長鏈烯烴羰基合成的熱力學網(wǎng)絡計算

化工論文編號:HG220  論文字數(shù):16576,頁數(shù):47

目錄
前言 1
1 文獻綜述 3
1.1 羰基合成 3
1.1.1 羰基合成的發(fā)展歷程 3
1.1.2 羰基合成的類型 3
1.1.3 羰基合成的反應機理 4
1.2 羰基合成的催化劑體系 5
1.2.1 鈷系催化劑 5
1.2.2 銠系催化劑 6
1.2.3 其他催化劑 11
1.3 羰基合成技術在工業(yè)上的應用 12
1.3.1 碳四烯烴羰基化合成精細化學品 12
1.3.2 C5～17烯烴羰基合成的應用 13
1.4 熱力學 14
1.4.1 化學熱力學 14
1.4.2 熱力學的應用 15
1.5 本論文的研究內(nèi)容和目的 16
2 羰基合成的熱力學網(wǎng)絡計算 17
2.1 反應方程式 17
2.2 熱力學數(shù)據(jù)的估算 20
2.2.1 298K條件下生成焓和熵值的估算 21
2.2.2 298K條件下液態(tài)組分生成焓的估算 21
2.2.3 298K條件下液態(tài)組分熵值的估算 24
2.2.4 液態(tài)有機組分熱容的估算 24
2.3 反應體系的熱力學計算 27
2.3.1 常壓下的熱力學數(shù)據(jù)計算 27
2.3.2 不同壓力下的熱力學數(shù)據(jù)計算 33
3結(jié)果討論與分析 34
3.1 烯烴的羰基合成反應 34
3.2 烯烴羰基合成的副反應 35
3.3 反應選用的催化劑 35
4結(jié)論 36
參考文獻 38
謝  辭 42

摘  要
 羰基合成又稱氫甲酰化，是烯烴與一氧化碳和氫氣在催化劑的作用下，在烯烴雙鍵上同時加上氫原子和甲酰基生成比原來多一個碳原子的醛、醇和酯等物質(zhì)的過程。由于羰基合成具有合成路線短、工藝簡單、原料利用率高等技術優(yōu)點，其在現(xiàn)代化學工業(yè)中得到了廣泛的研究和開發(fā)，現(xiàn)已成功應用于生產(chǎn)增塑劑和洗滌劑等方面。熱力學是解決實際問題中的一種非常有效的重要工具，在生產(chǎn)實踐中已經(jīng)和正在發(fā)揮著巨大的作用。在設計新的反應路線或試制新的化學產(chǎn)品時，通過熱力學能夠很容易判定反應變化的方向和限度。
 本文采用基團估算法估算了長鏈烯烴羰基合成反應體系中一系列參與反應的物質(zhì)在298K標準狀態(tài)的生成焓、標準熵、沸點和蒸發(fā)焓等數(shù)據(jù)，并且估算了這些物質(zhì)的的液態(tài)熱容隨溫度變化的關系式，計算了不同溫度條件下反應的生成焓和吉布斯自由能變。通過對這些反應體系的熱力學計算和分析，驗證了這些反應在熱力學上的可行性以及反應壓強對該類型反應影響不大。提出PETPP／Rh配合物作催化劑對反應有很好的效果。文獻報導反應通常在高壓下進行，而論文在常壓下計算，結(jié)果有一定偏差。
關鍵詞：長鏈烯烴；羰基合成；基團估算法；熱力學計算。

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.