混合C8烯烃氢甲酰化反应的实验研究

对几种铑膦络合物催化混合Ｃ８烯烃氢甲酰化反应作了实验研究了,结果表明,在一定反应条件下,「Ｒｈ（ＣＨ３ＣＯＯ）２」２,Ｒｈ（ＣＯ）ＰＰｈ３（ａｃａｃ）和Ｒｈ６（ＣＯ）１６均是有效的催化剂前体。配体。铑 的浓度及溶体对催化系性能影响的实验证明,外加ＯＰＰｈ３、选用适量Ｒｈ浓及加入二乙二醇二甲醚或四乙二醇二甲醚等溶剂对Ｃ８烯烃氢甲酰化反应生成Ｃ９醛是有利的。实验表明,对于「Ｒｈ（ＣＨ３ＣＯＯ２）２－Ｏ     

水溶性铑络合物催化1-十二碳烯氢甲酰化反应器构型的初步探索

Hydroformylation of 1-dodecene was studied in a biphasic system using water-soluble rhodium complex [RhCl(CO)(TPPTS)2] as catalyst in the presence of cetyl trimethyl ammonium bromide as surfactant to enhance the reaction rate. Efforts were devoted to improve the performance of hydroformylation by exploring reactor the reaction configuration which enhanced the mixing, dispersion and interphase mass transfer. Experiments were carried out in a 0.5L autoclave at the total pressure of 1.1MPa and temperature from 363K to 373K. Several surface aeration configurations were tested, and higher hydroformylation rate with higher normal/branched aldehyde ratio produced were achieved. The experience suggest that improved reactor configuration by taking reaction engineering, measures is beneficial to better process economy in alkene hydroformylation.     

混合C_8烯烃氢甲酰化反应的实验研究

对几种铑膦络合物催化混合 C8烯烃氢甲酰化反应作了实验研究 ,结果表明 ,在一定反应条件下 ,[Rh( CH3COO) 2 ]2 、Rh( CO) PPh3( acac)和 Rh6 ( CO) 16 均是有效的催化剂前体。配体、铑的浓度及溶剂对催化体系性能影响的实验证明 ,外加 OPPh3、选用适量 Rh浓度及加入二乙二醇二甲醚或四乙二醇二甲醚等溶剂对 C8烯烃氢甲酰化反应生成 C9醛是有利的。实验表明 ,对于 [Rh( CH3COO) 2 ]2 - OPPh3催化体系在 1 40℃及 1 0 .5MPa反应条件下 ,混合 C8烯烃氢甲酰化反应生成 C9醛的收率可达 90 %以上。     

水溶性铑-膦络合物催化烯烃氢甲酰化反应--阳离子表面活性剂的加速作用

介绍了以水溶性铑-膦络合物RhCl(CO)(TPPTS)₂作为催化剂前体在水/有机两相体系中催化烯烃氢甲酰化反应研究的进展,阐述了阳离子表面活性剂的加速作用和介稳态胶束-离子对协同作用机理关系.通过两相体系中界面分子组装和选择与烯烃分子链长相匹配的表面活性剂, 设计制备了高区域选择性复合催化剂体系.当采用双长链表面活性剂与铑-膦络合物组成的复合催化体系时,在不搅拌的情况下就显示出极高的催化活性.     

乙烯三聚制已烯—1催化剂的反应行为和动力学

采用微机采集数据的搅拌釜反应器对实验室自制的催化剂进行了反应行为和动力学研究。讨论了催化剂加入量、反应温度和压力对催化剂活性的影响。当催化剂加入量在0.5～2ml时,最大反应速率与催化剂加入量呈一级动力学关系;反应压力为4.0～6.0MPa时,最大反应速率与乙烯压力呈三级动力学关系,并据此求出反应温度为95～130℃时催化剂上乙烯三聚反应的表现活化能。     

几种鳞翅目昆虫性信息素10和11－十二碳烯－1－醇乙酸酯的简便合成

从芥酸出发，经臭氧化还原，乙酰化及四乙酸铅脱羧三步反应合成了茶长卷峨性信息素组份（４），再经ＣｏＣｌ２／Ｐｈ３Ｐ／ＮａＢＨ４体系异构化合成桦广翅小卷峨、豆荚小卷娥等昆虫性信息素组份（５）。     

H2S分压对1-十二烯在NiMo/Al2O3催化剂上加氢反应的影响

在加氢裂化反应过程中，裂化产生的痕量烯烃会与H2S结合生成硫醇。为研究H2S对烯烃加氢及硫醇生成的影响，实验室采用微反以正-十二烯为模型化合物，考察了H2S存在下1-十二烯在NiMo/Al2O3催化剂上的加氢反应。结果表明，在一定范围内H2S分压的变化对1-十二烯的转化率没有明显影响，但对产品中异构烯烃的选择性有很大影响，并直接影响产物中十二碳硫醇的收率与分布。     

A Study of the Separation of 1-Dodecene and 1-Tetradecene Hydroformylation Products in Aqueous Medium

Abstract

Experimental results of the solubilization of olefins in hydroformylation model systems, comprising 1-dodecene and 1-tridecanal or 1-tetradecene and 1-pentadecanal, water, butanol, sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and/or tri(m-sulfofenyl)phosphine trisodium salt (TPPTS-Na) are presented. The selected systems were used for the hydroformylation of 1-dodecene and 1-tetradecene whereby high yields of aldehydes were obtained. After the reaction, the mixture spontaneously separated into an organic phase with the reaction products and an aqueous phase comprising the catalyst and excess phosphine ligand.     

一步法制备丙烯氢甲酰化制丁醛铑膦络合催化剂研究

采用一步法制备铑膦络合催化剂,考察了反应温度、反应时间、铑膦比、还原剂用量、氢源用量等因素对催化剂制备过程铑利用率的影响。在优化的工艺条件下,铑利用率达99%以上。在适宜的评价条件下,丙烯转化率为97.1%,丁醛选择性为98.1%,产物醛正异构比15∶1以上。     

Structural and Catalytic Properties of Alkyl-Substituted Phosphanes. Effect of Ortho-Modification on Rhodium-Catalyzed 1-Hexene Hydroformylation

The influence of the alkyl-substituted phosphanes (o-methylphenyl)diphenylphosphane (o-MeP), (o-ethylphenyl)diphenylphosphane (o-EtP), bis(o-methylphenyl)phenylphosphane (o-Me₂P), bis(o-ethylphenyl)phenylphosphane (o-Et₂P), and (2,4,5-trimethylphenyl)diphenylphosphane (2,4,5-MeP) was screened in model reaction of rhodium-catalyzed 1-hexene hydroformylation. Compared with PPh₃, the prepared phosphanes afforded lower chemoselectivity towards aldehydes, but increased the normal to branched ratio. Catalyst results are discussed in relation to stereoelectronic properties of the phosphane ligands. Electron donor capacity of the ligands was studied in terms of spectroscopic data of the trans-RhCl(CO)P₂ species, formed in reaction between Rh₂(-Cl)₂(CO)₄ and the ligands (P). Furthermore, steric attributes of free and bound phosphanes were investigated by Tolmans cone angle method. Crystal structures for ligands o-EtP, o-Me₂P, o-Et₂P, and complexes trans-Rh(CO)Cl(o-MeP)₂ and trans-Rh(CO)Cl(o-Et₂P) were solved as well.     

反应动力学贯串的化学反应工程教学思路及教学案例

化学反应工程是一门工程学科.学生在掌握基本概念的同时,需要与实验研究、工程实践相结合,培养分析、解决工程问题的能力.我们基于化学反应工程课程教学,提出了以反应动力学作为主线,贯串化学反应工程的教学思路,同时结合自身科研实践及工程实例,使学生能直观、系统地掌握知识点,为工程实践打下坚实的基础.     

Tandem Hydroformylation/Acyloin Reaction – The Synergy of Metal Catalysis and Organocatalysis Yielding Acyloins Directly from Olefins

A novel, atom efficient, orthogonal tandem catalysis was developed yielding acyloin products (α‐hydroxy ketones) directly from olefins under hydroformylation conditions. The combination of a metal‐catalysed hydroformylation and an organocatalysed acyloin reaction provides three atom efficient C C bond formations to linear, multifunctional molecules via linkage of the intermediate n‐aldehydes. Additionally, the rhodium catalyst system gives a high n/bra ratio with an exclusive conversion of the terminal double bond in the hydroformylation and the n‐aldehydes are converted selectively to their acyloins.

     

微乳化对ECH和TMAC反应的影响及动力学

在微乳化和非微乳化条件下研究了环氧氯丙烷(ECH)和三甲胺盐酸盐(TMAC)的反应。采用液相色谱和气相色谱分析相结合的方法,分别测定两种条件下随反应时间变化的各物质的量。实验结果表明,反应温度在20~40℃时,微乳条件下10 min时ECH的转化率接近60%,是非微乳条件时转化率的3倍以上;微乳条件下1,3-二氯-2-丙醇(DCP)的生成量比非微乳条件下的高出1个数量级。由此证明微乳条件下生成DCP反应的速率远高于非微乳体系。并根据实验结果建立了微乳化条件下ECH和TMAC反应的动力学方程。     

HPO工艺羟胺反应动力学研究和工艺优化探讨

对HPO工艺硝酸盐加氢还原制备磷酸羟胺的反应进行了小试研究。其小试条件与工业装置相同，得出了羟胺反应动力学模型。对催化剂活性和选择性的影响因素进行了探讨；用侧线实验装置对小试研究结果进行了验证。同时考察了传质对反应的影响；提出了工业装置进一步提高产能，优化生产的途径。     

碳硫比对磷石膏分解率的影响研究

在氮气条件下,磷石膏在不同温度、碳硫比和保温时间下的分解情况不尽相同,提高煅烧温度和延长保温时间可有效的提高磷石膏的分解率。在1100℃和1150℃、碳硫比0.7、保温20 min时,磷石膏分解的分解率可达在99%以上;而在1200℃、保温5 min后,磷石膏的分解率可以达到99%以上。     

硼胺络合物/环氧树脂体系固化反应机理及其动力学的研究

用DSC和IR研究了含有噁硼杂环的硼胺络合物与环氧树脂体系的固化反应机理和固化反应动力学。