Wet Oxidation of Phenol with Homogeneous Catalysts

균일촉매를 이용한 페놀의 습식산화

The wet oxidation of phenol has been investigated at temperatures from 150 to $250^{\circ}C$ and oxygen partial pressures from 25.8 to 75.0 bar with initial pH of 1.0 to 12.0 and initial phenol concentration of 10 g/l. Chemical Oxygen Demand COD has bee measured to estimate the oxidation rate. Reaction intermediates have been identified and their concentration profiles have been determined using liquid chromatography. The destruction rate of phenol have shown the first-order kinetics with respect to phenol and the changes in COD during wet oxidation have been described well with the lumped model. The impact of various homogeneous catalysts, such as $Cu^{2+}$, $Fe^{2+}$, $Zn^{2+}$, $Co^{2+}$ and $Ce^{3+}$ ions, on the destruction rate of phenol and COD has also been studied. The homogeneous catalyst of $CuSO_4$ has been found to be the most effective for the destruction of phenol and COD during wet oxidations. The destruction rate of formic acid formed during wet oxidations of phenol have increased as increasing temperature and $CuSO_4$ concentration. The final concentrations of acetic acid which has been formed during wet oxidations and difficult to oxidize have increased with reaction temperature and with decrease in the catalyst load.

페놀 습식산화에 미치는 반응온도($150{\sim}250^{\circ}C$), 산소분압(25.8~75.0 bar) 및 초기 pH(1.0~12.0)의 영향을 10 g/l의 페놀 초기농도를 사용하여 조사하였다. 습식산화속도는 화학적 산소요구량 COD를 이용하여 산출하였으며 반응 중간 생성물들을 고성능액체크로마토그래피를 사용하여 측정하였다. 습식산화 중 페놀 분해속도는 페놀에 대하여 1차 반응차수를 나타냈으며, COD 변화는 lumped 모델로 잘 묘사할 수 있었다. 금속이온($Cu^{2+}$, $Fe^{2+}$, $Zn^{2+}$, $Co^{2+}$, $Ce^{3+}$) 균일촉매의 습식산화 중 페놀 분해속도 및 COD 제거속도에 미치는 영향도 조사하였다. 페놀 분해속도 및 COD 제거속도는 $CuSO_4$를 사용한 촉매습식산화에서 가장 크게 나타났으며 촉매농도를 증가시킴에 따라 증가하였다. 습식산화 중 생성되는 개미산의 분해속도는 반응온도 및 $CuSO_4$ 농도를 증가시킴에 따라 증가하였다. 난분해성 생성물 초산의 최종농도는 반응온도를 증가시킴에 따라 증가하였으나 $CuSO_4$ 농도를 증가시킴에 따라 감소하였다.