MCPVT测定1,3-丁二烯氧化动力学
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国家自然科学基金项目(面上项目,重点项目,重大项目)


Oxidation kinetics of 1,3-butadiene determined by MCPVT
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The National Natural Science Foundation of China (General Program, Key Program, Major Research Plan)

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    摘要:

    采用小型密闭压力容器试验 (MCPVT) 分别跟踪测定了1,3-丁二烯在氮气和氧气氛围下的温度随时间变化 (T-t) 和压力随时间变化 (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 K ~ 383.15 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。

    Abstract:

    Temperature change with time (T-t) and pressure change with time (P-t) during the oxidation of 1,3-butadiene were measured by mini closed pressure vessel test (MCPVT). The kinetics of initial oxidation of 1,3-butadiene was calculated by P-t plot. Results showed that 1, 3-butadiene not reaction was detected under nitrogen even when the temperature reached 388.15 K. The oxidation of 1,3-butadiene with oxygen occurred in the range of 343.15 K ~ 383.15 K, and the pressure in the reactor decreased. The kinetics of the initial oxidation of 1,3-butadiene with oxygen is a second-order reaction. In addition, the pseudo first-order oxidation kinetics of two special conditions of oxygen excessive and 1,3-butadiene excessive were studied. The thermodynamic parameters of the transition state are also discussed. The results showed 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.

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赵惠霞,刘雄民. MCPVT测定1,3-丁二烯氧化动力学[J].精细化工,2020,37(7):

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  • 收稿日期:2020-02-05
  • 最后修改日期:2020-04-08
  • 录用日期:2020-04-09
  • 在线发布日期: 2020-06-08
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