Water/Oil Diphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO_2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

Cloud Points of Water—soluble Polyether Phosphites and Their Application in the Biphasic Hydroformylation of Higher Olefins

Wate-soluble polyether phosphites alkyl polyethylene glycol ophenylene phosphite(APGPPS)were alcoholysis of phosphorus chloride with plyoxyethylene alkyl ether.With appropriate HLB(hydrophile-lypophile balance),the phosphites possess clear cloud points below 100℃，Addition of some inorganic salts decreases cloud points of the phosphites.When the phosphiites have long polyether chain binding to short-chain alkyl group,their cloud points could be extrapolated from figure of dependece of cloud points on addition of inorganic salts.Utilizing octylpolyglycol-phenylene-phosphite(OPGPP)(APGPP,R:Octyl)/Rh complex formed in situ as catalyst,over 90% conversion of 1-decene was obtained ,avoiding the limitation of water insolubility of substrates.Preliminary results indicated that micellar catalysis and thermoregulated phase-transfer catalysis(TRPTC)coexist in the reaction system.Below cloud point,micellar catalysis induced by plyether phosphites may be existed.When temperature is increased to above cloud point of the phosphies,this reaction works mainly in TRPTC.The catalysts could be easily spearated by simple decantation,but followed by considerable loss in activity after three successive reaction runs.Preliminary results indicated hydrolysis of OPGPP happened during the reaction.which may explain for the bad loss in activity.The catalyst was reused up to seven times with-out clear decrease in activity when OPGPP/Rh ratio was increased to 50.     

Biphasic Catalytic Hydroformylation of 1-Dodecene in Micellar System with Cationic Gemini Surfactants

The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.     

Reaction Chemistry of W—Mn／SiO2 Catalyst for the Oxidative Coupling of Methane

Reaction chemistry of the OCM reaction on W-Mn/SiO2 catalyst has been reviewed in this account.Initial activity and selectivity,stability in a long-term reaction,reaction at elevated pressures and a modelling test in a stainless-steel fluidized-bed reactor show that W-Mn/SiO2 has promising performance for the development of an OCM process that directly produces ethylene from natural gas.A study on surface catalytic reaction kinetics and used cataly st structure characterization revealed a possible reason why C2 and COx selectivity changed during the long-term reaction.Further improvement of the catalyst composition and preparation metbod should be a future direction of study on OCM reaction over W-Mn/SiO2 catalyst.     

超细SiO2负载型水溶性铑膦配合物催化剂研究

用超细SiO2负载水溶性铑膦配合物,并研究其对1-已烯氢甲酰化的催化性能。结果表明,粒径为10-20nm的超细SiO2负载水溶性铑膦配合物所表现的催化活性比颗粒SiO2负载型催化剂高3倍多,且可在较宽的含水量范围内保持高反应活性。当膦铑摩尔比为50,超细SiO2负载型催化剂含水量为25%-55%（质量分数）、烯铑摩尔比为2500、反应温度373K和CO/H2（1/1,体积比）压力4.0MPa的反应条件下,其1-已烯氢甲酰化的反应转化数为450h^-1,产物醛的选择性为100%,醛的n/i比值达3.2。     

Study of Electron Transfer Reactions Between a Water／1,2-Dichloro-ethane Interface by Scanning Electrochemical Microscopy

Electron transfer (ET) from ascorbic acid (AA) in aqueous to ferrocene (Fc) in 1,2-dichloroethane (DCE) was probed by the scanning electrochemical microscopy (SECM). Therate constants were extracted from the dependence of the steady-state current at ultramicro- electrode (UME, tip) on the distance between the tip and the phase boundary by comparison to theoretical working cures.     

Rapid Synthesis of 1,2,3,4-Tetrahydropyrimidin-2-ones Using Zn（NH2SO3）2 as a Catalyst under Microwave Irradiation

Rapid synthesis of 1,2,3,4-tetrahydropyrimidin-2-ones （THPO） from aromatic aldehydes, β-ketoester and urea （or thiourea） using zinc sulfamate as the catalyst under microwave irradiation was described here. Compared with the classical Biginelli reaction, this new method consistently has the advantages of good yields （76%-96%）, short reaction time （3-15 min）, no corrosion to equipments, ease of manipulation, and low cost catalyst.     

Water/Oil Biphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous highsurface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

Hydroformylation of methyl-3-pentenoate over a phosphite ligand modified Rh/SiO2 catalyst

A phosphite ligand modified Rh/SiO2 catalyst has been developed for hydroformylation of internal olefins to linear aldehydes, which showed high activity and regioselectivity and could be separated easily by filtration after reaction in an autoclave. Effects of reaction temperature and syngas pressure on the performances of the catalyst in the reaction were also investigated.     

高碳烯烃氢甲酰化研究

高碳烯烃氢甲酰化是最重要的石化技术之一.本文从均相催化体系和两相催化体系两个方面介绍了国内外近年来在研究与开发上取得的进展.两 相催化体系的开发正在成为研究的主流引人瞩目,预期新催化剂体系和两相体系在高碳烯烃氢甲酰化应用上将有突破.     

Hydroformylation of methyl-3-pentenoate over a phosphite ligand modified Rh/SiO2 catalyst

A phosphite ligand modified Rh/SiO2 catalyst has been developed for hydroformylation of internal olefins to linear aldehydes, which showed high activity and regioselectivity and could be separated easily by filtration after reaction in an autoclave. Effects of reaction temperature and syngas pressure on the performances of the catalyst in the reaction were also investigated.     

温控离子液体/有机两相体系中纳米Rh催化烯烃氢甲酰化反应

将具有"高温混溶、室温分相"功能的离子液体[CH3(OCH2CH2)16N+Et3][CH3SO3–](ILPEG750)与甲苯-正庚烷组成的两相体系用于纳米Rh催化的烯烃氢甲酰化反应中,在优化的反应条件下,1-辛烯转化率和醛收率分别为99%和91%.催化剂经简单分相即可与产物分离,且可连续使用8次,其活性基本保持不变.     

膦配体修饰的Rh／SiO2用于3-戊烯酸甲酯氢甲酰化反应

制备了膦配体修饰的Rh/SiO2多相催化剂(L-Rh/SiO2),该催化剂在内烯烃氢甲酰化制备正构醛反应中表现出了高活性和高区域选择性,而且在高压釜反应器中可以通过简单的过滤与产物分离.通过使用不同的单齿和螯合双齿膦配体考察了配体的电子及空间效应对L-Rh/SiO2催化剂催化性能的影响。     

烯烃的氢甲酰化串联反应研究

氢甲酰化串联反应是在氢甲酰化反应的基础上,与一个或多个不同类型的反应“一锅法”实现醛类化合物的后续定向转化,得到新的有机分子的合成方法。该反应的产物在日化工业、农业、医药中间体的生产中具有十分重要的用途。本文首先简述了近年来烯烃氢甲酰化串联反应制备高附加值化学品的重要性,随后重点介绍了几种常见的烯烃氢甲酰化串联反应:“异构化-氢甲酰化”串联反应、“氢甲酰化-缩醛化”串联反应、“氢甲酰化-氢化”串联反应和“氢甲酰化-(还原)胺化”串联反应等,以及其在设计新型(多功能)催化剂体系和高效合成目标产物方面的研究进展,最后总结了烯烃氢甲酰化串联反应存在的问题以及对未来发展趋势进行了展望。     

温控相转移纳米铑催化高碳烯烃氢甲酰化反应

 基于温控配体 Ph₂P(CH₂CH₂O)₁₆CH₃ 稳定的 Rh 纳米催化剂在水/1-丁醇两相体系中具有温控相转移功能, 将其用于高碳烯烃氢甲酰化反应中. 在优化的反应条件下, 1-辛烯转化率和醛收率分别达 98% 和 96%, 对其它高碳烯烃氢甲酰化反应也具有较高的催化性能. 催化剂和产物通过简单的相分离即可分开, 连续使用 3 次后, 催化剂性能未见明显降低.