摘要
用小型密闭压力容器实验(MCPVT)分别跟踪测定了1,3-丁二烯在氮气和氧气氛围下温度随时间的变化(T-t)和压力随时间的变化(p-t)。利用p-t曲线构建了1,3-丁二烯初期氧化反应动力学。结果表明,在氮气条件下,即使温度达到388.15 K也未检测到1,3-丁二烯发生化学反应。1,3-丁二烯与氧气在343.15~363.15 K范围内发生了氧化反应,反应器内的压力减小。1,3-丁二烯与氧气的初期氧化反应动力学是二级反应。另外,还考察了氧气过量和1,3-丁二烯过量时两种特殊情况下的假一级氧化反应动力学。探讨了过渡态的热力学参数,计算结果表明,1,3-丁二烯的热氧化是一个有序的分子数减少过程。用气相色谱-质谱联用仪和碘量法分析了氧化反应产物,其产物有呋喃和过氧化物。
The changes of temperature with time(T-t)and pressure with time(p-t)of 1,3-butadiene in nitrogen and oxygen were measured by mini closed pressure vessel test(MCPVT).The initial oxidation kinetics of 1,3-butadiene was constructed by p-t plots.The results showed that no chemical reaction of 1,3-butadiene was detected even when the temperature reached 388.15 K in the presence of nitrogen.The oxidation reaction of 1,3-butadiene and oxygen occurred at 343.15~363.15 K,and the pressure in the reactor decreased.The initial oxidation kinetics of 1,3-butadiene and oxygen was a second-order reaction.In addition,the kinetics of pseudo first-order oxidation of two special conditions of oxygen excessive and 1,3-butadiene excessive were investigated.The thermodynamic parameters of transition state were also discussed.It was found that the thermal oxidation of 1,3-butadiene was an orderly molecular number reduction process.The oxidation products were analyzed by gas chromatography-mass spectrometry and iodometry.The products were furan and peroxides.
作者
赵惠霞
刘雄民
梁敏
于唱
戴素仪
段鹏志
ZHAO Huixia;LIU Xiongmin;LIANG Min;YU Chang;DAI Suyi;DUAN Pengzhi(College of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,Guangxi,China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2020年第7期1501-1506,1512,共7页
Fine Chemicals
基金
国家自然科学基金(21776050)
广西科技重大专项(桂科AA17204087-20)。
