Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Autothermal Reforming of Propane over Ni/CexZr1-xO2 Catalysts

Ni 담지 CexZr1-xO2 촉매상에서 프로판의 자열개질반응

  • Kong, Jin-Hwa (Department of advanced chemical engineering, Chonnam National University) ;
  • Park, Nam-Cook (Faculty of Applied Chemical Engineering, Chonnam National University) ;
  • Kim, Young-Chul (Faculty of Applied Chemical Engineering, Chonnam National University)
  • 공진화 (전남대학교 대학원 신화학소재공학과) ;
  • 박남국 (전남대학교 응용화학공학부 및 촉매연구소) ;
  • 김영철 (전남대학교 응용화학공학부 및 촉매연구소)
  • Received : 2012.08.14
  • Accepted : 2012.09.21
  • Published : 2013.02.01
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Abstract

In this study, the catalytic performance and characterization of $Ni/Ce_xZr_{1-x}O_2$ were investigated using an autothermal reforming (ATR) process for hydrogen production. The $Ni/Ce_xZr_{1-x}O_2$ catalysts were prepared using the following methods: the water method (CZ-W), urea water method (CZ-UW) and urea, water and ethanol method (CZ-UWA). The performance of $Ni/Ce_xZr_{1-x}O_2$ catalysts in autothermal reforming of propane for hydrogen production was studied in a fixed-bed flow reactor. Reaction tests were conducted by using a feed of $H_2O/C_3H_8/O_2$=3/1/0.37 and $300{\sim}700^{\circ}C$. The CZ-UW and CZ-UWA catalysts showed higher propane conversion and hydrogen yield than the CZ-W catalyst. The activity test confirmed that the improvement in the water-ethanol catalyst was due to the low level of carbon deposition. SEM showed that the surface carbon consisted of clusters on the used CZ-UW catalyst, which is incontrast to the nano-fiber morphology observed on the used CZ-UWA catalyst. It was found that the amount of carbon deposition depends on the preparation method. Especially the $Ni/Ce_{0.75}Zr_{0.25}O_2$ was showed higher propane conversion and hydrogen yield than the other catalysts. Also TGA showed that the resistance of carbon deposition increase to Co addition.

본 연구는 $Ni/Ce_xZr_{1-x}O_2$ 촉매를 이용하여 프로판의 자열개질반응을 통한 수소제조에 관한 것이다. $Ni/Ce_xZr_{1-x}O_2$ 촉매는 용매로서 물을 사용한 방법(CZ-W), 우레아와 물을 사용한 방법(CZ-UW), 우레아, 에탄올 및 물을 사용한 방법(CZ-UWA)으로 각각 제조하였다. 반응물질의 조성은 $Steam/C_3H_8$=3, $C_3H_8/O_2$=2.70 이었고, 반응은 상압 고정층 유통식 반응기에서 $300{\sim}700^{\circ}C$ 온도범위에서 진행하였다. 촉매제조시 용매에 우레아 및 에탄올을 첨가할 경우 촉매의 활성이 증가하였다. CZ-UW 촉매의 경우 클러스터형태의 탄소생성에 기인한 활성점 피막으로 인해 쉽게 비활성화가 초래됐다. 하지만 CZ-UWA 촉매의 경우 반응 후 탄소가 활성에 영향을 미치지 않는 나노파이버형태로 존재하여 활성저하가 발생되지 않음을 SEM을 통해 확인했다. 또한 $Ni/Ce_{0.75}Zr_{0.25}O_2$ 촉매의 전환율 및 수율이 더 좋게 나타났으며 또한 소량의 Cobalt를 첨가했을 때 탄소에 대한 저항성이 크게 향상됨을 TGA로 확인하였다.

Keywords

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