Kinetic modeling of homogeneous catalytic processes

Homogeneous catalysis by soluble metal complexes is gaining considerable attention due to their unique applications and features like high activity and selectivity. In this paper, a brief review of kinetic modeling in homogeneous catalysis has been presented. Approaches using empirical as well as molecular level rate models have been discussed. Special features relevant to asymmetric catalysis and multiple rate controlling steps have also been addressed. A case study on kinetics of carbonylation of 1-(4-iso-butylphenyl)ethanol using a homogeneous palladium catalyst has been discussed.     

羰基化反应研究与应用

在有机化合物分子内引入CO的羰基化反应因具有"原子经济性"反应的高选择性和对环境友好而备受学术界及工业界关注.作者通过典型实例综述了氢甲酰化、氢酯基化、氢羧基化及不对称羰基化反应的研究与应用进展.对羰基化反应的催化剂和催化反应机理进行了探讨.     

Synthese von aliphatischen Aldehyden aus Alkanen und Kohlendioxid: Valeraldehyd aus Butan und CO2 – Machbarkeit und Grenzen

During the last decades, the engineering of chemical processes has focused more and more on energy efficiency and reduction of climate‐changing emissions. Regarding the synthesis of aldehydes, the photocatalytic dehydrogenation of alkanes to olefins, using visible (sun) light, and the subsequent hydroformylation of such olefins with CO₂ seem to be capable to achieve both targets. This work deals mainly with catalyst concepts for both reaction steps. Here, kinetic studies of the photocatalytic alkane dehydrogenation are presented, and the feasibility of hydroformylation using CO₂ is described in a continuous gas phase reaction. The problems that have to be solved befoe the technical application are discussed and an economic and ecological evaluation for both processes is carried out.     

新型烯烃氢甲酰化催化剂的合成及其催化作用

用膦化的交联聚氯乙烯与YCCo_3(CO)_9(Y=Ph,Cl,H及—C_3H_7)制备了A,B,C,D四个担载羰基钻原子簇催化剂。利用红外光谱、紫外漫反射光谱鉴定了它们的结构。在4.0MPa(CO:H_2=1:1)条件下,考察了它们对烯烃氢甲酰反应的催化作用。实验表明,该原子簇催化剂以A和B的活性低,C和D活性高。当温度140℃,反应23h,用D作催化剂,1-庚烯的转化率达97.4％,选择性93.4％。     

CHEMICAL AND TECHNICAL ASPECTS OF HYDROFORMYLATION OF OLEFINS WITH SUPPORTED LIQUID-PHASE RHODIUM CATALYSTS

Supported liquid-phase catalysts containing RhH(CO)(PPH₃)₃ dissolved in PPH₃ are used in the gas-phase hydroformylation of several olefins. Their activity in the hydroformylation of ethylene, propylene and the butenes is reported.

Various physicochemical aspects of the rhodium SLP catalysts, such as the adsorptive withdrawal of the rhodium complexes by the supports, the activity of the rhodium complexes at the gas-liquid interface and the solubility of the reactants and products in the liquid part of the catalysts, are discussed.

The results are presented of a bench-scale process study of the hydroformylation of propylene, from which the design parameters of a future plant are calculated.     

烯丙基衍生物氢甲酰化合成精细化学品

介绍了烯丙基衍生物——烯丙醇、烯丙醇酯、丙烯腈、丙烯酸、烯丙胺等的氢甲酰化反应,利用该反应可合成丁二醇、2-羟基四氢呋喃、α-氨基酸和吡咯啉酮等多种精细化工产品。综述了近年来的研究成果。     

Hydroformylation of 1-hexene for oxygenate fuels via promoted cobalt/active carbon catalysts at low-pressure

The hydroformylation of 1-hexene was catalyzed with active carbon-supported cobalt catalysts under the low syngas pressure. Small amount of Pt, Pd and Ru, added as promoters in Co/AC, led to a great improvement of catalytic activity for hydroformylation of 1-hexene. The promotional effect of Ru for Co/AC catalyst was the best in this study as the highest activity and selectivity for oxygenate formation. Meanwhile, the activity of 1-hexene hydroformylation increased with increasing Ru loading. Ru added was bulk-rich in the active carbon supported cobalt particles, showing very low surface Ru density. This kind of unbalanced alloy formation determined the highest performance of Ru added Co/AC catalyst, via small particles but high reduction degree, keeping more CO in non-dissociative state and lowering surface hydrogen pressure.     

聚苯乙烯基2，2′─联吡啶担载的羰基钌和羰基铑络合物催化剂的合成及其对烯烃氢甲酰化反应的催化作用

聚苯乙烯基２，２′─联吡啶与Ｒｕ３（ＣＯ）１２和Ｒｈ１２（ＣＯ）４Ｃｌ２反应，制备了担载金属羰基络合物（Ａ）和（Ｂ）．利用红外光谱进行了结构鉴定．对１─庚烯的氢甲化反应的实验结果表明，Ａ的活性低，选择性差；Ｂ的活性高，选择性好．当催化剂Ｂ０．２６克，１─庚烯１．０ｍｌ，甲苯５．０ｍｌ，压力４．０ＭＰａ（ＣＯ：Ｈ２＝１：１），温度１１０℃，反应时间２０ｈ，１─庚烯转化率达９０％以上，选择性超过９５％．进行５６０ｈ时寿命实验，Ｂ仍有很高的催化活性．     

双环戊二烯在水溶性铑膦络合催化体系中的氢甲酰化反应

研究了采用水溶性铑膦络合催化体系对双环戊二烯的氢甲酰化反应，考查了反应温度、相转移剂ＣＴＡＢ、铑催化剂浓度等对反应的影响。氢甲酰化反应的产物经ＧＣ／ＭＳ鉴定是不饱和的三环癸单醛     

Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity

Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. Both acids contain an exocyclic methylenic double bond that allows further functionalization on their structure. In an attempt to expand the number of derivatives of these two natural products, we have undertaken a study on the hydroformylation of the methyl esters of the two acids and the trimethylsilyl ether of kaurenol. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh₃ and Rh/tris-(o-t-butylphenyl)phosphite catalytic systems at 100 °C and 20 bar of CO/H₂ (1:1). For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes. In all cases, the stereoselectivity observed is strongly dependent of the system used, being the most diastereoselective the least hindered unmodified Rh/CO catalyst. A correlation between the higher diastereoselectivity and the faster β-elimination of the metal-alkyl intermediate observed in the unmodified system is discussed.