苯高压氧化实验和模型研究

Experimental and Kinetic Study of benzene Oxidation at Elevated Pressure

利用射流搅拌反应器研究了1.2MPa、当量比为1、温度范围880~1010K下苯的氧化反应动力学。利用气相色谱和色谱质谱联用仪检测到了20种产物和中间组分。根据实验结果发展了一个272种组分、1702个反应的动力学模型,合理地模拟了实验结果。与常压实验相比,检测到乙醛、丙烯醛、甲苯、苯乙烯、苯甲醛、萘、茚和二苯并呋喃等新组分;反应的初始温度由1000K降低为950K,反应区间由300K减少至70K;探明了高压低温下苯通过苯醌消耗的新分解路径。根据敏感性分析,A_(1)+OH=A_(1^(-))+H_(2)O是促进其消耗最重要的反应,A_(1)OH+O_(2)=A_(1)O+HO_(2)是抑制苯消耗最重要的反应。本模型合理预测了苯在常压的氧化和不同压力下的层流火焰速度。

The high-pressure oxidation of benzene was studied in a jet-stirred reactor under the conditions of 1.2 MPa,equivalence ratio of 1 and temperature range of 880~1010 K.20 products and intermediates were detected by GC and GC-MS.According to the experimental results,a kinetic model of 272 species and 1702 reactions was developed with reasonable predictions.Compared with experimental results obtained at atmospheric pressure,some new species were detected,such as acetaldehyde,acrolein,toluene,styrene,benzaldehyde,naphthalene,indene and dibenzofuran.The initial reaction temperature was shifted from 1000 K to 950 K,and the reaction interval was reduced from 300 K to 70 K.A new decomposition pathway of benzene through benzoquinone consumption under high pressure and low temperature was clarified.The sensitivity analysis shows that the reaction A_(1)+OH=A_(1^(-))+H_(2)O is the most sensitive reaction to promote benzene consumption,while the reaction A_(1)OH+O_(2)=A_(1)O+HO_(2) is the most sensitive reaction to inhibit benzene consumption.This model reasonably predicts the oxidation of benzene at atmospheric pressure and the laminar burning velocity at different pressures.