长链烯烃羰基合成的热力学网络计算

论文编号:HG220  论文字数:16576,页数:47

摘  要
 羰基合成又称氢甲酰化，是烯烃与一氧化碳和氢气在催化剂的作用下，在烯烃双键上同时加上氢原子和甲酰基生成比原来多一个碳原子的醛、醇和酯等物质的过程。由于羰基合成具有合成路线短、工艺简单、原料利用率高等技术优点，其在现代化学工业中得到了广泛的研究和开发，现已成功应用于生产增塑剂和洗涤剂等方面。热力学是解决实际问题中的一种非常有效的重要工具，在生产实践中已经和正在发挥着巨大的作用。在设计新的反应路线或试制新的化学产品时，通过热力学能够很容易判定反应变化的方向和限度。
 本文采用基团估算法估算了长链烯烃羰基合成反应体系中一系列参与反应的物质在298K标准状态的生成焓、标准熵、沸点和蒸发焓等数据，并且估算了这些物质的的液态热容随温度变化的关系式，计算了不同温度条件下反应的生成焓和吉布斯自由能变。通过对这些反应体系的热力学计算和分析，验证了这些反应在热力学上的可行性以及反应压强对该类型反应影响不大。提出PETPP／Rh配合物作催化剂对反应有很好的效果。文献报导反应通常在高压下进行，而论文在常压下计算，结果有一定偏差。
关键词：长链烯烃；羰基合成；基团估算法；热力学计算。

Abstract
 OXO, also called hydroformylation, is a process using alkenes with carbon monoxide and hydrogen in the effect of catalyst to gain aldehyde, alcohol and ester substances, which are more one carbon atom than raw materials. Since several advantages exist in the process of the synthesis, such as the route is short, the craft is simple, the raw material utilization ratio is high and so on, extensively study and development are obtained in modern industry and it has been successfully used in producing plasticizer, detergent and on other aspects.It is thermodynamic that is an effective important tool in solving practice problems, especially at produce practice; it has been taking an significant role. It is relatively easy to conclude the direction and limitation of the action when design new action routes or try new chemistry products.
 Using the mthod of group estimation, we estimate the data which is involved in the system of the reactant on the standard state, such as the formation enthalpy, standard entropy, boiling point and evaporation entropy at the temperature of 298K, and estimate the relationship between the liquid heat capacity and the temperature, and calculate the formation enthalpy of the action and the change of the Gibbs free energy at different temperatures.With thermodynamic calculation and analysis of reaction system, it is feasible on thermodynamic for these reactions and the pressure of the reactions have little effect on these actions and good result can be gained when using PETPP/Rh complexes as the catalyst.The reactions that had been reported are commonly testing at high pressure while the data of this paper is calculated at normal pressure, which results in deviation in the experiment.
Key words: long chain alkenes; OXO; group estimation; thermodynamic calculation.

目录
前言 1
1 文献综述 3
1.1 羰基合成 3
1.1.1 羰基合成的发展历程 3
1.1.2 羰基合成的类型 3
1.1.3 羰基合成的反应机理 4
1.2 羰基合成的催化剂体系 5
1.2.1 钴系催化剂 5
1.2.2 铑系催化剂 6
1.2.3 其他催化剂 11
1.3 羰基合成技术在工业上的应用 12
1.3.1 碳四烯烃羰基化合成精细化学品 12
1.3.2 C5～17烯烃羰基合成的应用 13
1.4 热力学 14
1.4.1 化学热力学 14
1.4.2 热力学的应用 15
1.5 本论文的研究内容和目的 16
2 羰基合成的热力学网络计算 17
2.1 反应方程式 17
2.2 热力学数据的估算 20
2.2.1 298K条件下生成焓和熵值的估算 21
2.2.2 298K条件下液态组分生成焓的估算 21
2.2.3 298K条件下液态组分熵值的估算 24
2.2.4 液态有机组分热容的估算 24
2.3 反应体系的热力学计算 27
2.3.1 常压下的热力学数据计算 27
2.3.2 不同压力下的热力学数据计算 33
3结果讨论与分析 34
3.1 烯烃的羰基合成反应 34
3.2 烯烃羰基合成的副反应 35
3.3 反应选用的催化剂 35
4结论 36
参考文献 38
谢  辞 42