Abstract
Hydrogenolysis reactions of CFC-113a catalyzed by various heterogeneous catalysts $(Rh/Al_2O_3,\;Pd/C,\;Ni,\;Al_2O_3,\;Active\;carbon)$ were investigated in the liquid and gas phases. In the liquid phase reaction, different catalysts showed different activities, but all catalysts used gave high selectivities toward HCFC-123 over 95%. It was noticeable that the neutral $Al_2O_3$ showed both a high activity and a selectivity in the liquid phase reaction. In the gas phase reaction, transition metals on carbon(Pd/C, Pt/C) were so active for hydrogenolysis of CFC-113a that they even catalyzed the production reaction of overhydrogenated compounds such as $HCFC-133a(CF_3CH_2Cl)\;and\;HFC-143a(CF_3CH_3)$. $Al_2O_3$, which showed the high activity in the liquid phase reaction, did not show a remarkable activity. When $Al_2O_3$ was used in the liquid phase reaction, the hydrogenolysis of CFC-113a proceeded without any side products in THF. However, the same reaction in MeOH produced side products, such as $CH_3OCH_3\;and\;CH_3CH_2OCH_3$ from solvent. Based on this result, including heterogeneous catalysts, it was concluded that the solvent played an important role in the liquid phase reaction.
여러가지 불균일 촉매$(Rh/Al_2O_3,\;Pd/C,\;Ni,\;Al_2O_3,\;Active\;carbon)$를 이용하여 CFC-113a의 가수소 분해반응을 액상과 기상에서 각각 조사하였다. 액상반응에서는 각 촉매에 따라 반응성은 차이가 났지만, 95% 이상의 높은 선택성으로 $HCFC-123(CF_3CHCl_2)$을 주었다. 특히 $Al_2O-3$가 액상반응에서 상당히 높은 반응성과 선택성을 보인 것은 주목할 만하다. 기상반응의 경우, 전이금속이 포함된 촉매(Pd/C, Pt/C)를 사용하였을 때에는 과수소화물인 $HCFC-133a(CF_3CH_2Cl)$와 HFC-143a(CF_3CH_3)$가 생성되었다. 한편, 액상반응에서 활성을 보이던 $Al_2O_3$는 기상반응에서는 거의 반응성을 보이지 않았다. $Al_2O_3$의 경우 용매로 THF를 사용하였을 경우에는 비교적 부반응 없이 깨끗하게 반응이 진행되었지만, MeOH를 사용하였을 때는 용매로 부터 $CH_3OCH_3$과 $CH_3CH_2OCH_3$ 등이 생성되면서 가수소 분해반응이 진행되었다. 따라서 액상반응에서는 용매의 역할이 중요한 것으로 해석하였다.
