Ammoxidation of Methylpyrazine over Molybdenum Phosphate Catalyst

몰리브덴인산화물 촉매에 의한 메틸피라진의 가암모니아 산화반응

  • Shin, Chae-Ho (Chemical Technology Research Division, Korea Research Institute of Chemical Technology) ;
  • Chang, Tae-Sun (Chemical Technology Research Division, Korea Research Institute of Chemical Technology) ;
  • Cho, Deug-Hee (Chemical Technology Research Division, Korea Research Institute of Chemical Technology) ;
  • Lee, Dong-Koo (Chemical Technology Research Division, Korea Research Institute of Chemical Technology) ;
  • Lee, Young K. (Chemical Technology Research Division, Korea Research Institute of Chemical Technology)
  • 신채호 (한국화학연구소 화학기술연구단) ;
  • 장태선 (한국화학연구소 화학기술연구단) ;
  • 조득희 (한국화학연구소 화학기술연구단) ;
  • 이동구 (한국화학연구소 화학기술연구단) ;
  • 이영길 (한국화학연구소 화학기술연구단)
  • Received : 1997.04.03
  • Accepted : 1997.08.14
  • Published : 1997.10.10

Abstract

Molybdenum phosphate(P/Mo = 0.6) has been synthesized with ammonium molybdate and phosphoric acid under aqueous solution. The kinetics of the ammoxidation of methylpyrazine over molybdenum phosphate catalyst was investigated with the variation of reaction temperature and partial pressure of methylpyrazine, oxygen and ammonia, respectively at atmospheric pressure. The catalytic activity was constant for 300hrs operation under our experimental conditions. Under the steady-state condition, the rate equation of methylpyrazine was shown as $-r=kP_{MP}P_{NH3}{^0}P_{O2}{^{\gamma}}({\gamma}=2.2;1.3{\leq}P_{O2}(kPa){\leq}4)$. The apparent activation energy was 29.6kcal/mol below 623K. The main product obtained in the ammoxidation of methylpyrazine is cyanopyrazine whose selectively was kept always over 90% regardless of conversion.

몰리브덴산암모늄염과 인산의 반응으로 P/Mo=0.6의 비율을 가진 몰리브덴인산화물을 제조하고 이를 촉매로 사용하여 메틸피라진의 가암모니아 산화반응에 대한 메틸피라진, 산소, 암모니아의 각각의 분압과 반응온도 등의 반응변수의 영향을 살펴보았다. 표준실험조건하의 반응에서 300시간까지의 촉매활성은 안전상태를 유지하였다. 안정화 상태에서의 메틸피라진의 가암모니아 산화반응 속도식은 $-r=kP_{MP}P_{NH3}{^0}P_{O2}{^{\gamma}}({\gamma}=2.2;1.3{\leq}P_{O2}(kPa){\leq}4)$으로 메틸피라진에 대해서는 1차, 암모니아에 대해서는 0차, 산소에 대해서는 분압 4kPa이하에서 2.2차로 나타났다. 623K이하의 반응온도 하에서의 겉보기 활성화에너지는 29.6kcal/mol이었다. 메탈피리진의 주생성물은 시아노피라진으로서 선택도는 전환율에 관계없이 항상 90%이상을 유지하였다.

Keywords

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