1-十二碳烯双液相氢甲酰化宏观反应动力学和反应器选型
文献类型：学位论文
| 作者 | 张永强 |
| 学位类别 | 博士 |
| 答辩日期 | 1999-08-30 |
| 授予单位 | 中国科学院研究生院 |
| 导师 | 陈家镛 ; 毛在砂 |
| 关键词 | 1-十二碳烯 氢甲酰化 宏观反应动力学 气液传质 液液分散 数值模拟 气-液-液反应器 |
| 其他题名 | Macro-Kinetics and Reactor Configuration of Biphasic Hydroformylation of 1-Dodecene |
| 学位专业 | 化学反应工程 |
| 中文摘要 | 用正交试验设计方法，研究了温度、压力、反应物、催化剂及其配体、表面活性剂和有机相与水相体积比对1-十三碳烯双液相氢甲酰化的影响，找出了影响氢甲酰化初始反应速率、产物醛的正异比和反应选择性的主次因素顺序，确定了最佳的氢气甲酰化反应条件。根据气液传质和液液分散的实验研究结果，对氢气甲酰化反应条件下的气液传质进行了分析，求得了校正传质影响的经验反应动力学方程。结合对氢甲酰化反应机理的分析，获得了半经验的反应动力学方程。在层流平底高压反应器中，用数值计算和实验相结合方法，得到了了分离开传质影响的双液相氢气甲酰化界面反应动力学方程。提出了优化的1-十二碳烯双液相氢气甲酰化反应器构型并得到了实验验证。 |
| 英文摘要 | An orthogonal experiment design is adopted for the macroscopic reaction kinetics. The effects of temperature, pressure, ratio of partial pressure of hydrogen to carbon monoxide, concentration of catalyst, surfactant and 1-dodecene, molar ratio of ligand to catalyst, and volume ratio of organic to aqueous phases on reaction rate, ratio of normal/isomeric aldehyde, and selectivity are quantified. The relative importance of the factors to the process indexes and the optimal set of factor levels are determined by margin and variance analysis. The optimal hydroformylation reaction conditions are determined. In order to analyse the effect of mass transfer on hydroformylation reaction, the sodium sulfite oxidation method is used to determine gas-liquid volumetric mass transfer coefficients of oxygen-decane-sodium sulfite aqueous solution with the presence of surfactant. The influences of speed of stirrer, spacing between the disc turbine and the reactor bottom, volumetric ratio of organic to aqueous phases, and surfactant concentration on gas-liquid volumetric mass transfer coefficients are investigated and correlated. The type of liquid-liquid dispersion of system for gas-liquid mass transfer and system for biphasic hydroformylation is determined by electric conductivity. In all cases, the organic phase is dispersed in the aqueous phase and the stable emulsion of oil in water is formed. In view of the results of gas-liquid mass transfer and liquid-liquid dispersion, the possible mass transfer limitation on hydroformylation of 1-dodecene is analyzed. It is found that in some cases the gas-liquid mass transfer rate is still controlling. After correcting the effect of mass transfer, the initial reaction rates are correlated with all variables, and the macro-kinetic equation is obtained. Combining mechanisms of homogeneous hydroformylation with interfacial reaction of biphasic hydroformylation, a semi-empirical kinetic equation is determined. This semi-empirical kinetic equation indicates that the reaction rate is proportional to fractional orders of concentration of all reactants and catalyst in accordance with the empirical macro-kinetics. In order to exclude the interference of mass transfer on evaluation of interfacial redaction kinetics completely, a flat-bottomed autoclave is designed. Combining numerical simulation with the experimental results of biphasic hydroformylation under the laminar flow condition, true interfacial reaction kinetics is obtained. The kinetic equation in accordance with the above empirical and semi-empirical kinetics. An optimized configuration of hydroformylation reactor is suggested by combining the results of kinetics, mass transfer, liqui-liquid dispersion and the advantage of the reactor is confirmed by experiments on biphasic hydroformylation of 1-dodecene. |
| 语种 | 中文 |
| 公开日期 | 2013-09-27 |
| 页码 | 188 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1964]  |
| 专题 | 过程工程研究所_研究所（批量导入） |
| 推荐引用方式 GB/T 7714 | 张永强. 1-十二碳烯双液相氢甲酰化宏观反应动力学和反应器选型[D]. 中国科学院研究生院. 1999. |
入库方式： OAI收割
来源：过程工程研究所
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