화학공학소재연구정보센터
Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.1, 58-66, February, 1999
크롬 산화물 촉매를 이용한 Vinyl Chloride의 산화 분해반응
Catalytic Oxidation of Vinyl Chloride on Chromium Oxide Catalysts
초록
알루미나에 담지한 CrOx 촉매를 이용하여 200∼400℃의 온도 구간에서 공기 중 vinyl chloride의 산화반응을 조사하였다. 탄소를 포함하는 주생성물은 CO 및 CO2로, 온도의 증가에 따라 CO2의 선택도는 증가하고 CO는 감소하였다. 이로부터 CrOx 촉매상에서 vinyl chloride는 먼저 CO로 일차산화 후 다시 CO2로 완전산화됨을 알 수 있었다. 반응물에 HCl을 첨가하였을 때 vinyl chloride의 전환율은 변화가 없었으나 CO2의 선택도는 감소하였는데 이는 주반응생성물인 HCl이 vinyl chloride의 CO2로 완전산화를 방해함을 의미한다. 반응물에 물이 없는 조건하에서 vinyl chloride를 산화시킬 때 상당량의 Cl2가 생성되었으나 물을 첨가 시 Cl2는 검출되지 않았다. Vinyl chloride 분해활성은 1% Pt 담지촉매를 제외한 다른 촉매에 비해 높았으며, 275℃에서 12% CrOx/Al2O3의 반응속도를 기준으로 각 촉매의 활성을 비교시 1% Pt/Al2O3 보다 1.2배정도 활성이 떨어지나 다른 촉매에 비하여 각각 3배에서 8배 가량 높은 활성을 나타내었다.
The catalytic oxidation of vinyl chloride was investigated over CrOx impregnated on Al2O3 at temperature between 200 and 400℃. The major carbonaceous products were CO and CO2, and the selectivity of CO2 was gradually increased with increasing reaction temperature, while that of CO was dropped consequently. This suggests that CO is the first product which is further oxidized to CO2 in the oxidation of vinyl chloride over CrOx/Al2O3. The addition of HCl in the feed didn't affect the conversion of vinyl chloride, but the selectivity of CO2 decreased by adding HCl. It implies that HCl inhibits, the complete oxidation of vinyl chloride to CO2. When oxidizing vinyl chloride in dry air, significant amounts of Cl2 were observed, while no Cl2 was detected in the humid condition. The activities of several catalysts including various precious metals and other transition metal oxides were measured, it was found that the catalytic activity of 12% CrOx/Al2O3 was 1.2 times lower than that of 1% Pt/alumina, but it was 3 to 8 times more active than other catalysts for vinyl chloride oxidation at 275℃.
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