【作者】 吴向阳；

【导师】 张敬畅；

【作者基本信息】 北京化工大学 ， 工业催化， 2001， 硕士

【摘要】 超临界流体（SCF）具备有高度溶解性、扩散性、传质快等优点，广泛应用于超临界萃取和化合物制备，近几年超临界催化反应才刚刚起步。本文初步探索了超临界条件下丙烯氢甲酰化反应，并取得了显著的效果，超临界条件下该反应的催化活性和选择性都远大于常规条件下的氢甲酰化反应。由于采用水溶性的膦配体，很好地解决了铑的流失问题，并实现了催化剂回收和循环使用，证明对超临界条件下催化反应的研究具有理论的研究意义和实际的应用价值。在超临界流体中加入少量的共溶剂能对其溶剂性能产生很大的影响，它能提高超临界流体的溶剂强度和选择性。这些超临界流体—共溶剂体系的临界点数据对于超临界萃取和反应来说是非常重要的理论参数，因此研究这些二元和三元体系的临界点数据是非常有意义的。 本文首先采用固定体积的可视化观察法（乳光法）研究了在超临界CO₂加入甲苯、环己烷、正丁醛、异丁醛、甲醇和乙醇等共溶剂之后，整个体系临界性质的变化情况。发现二元体系的临界温度和压力随着共溶剂的浓度增加不断增加，呈一种线性关系，并且共溶剂的临界温度和临界压力对二元体系的临界温度和压力具有一定的影响。北京化工大学硕士研究生论文 本文还首次测试了在超临界CO:中加入三磺化三苯基麟 （TPPTs）以及共溶剂（正丁醛、异丁醛和乙醇）组成的三元体系的临界点数据，发现三元体系中临界温度也随共溶剂的浓度增加逐渐增加，呈一种线性关系。但是三元体系的临界压力随着共溶剂浓度的增加，趋于一个固定值。本文还将相应二元体系的临界点数据与三元体系进行了比较，发现加入TPPTS的三元体系的临界温度和压力低于未加入TPPTS的二元体系的临界值，并探讨了其原因。 本文通过加入共溶剂的方法，在超临界条件下实现了丙烯氢甲酞化反应，对反应条件进行了初步探讨，并与常规条件下的反应进行了比较。通过对产物正异比、转化率以及时空收率的比较，本文认为在[灿」=2.6 xlo一5，P/Rh=25的条件下，反应温度在45一50℃时为最佳的反应温度。在此条件下，丙烯转化率可达17.2%左右;正异比可高达31一47.9;反应结束后催化剂与体系分离，锗溶于水相，基本上消除了锗的流失，克服了均相反应中催化剂锗的回收和循环使用的困难。表明在超临界条件下的丙烯氢甲酞化反应中，催化剂具有较高的活性和选择性，并且可降低反应温度。说明超临界条件下的化学反应是实现均相反应的极好途径，存在很多优势，是很有研究和应用前景的。关越词:超临界CoZ，二元体系，三元体系，临界点，氢甲酞化，共溶剂，三磺化三苯基麟，丙烯更多还原

【Abstract】 Supercritical fluid(SCF) has the advantage of high diffusitivity, good solubility and transimissibility, and it is widely used in supercritical extraction and material synthesis, SCF has been used in catalysis reaction only in recent years. This work has explored hydroformylation of propylene in SCF elementarily, remarkable result has been got, the catalysis ability and selectivity in SCF is better than that in normal condition. Because the water-soluble Rhodium phosphine complex is used, the lose of Rh has been controlled, and the recycle problem of the Rh catalyst has been solved. It is proved that the research of catalysis reaction in SCF has both the research significance in academic and actual value in application. The performance of SCF as a solvent can be greatly affected by addition of a cosolvent to the system. A cosolvent can be added to a SCF to enhance its solvent strength and/or selectivity. Critical point data for these dilute SCF-cosolvent binary and ternary systems are imperative for the design of efficient supercritical separation and reaction processes. So that, it is very important to study the critical point data in binary and ternary systems.The constant volume visual method is used to measure the critical properties of CO2+toluene, CO2+cyclohexane, CO2+n-butyraldehyde, CO2+i-butyraldehyde, CO2+ methanol and CO2+alcohol binary systems. With the increase of mol% of the cosolvent, critical temperature and pressure of binary system increased, and the experimental data show a linear dependence of critical temperature and pressure with mol% of the binary system over the concentrationranges studied, and the critical temperature and pressure of cosolvent has some infection to that of binary system.In this study, the critical point data of ternary systems which is composed of supercritical carbon dioxide, trisodium salt of tri-(m-sulfonphenyl)phosphine(TPPTS) and cosolvent were measured the first time. With the increase of mol% of the cosolvent, critical temperature of ternary system increased, and the experimental data show a linear dependence of critical temperature with mol% of the ternary system over the concentration ranges studied too. But with the increase of mol% of the cosolvent, the critical pressure of ternary system close to a constant value. The comparison of the critical point of binary systems and that of ternary systems have been discussed, all the data shows that the critical temperature and pressure of ternary system is lower than that of binary system, and the reason has also been explored.With the addition of cosolvent, hydroformylation of propylene in SCF is realized, the reaction condition is explored. The reaction in SCF is compared with normal condition. With the comparison of product n/i ratio , translation rate and TON, under the condition of [Rh]=2.6. 10’5,P/Rh=25, the best reaction temperature has been got, which is T=45~50癈. It is found that under this condition, the translation rate of propylene can reach 17.2%, n/i ratio is 31~47.9. When the reaction is over, catalyst can separates from product easily, the Rh catalyst dissolves in water, the lose and recycle problem of the Rh catalyst has been solved. Under supercritical condition, the catalyst has high activity and selectivity, and the reaction temperature decreased. It proves that reaction in SCF is one of the best ways to realize homogeneous reaction and has many advantages, it has good development prospect both in the area of research and application.更多还原