support to improve the mechanical strength, the hydrothermal stability of the catalyst particle, and the catalytic performance as well. Surface characterization techniques such as FT-IR revealed that AlPO4 phase was generated on the surface of the P-modified catalyst. The addition of phosphorus was found to alleviate the interaction between cobalt and alumina surface, and to increase reducibility of catalyst. The catalytic activity such as C5+ productivity and turnover frequency (TOF) was calculated to evaluate catalytic performance. The influence of calcination temperature of the Al2O3 containing 2 wt.% P on the catalytic performance was also investigated. Through hydrothermal stability test and XRD analysis, the P-modified catalyst had strong resistant to the pressurized and hot H2O. The mechanical strength of the P-modified catalyst was also examined through an in-house fluidized-bed vessel, and it was found that the catalyst fragmentation could be successfully suppressed with P. Taken as a whole, the best performance was shown to be at 1~2 wt.% P in alumina and at the calcination temperature of 500 ℃.
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Iwamoto R, Grimblot J, Adv. Catal., 44, 417 (1999)
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