Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Kinetics of Ethyl Phenylcarbamate Synthesis by the Oxidative Carbonylation of Aniline

아닐린의 산화적 카르보닐화에 의한 에틸페닐카바메이트의 합성의 속도론적 고찰

  • Park, Nae-Joung (Dept. of Chem. Eng., College of Eng., Hong-Ik University) ;
  • Park, Jae-Keun (Dept. of Chem. Eng., College of Eng., Hong-Ik University)
  • 박내정 (홍익대학교 공과대학 화학공학과) ;
  • 박재근 (홍익대학교 공과대학 화학공학과)
  • Received : 1992.09.15
  • Accepted : 1992.10.15
  • Published : 1992.12.31
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Abstract

Ethylphenyl carbarmate(EPC) was synthesized by oxidative CO carbonylation of aniline in the presence of transition metal catalysts and alkali metal halide cocatalysts at $120^{\circ}C$ under the pressure of 79atm. Oxygen gas was used for oxidizing agent. Kinetics of the reaction was studied and activation energies with different catalysts were estimated. About 100% conversion to EPC and 95% selectivity was obtained in 5 hour reaction. 5% Pd/C was more effective than 5% Rh/C. Effectiveness of cocatalysts was in the order of KI>KBr>KCl. As the temperature increased from $75^{\circ}C$ to $120^{\circ}C$, the conversion rate increased. The reaction was apparent first order and the activation energies with 5% Pd/C and 5% Rh/C were 5.647 and 5.780 kcal/mol, respectively.

에틸페닐카바메이트를 $120^{\circ}C$, 79 atm에서 전이금속촉매와 할로겐화 알칼리금속을 조촉매로하여 아닐린의 산화적 카르보닐화반응에 의하여 합성하였다. 산화제로서 산소를 사용하였으며 반응속도를 조사하고 활성화에너지를 추정하였다. 5시간 반응후 전환율은 100%, 선택도는 95%이었고 촉매로서는 Pd촉매가 Rh촉매보다 약간 효과가 좋았으며 조촉매로서의 효율은 KI>KBr>KCl 순이었다. $75^{\circ}C$에서 $120^{\circ}C$사이에서 온도의 증가에 따라 반응속도가 증가되었으며 반응은 겉보기 1차반응이었고 활성화 에너지는 5% Pd/C와 5% Rh/C에서 각각 5.647, 5,780 kcal/mol이었다.

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