Abstract: The optimum technology and reaction kinetics of toluene oxidation to benzaldehyde in supercritical carbon dioxide and subcritical water without catalyst were studied.The experimental results showed that the oxidation in supercritical carbon dioxide was a zero order reaction with activation energy 50.9 kJ•mol^-1 and the oxidation in subcritical water was a consecutive reaction consisting of two first order reactions with activation energy 89 kJ•mol^-1 and 76 kJ•mol^-1 respectively.The optimum conditions for supercritical carbon dioxide were:P=25 MPa，T=180 ℃，t=4 h，η=2.5 and those for subcritical water were:P>P₀，T=350 ℃，t=1 h，η=3.5.

Key words: 清洁生产, 近临界水, 超临界二氧化碳, 苯甲醛, 超临界流体

摘要： 分别研究了在超临界二氧化碳和近临界水中以过氧化氢为氧源、无催化剂条件下，甲苯氧化成苯甲醛的工艺优化及氧化反应动力学.研究结果表明，在超临界二氧化碳中的最佳工艺条件为：P=25 MPa，T=180 ℃，t=4 h，η=2.5.氧化反应呈现零级反应特征，反应活化能E_a=50.9 kJ•mol^-1.在近临界水中的最佳工艺条件为：P>P₀，T=350 ℃，t=1 h，η=3.5.氧化反应由两个一级反应组成连串反应，反应活化能分别为E_a1=89 kJ•mol^-1，E_a2=76 kJ•mol^-1.

关键词: 清洁生产, 近临界水, 超临界二氧化碳, 苯甲醛, 超临界流体