HWAHAK KONGHAK, Vol.40, No.1, 16-21, February, 2002
제자리 연소에 의한 열공급을 통한 메탄의 CO2 개질
CO2 Reforming of Methane with Heat Supply by In Situ Combustion
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초록
메탄 연소-CO2 개질반응은 흡열반응인 CO2 개질과 발열반응인 메탄 연소가 함께 일어남으로써 촉매층 온도강하가 완화된 것을 기대할 수 있다. Al2O3에 담지된 Pt, Ni, Ce 등의 촉매작용을 조사하였는데, 활성성분으로서의 백금은 메탄연소에서 뿐만 아니라 메탄의 CO2 개질과 수증기 개질에서도 효과적이다. 그러나 촉매성분의 함침순서가 활성에 큰 영향을 미쳤다. 본 반응은 메탄 연소가 먼저 일어나고 그 다음으로 메탄의 CO2 개질과 수증기 개질이 일어난다고 추론된다. 조사한 촉매 중에서 Ce-Ni-Pt/Al2O3 촉매가 가장 좋은 성능을 보여주었는데, CH4 20%, O2 5%, CO2 10%로 공급한 경우 800 ℃에서 93%의 CO2 제거율과 98%의 CO 수율을 얻었다. 메탄 및 산소의 공급량을 증가시킴에 따라 메탄전화율과 CO2 제거율은 감소하였고 온도강하 방지효과는 기대만큼 나타나지 않았다. CO2 제거율이 높을 때에 10-30 ℃의 온도강하가 관찰되었다.
In this work, CH4 combustion-CO2 reforming was investigated. In this reaction system, CO2 reforming which is an endothermic reaction occurs together with CH4 combustion which is an exothermic reaction and thus it is anticipated that the temperature lowering of the catalyst bed would be alleviated. The catalytic actions of Pt, Ni and Ce supported on Al2O3 were investigated, and Pt was found to be a very active catalyst for the combustion of the methane as well as for CO2 reforming and steam reforming of methane. It was shown that the sequence of impregnation of the catalyst constituents affected the activity significantly. In the CH4 combustion-CO2 reforming, it is inferred that the combustion occurs in the first place and the CO2 reforming as well as steam reforming follow it. Among the catalysts tested, a Ce-Ni-Pt/Al2O3 catalyst showed the best result: at the CH4 : O2 : CO2 feed ratio of 20 : 5 : 10 and at 800 ℃, 93% of CO2 removal and 98% of CO yield were obtained. As the feed rates of CH4 and O2 increased, the methane conversion and CO2 removal ratio were decreased but the lowering of the catalyst bed temperature was not reduced significantly contrary to the expectation. When the extent of CO2 removal was high, it was observed that the measured bed temperature was lower by 10-30 ℃ than that when no reaction occurred.
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