Steam Reforming of Methanol for the Production of Hydrogen

수소제조를 위한 메탄올의 수증기 개질반응

  • 김상채 (목포대학교 환경공업교육과) ;
  • 정찬홍 (전남대학교 화학공학과) ;
  • 유의연 (전남대학교 화학공학과)
  • Received : 1995.08.28
  • Accepted : 1996.02.21
  • Published : 1996.04.10

Abstract

Various $Cu/SiO_2$ catalysts with copper concentration ranging from 0 to 50wt% were prepared by kneading method for the steam reforming of methanol. These catalysts were calcined at temperatures in the range of $400^{\circ}C{\sim}900^{\circ}C$ and then reduced in a $H_2$ atmosphere in the range of $150^{\circ}C{\sim}350^{\circ}C$. Steam reforming of methanol was carried out at atmospheric pressure over a temperature range of $200^{\circ}C{\sim}400^{\circ}C$, steam/methanol molar ratio of 0.4~1.6 and W/F of 3~25 g.-cat.hr./mol. Characterization of the catalysts was studied using IR, BET and XRD. Using copper nitrate as a precursor for catalysts, pH in the preparation of catalysts had a great effect on the catalytic activity, but pH in the preparation of catalysts, calcination temperature, and reducing temperature in $H_2$ atmosphere had no effect on the product distribution. Optimum copper concentration, calcination temperature and reducing temperature were 40wt%, $700^{\circ}C$ and $300^{\circ}C$, respective)y. Reaction temperature for maximum $H_2$ production was $275^{\circ}C$, and the formation of methane which lowered quantity and quality of $H_2$ would be inhibited below $275^{\circ}C$. $Cu^{\circ}-Cu_2O$ might be active species in $Cu/SiO_2$ catalyst.

Copper 담지량을 0~50wt% 범위에서 달리한 $Cu/SiO_2$ 촉매를 kneading법으로 제조하였다. 이 촉매들을 $400{\sim}900^{\circ}C$에서 소성하였고 반응전에 수소분위기하에서 $150{\sim}300^{\circ}C$에서 환원하였다. 메탄올의 수증기 개질반응을 반응온도; $200{\sim}400^{\circ}C$, 수증기/메탄올 몰비; 0.4~1.6, 그리고 접촉시간(W/F); 3~25g.-cat.hr./mol 범위에서 수행하였다. 촉매의 특성은 IR, BET와 XRD를 사용하여 조사하였다. 촉매의 precursor로 copper nitrate를 사용할때 촉매제조시의 pH가 촉매의 활성에 큰 영향을 미쳤으나 pH, 소성온도 및 환원온도는 생성물분포에 영향을 미치지 않았다. 최적담지량, 소성온도 및 환원온도는 각각 40wt%, $700^{\circ}C$ 그리고 $300^{\circ}C$였다. 수소생성을 위한 최적반응온도는 $275^{\circ}C$였고 수소의 양과 질을 저하하는 메탄의 생성은 이 온도까지 억제되었다. $Cu/SiO_2$ 촉매계에서 반응활성종은 $Cu^{\circ}-Cu_2O$임을 추정할 수 있었다.

Keywords

References

  1. 화학공업과 기술 v.13 고용태;노용우
  2. Chem. Lett. H. Kobayashi;N. Takezawa;C. Minochi
  3. Chem. Lett. H. Kobayashi;N. Takezawa;C. Minochi;K. Takahashi
  4. J. Chem. Eng. J. C. Amphlett;M. Evans;R. A. Jones;R. D. Weir
  5. Applied Catal. v.2 M. Shimokawabe;N. Takezawa;H. Kobayashi
  6. Applied Catal. v.31 M. A. Kohler;J. C. Lee;D. L. Trimm;N. W. Cart
  7. Ind. Eng. Chem. Res. v.33 R. O. Idem;N. N. Bakhsai
  8. Ind. Eng. Chem. Res. v.33 R. O. Idem;N. N. Bakhsai
  9. J. Catal. v.69 H. Kobayashi;N. Takezawa;C. Minochi
  10. Appl. Catal. A: General v.125 N. Iwasa;S. Masuda;N. Ogawa;N. Takezawa
  11. Microporous Materials v.3 J. K. Suh;B. H. Ha;S. Y. Jeong;J. C. Koh;J. M. Lee