Hydrogenation of nitriles with iridium-triphenylphosphine complexes

Reactions of cationic iridium(I)-COD (COD = 1,5-cyclooctadiene) complexes, [Ir(COD)(PhCN)(PPh₃)]ClO₄ (1), [Ir(COD)(PPh₃)₂]ClO₄ (2) and [Ir(COD)(PhCN)₂]ClO₄ (3) with nitriles under H₂ catalytically produce primary, secondary and tertiary amines. Hydrogenation of nitriles (RCN) gives HCl salts of amines (RCH₂NH₂HCl, (RCH₂)₂NH HCl) in CH₂Cl₂. Secondary and tertiary amines seem to be produced by the reactions of RCN with primary and secondary amines, respectively under H₂ in the presence of catalysts. The hydrogenation in the presence of1 and2 is homogeneously catalyzed by soluble iridium-PPh₃ complexes formed in the reactions of1 and2 with H₂ and RCN whereas the hydrogenation in the presence of3 is heterogeneous by metallic iridium powders produced in the reduction of3 by H₂.     

Selective hydrogenation of oleic acid to 9-octadecen-1-ol: Catalyst preparation and optimum reaction conditions

A new catalyst, ruthenium-tin-alumina is found to selectively hydrogenate oleic acid to 9-octadecen-1-ol (oleyl + elaidyl alcohol) at low pressure with high yield. Catalyst preparation methods, catalyst raw materials and activation conditions have a significant effect on the activity of the catalyst. The optimum atomic ratio of ruthenium to tin is about 1:2. Catalyst prepared by an improved sol-gel method shows higher activity and selectivity than catalysts prepared by impregnation and coprecipitation methods. Chloride is found to have a negative effect on catalytic activity. The best catalyst is prepared from chloride-free ruthenium and tin raw materials. Under the optimum reaction conditions of 250°C and 5.6 MPa, the selectivities for 9-octadecen-1-ol and total alcohol (9-octadecen-1-ol + stearyl alcohol) formation are 80.9% and 97%, respectively, at a conversion of 81.3%.     

Determination of effectiveness factor of a partial internal wetting catalyst from adsorption measurement

The effect of partial internal wetting of catalyst pellets on apparent reaction kinetics at elevated temperatures and pressures is investigated experimentally and by modeling for benzene hydrogenation. A new method that combines adsorption and chemical reaction is introduced to study the kinetics influenced by capillary condensation of reagents at steady-state conditions. It is shown that the extent of liquid filling in the pellet interior has a critical effect on the global kinetics, and the current state of the catalyst depends on the history. Under certain conditions two steady states of the effectiveness factor exist. Moreover, either a decrease in temperature or increase in total pressure can increase the effectiveness factor. The model exhibits good agreement with experimental results.     

加氢还原新工艺及设备

介绍了二硝基甲苯液相加氢还原制备二氨基甲苯的生产工艺 ,催化剂采用含 0 1%～ 0 3%骨架镍的浆状催化剂 ,反应温度为 10 0℃ ,氢气压力在 15～ 2 0MPa,所得二氨基甲苯的纯度为 99%。还介绍了带复合式搅拌器的加氢反应釜、环式加氢反应器、循环反应器、卧式连续加氢反应器和三相固定床反应器。     

加氢富气干法脱队硫化氢催化剂的研究

以γ-Al2O3为载体,以钒、铋为活性组分,镧、钠等为助剂制成用于干法选择氧化脱除加氢富气中硫化氢的催化剂。其最佳反应条件是：反应温度180℃;空速1400h^-1;常压。在该反应条件下加氢富气中H2S的平均转化率为93％,平均选择性为90．5％。小试及工业放大试验结果表明该催化剂具有寿命长、性能稳定、再生效果好等优点,适用于脱除加氢富气中的硫化氢。     

石蜡加氢精制催化剂工业化应用现状和选用建议

介绍 4 8 1 - 2B、RJW - 1、RJW - 2、FV - 1和SD - 1五种石蜡加氢精制催化剂的工业化应用现状和特点 ,对不同石蜡加氢装置催化剂的选用提出了建议     

吲哚甲基海因的制备 I.加氢过程研究及催化剂的磁分离

采用30%T-1型Raney-Ni催化剂,以NaOH(1mol/L)为溶剂,在45℃,初始压力为3.0MPa的条件下,吲哚亚甲基海因加氢可以得到吲哚甲基海因,收率为85.6%。实验结果表明,吲哚亚甲基海因加氢速度对催化剂浓度为一级关系;在一定范围内,与初始氢压成正比关系。由不同反应温度下的反应初速度计算吲哚亚甲基海因加氢反应的表观活化能Ea为15.92kJ/mol。采用磁性材料固定方法可实现催化剂的回收利用。经20批次吲哚亚甲基海因加氢反应结果可知,催化剂的使用量降低为4.5%,吲哚甲基海因的收率可稳定在80%左右。     

对苯二甲酸精制钯碳催化剂内扩散有效因子的估算

在高压磁力搅拌间歇反应釜中研究了粗对苯二甲酸在不同反应温度下,两种粒径的Pd/C催化剂上加氢精制反应的规律。按照该反应对于对羟基苯甲醛(4 CBA)是拟一级反应估算了催化剂的内扩散有效因子η值。本试验估算的η值与动力学研究拟合得到的η值吻合良好。     

Improved Palladium and Nickel Catalysts Heterogenised on Oxidic Supports (Silica,MCM‐41, ITQ‐2, ITQ‐6)

Two series of solid catalysts in which a chiral palladium or nickel complex with Schiff bases as ligands have been immobilized on ordered mesoporous silica supports (MCM‐41), delaminated ITQ‐2, ITQ‐6 zeolites and amorphous silica have been prepared. Hydrogenation of alkenes and imines was studied with the homogeneous as well as with the counterpart heterogenized catalysts. The high accessibility introduced by the structure of the supports allows the preparation of highly efficient immobilized catalysts with TOFs of 1,000,000 h⁻¹. A moderate acidity in the support increases the catalytic activity considerably, and the easy recoverable immobilized catalysts can duplicate the activity of the homogeneous analogues. No deactivation of the catalysts was observed after repeated recycling.     

Premodification of Pt/γAl2O3 with Cinchonidine for the Enantioselective Hydrogenation of Ethyl Pyruvate: Effect of Premodification Conditions on Reaction Rate and Enantioselection

The premodification of a 5 wt% Pt/-Al₂O₃ catalyst with cinchonidine (0.01 and 0.2 g g^-1 _catalyst) is described and discussed. Premodification is carried out by treating the catalyst with a solution of cinchonidine followed by solvent removal. Catalysts premodified in this way give the same ee and initial rate of reaction for the enantioselective hydrogenation of ethyl pyruvate as those using the standard in situ modification procedure. Investigations of different solvents for premodification and reaction (dichloromethane, ethanol) show that it is the solvent used for the reaction that controls the observed enantioselection. Premodified catalysts also display the initial transient behavior typically observed with in situ modified catalysts in which the ee increases with conversion in the early part of the reaction. Premodified catalysts show an enhanced rate of reaction when ethanol is used as the reaction solvent compared with in situ modified catalysts under the same conditions. Premodification using aerobic conditions gives the best results and premodified catalysts can be stored prior to use for up to a week without loss of catalytic performance.