화학공학소재연구정보센터
Korean Chemical Engineering Research, Vol.48, No.2, 259-267, April, 2010
아조염료 Reactive Black 5 폐수의 촉매습식산화
Catalytic Wet Oxidation of Azo Dye Reactive Black 5
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초록
불균일 촉매 CuO를 이용한 반응성 아조계 염료 Reactive Black 5(RB5) 폐수의 촉매습식산화에서 반응온도(190~230 ℃) 및 촉매농도(0.00~0.20 g/l)가 폐수의 색도 및 총 유기탄소 TOC 제거에 미치는 영향을 조사하였다. 폐수의 색도는 분광광도계를 사용하여 측정하였고, 습식산화속도는 TOC를 이용하여 산출하였다. 열분해 조건(230 ℃, 120 min)에서 폐수의 색도는 약 90%까지 제거되었지만 TOC는 제거되지 않았다. RB5 폐수 촉매 습식산화에서의 폐수의 색도 및 TOC 제거속도는 반응온도 및 촉매농도를 증가시킴에 따라 증가하였다. 촉매의 영향은 0.01 g CuO/l에서 이미 상당히 크게 나타났으며 0.05 g CuO/l 이상에서의 촉매농도 증가에 따른 효과는 작았다. 폐수 색도의 초기변화는 색도에 대한 1차 반응속도론으로 나타낼 수 있었으며, TOC 변화는 폐수 TOC를 쉽게 산화되는 TOC와 난분해성 TOC로 구분한 global 모델로 묘사할 수 있었다. 반응온도의 폐수 색도 및 TOC 제거속도에 미치는 영향은 Arrhenius 상관 관계식으로 묘사할 수 있었다. RB5 폐수의 열분해, 습식산화 및 0.20 g CuO/l의 촉매농도를 사용한 촉매습식산화 조건에서의 색도 제거반응의 활성화에너지는 각각 108.4, 78.3 및 74.1 kJ/mol의 값을 나타내었다. RB5 폐수 촉매습식산화에서의 TOC 제거반응에서 산화 최종산물로의 전환에 대한 난분해성 중간산물로의 전환 비는 페놀 습식산화에 비하여 상대적으로 높았다.
The catalytic wet oxidations of the wastewater containing azo dye Reactive Black 5(RB5) with heterogeneous catalyst of CuO have been carried out to investigate the effects of temperature(190~230 ℃) and catalyst concentration(0.00~0.20 g/l) on the removals of colour and total organic carbon TOC. The wastewater colour was measured with spectrophotometer, and the oxidation rate was estimated with TOC. About 90% of colour was removed during 120 min in thermal degradation of the RB5 wastewater at 230 ℃, while TOC was not removed at all. As increasing reaction temperature and catalyst concentration, the removal rates of colour and TOC increased in the catalytic wet oxidations of RB5 wastewater. The effects of catalyst were already considerable even at 0.01 g CuO/l, while the removal rates of colour and TOC increased negligibly with increasing the catalyst concentration above 0.05 g CuO/l. The initial destruction rates of the wastewater colour have shown the first-order kinetics with respect to the wastewater colour. TOC changes during catalytic wet oxidations have been well described with the global model, in which the easily degradable TOC was distinguished from non-degradable TOC of the wastewater. The impacts of reaction temperature on the destruction rate of the wastewater colour and TOC could be described with Arrhenius relationship. Activation energies of the colour removal reaction in thermal degradation, wet oxidation, and catalytic wet oxidation(0.20 g CuO/l) of the RB5 wastewater were 108.4, 78.3 and 74.1 kJ/mol, respectively. The selectivity of wastewater TOC into the non-degradable intermediates relative to the end products in the catalytic wet oxidations of RB5 wastewater was higher compared to that in phenol wet oxidations.
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