Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Oxidative Dehydrogenation of n-Butenes over BiFe0.65MoP0.1 Oxide Catalysts Prepared with Various Synthesis Method

다양한 합성 방법으로 제조된 BiFe0.65MoP0.1 산화물 촉매 상에서 n-부텐의 산화탈수소화 반응

  • Park, Jung-Hyun (Department of Chemical Engineering, Chungbuk National University) ;
  • Shin, Chae-Ho (Department of Chemical Engineering, Chungbuk National University)
  • Received : 2014.08.22
  • Accepted : 2014.10.11
  • Published : 2015.06.01
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Abstract

To investigate the effect of the catalyst synthesis method on the oxidative dehydrogenation (ODH) of nbutenes, $BiFe_{0.65}MoP_{0.1}$ oxide catalysts were prepared with various synthesis methods such as co-precipitation, citric acid method, hydrothermal method, and surfactant templated method. The catalysts were characterized by X-ray Diffraction (XRD), $N_2$ sorption, and $NH_3/1$-butene-temperature programmed desorption ($NH_3/1$-butene-TPD) to correlate with catalytic activity in ODH reaction. Among the catalysts studied here, $BiFe_{0.65}MoP_{0.1}$ oxide catalyst prepared with co-precipitation method marked the highest activity showing 1-butene conversion, 79.5%, butadiene selectivity, 85.1% and yield, 67.7% after reaction for 14 h. From the result of $NH_3$-TPD, the catalytic activity is closely related to the acidity of the $BiFe_{0.65}MoP_{0.1}$-x oxide catalyst and acidity of the $BiFe_{0.65}MoP_{0.1}$ oxde catalyst prepared with co-precipitation method was higher than that of other catalysts. In addition, combined with the 1-butene TPD, the higher catalytic activity is closely related to the amount of weakly adsorbed intermediate (< $200^{\circ}C$) and the desorbing temperature of strongly adsorbed intermediates (> $200^{\circ}C$).

n-부텐의 산화탈수소화에서 제조방법이 촉매의 반응활성에 미치는 영향을 조사하기 위하여 $BiFe_{0.65}MoP_{0.1}$ 산화물 촉매를 모델 촉매로 선정하여 공침법, 시트르산법, 수열합성법, 주형법 등의 방법으로 촉매를 제조하였다. 제조한 촉매의 물리 화학적 특성을 알아보고 반응 활성과 연관시키기 위하여 X-선 회절분석(XRD), 질소 흡착 탈착분석($N_2$ sorption), 암모니아/1-부텐-승온탈착분석($NH_3/1$-butene-TPD) 등의 특성분석을 수행하였다. 공침법으로 제조한 촉매의 활성이 가장 높게 관찰되었으며, 14시간 동안의 산화탈수소화 반응 기준으로 n-부텐의 전환율은 79.5%, 1,3-부타디엔의 선택도는 85.1%, 1,3-부타디엔 수율은 67.7%의 수치를 보였다. 암모니아 승온탈착 실험으로부터 촉매의 반응 활성은 촉매의 산특성과 밀접하게 관련이 있으며, 공침법으로 제조한 산화물 촉매가 다른 합성방법으로 제조한 촉매와 비교하여 가장 큰 산량을 갖는 것으로 관찰되었다. 또한, 1-부텐의 승온탈착 분석결과, 촉매의 활성은 흡착된 1-부텐과 촉매의 표면반응에 기인한 중간체의 흡 탈착 특성, 즉 약하게 흡착된 중간체(< $200^{\circ}C$)의 상대적인 양과 강하게 흡착된 중간체의 탈착 온도(> $200^{\circ}C$)와 밀접하게 관련이 있었다.

Keywords

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