Ethylene glycol (EG) in supercritical water was oxidized in an isothermal tubular flow reactor in the temperature range of 380~425℃. The ethylene glycol concentration ranged from 1000 to 5000 ppm. The initial amount of air spanned from 100 to 400% of stoichiometrically required amount of air for complete oxidation, while the operating pressure was maintained at 250 bar for all the runs. At temperature higher than 400℃, the decomposition of ethylene glycol and total organic carbon increased rapidly. High initial EG concentration resulted in fast decomposition of EG, but oxygen was found to have no effect on the decay of EG. Analysis of the kinetic data showed that the overall oxidation rate law was 1.38 th order for EG and 0th order for oxygen. The overall reaction rate constant was a pre-exponential factor 10^10 liter^-0.38 , mol^-0.38·sec^-1, and the activation energy was 30.2 kcal/mol. The loss of EG based on these estimated kinetic parameters agreed well with the experimental observations. The major products observed were acetaldehyde, acetic acid and formaldedyde. Glyoxylic acid, oxalic acid formic acid and malonic acid were found to be minor products. A reaction mechanism based on the kinetic parameters and intermediate product distribution was proposed.

등온관형반응기를 이용하여 38O~425 ℃ 영역에서 초임계순 산화법을 이용하여 ethylene glyrol (EG)외 분해반응연구를 수행하었다. Ethylene glycol의 농도범위는 1000~5000 ppm이며, 주입 산소량은 EG를 산화시키 위한 필요 공기량의100~400%로 하였으며 운전압력은 250 bar로 고정시켜 실험을 진행하였다. 400℃ 이상에서 EG와 total organic carbon (TOC)는 분해반응이 급격히 종가하기 시작하였으며 초기농도가 높을수록 분해율은 높았으며 산소농도에는 분해율이 영향을 미치지 못했다. 반응속도인자 분석결과 EG 분해반응차수는 EG에 대하여 1.38차, 산소에 대해서는 0차이며, 활성화 에너지는 30.2 kcaㅣ/mol이었다. EG 분해시 생성되는 주요 중간생성물질로는 acetaldehyde, acetic acid, formaldedyde이었으며, 미량 생성물로는 glyoxylic acid, oxalic acid, formic acid, malonic acid 등이 검출되었다.