多相铂催化剂在芳香族化合物加氢中的应用

介绍了负载型铂催化剂、高分子铂络合物催化剂和负载型含铂双金属催化剂等几种多相铂催化剂在芳香族化合物加氢中的应用及各自特点，展示这类催化剂在反应中具有良好的催化活性。     

多相加氢数学模型的回归

详细介绍了多相催化加氢数学模型回归的计算方法。对无副反应存在下数学模型可以处理成为线性模型进行简化,从而求得参数。但该法直接使用的dC/dt值,是使用作图镜面法获得,会引入误差。本文着重介绍使用计算机对反应数据进行dC/dt值和参数同时回归的实现方法、原理、流程,以及应用Matlab语言回归时所需的命令和求解方法。同时,该方法也可应用于多组份多副反应动力学的回归。     

Heterogeneous Asymmetric Hydrogenation of N-Heterocyclic Compounds: Hydrogenation of Tetrahydroisoquinoline Derivatives

The preparation and application of heterogeneous chiral catalysts are described. Heterogeneous Pd, Ir and Ru catalysts were tested in the enantioselective hydrogenations of N-heterocyclic compounds, namely 6,7-dimethoxy-3,4-dihydroisoquinoline and 1-methylene-2-ethoxycarbonyl-6,7-dimetoxy-3,4-dihydroisoquinoline in the presence of optically pure cinchonidine, (S,S)- and (R,R)-Ts-DPEN ligands. Cinchonidine-modified metal catalysts exhibited low ee, whereas catalysts stabilized by triphenylphosphane and modified by (S,S)-Ts-DPEN afforded promising ee values (70–80 %). Immobilized Ru(II)-aminophosphane complexes were found to be active in these hydrogenations producing the corresponding tetrahydroisoquinoline derivatives in high optical purities (up to 97 %). The latter catalysts were characterized by infrared spectroscopy, solid-state MAS NMR spectroscopy and elemental analysis. Recycling of these catalysts showed constant or increasing activities in racemic hydrogenation, whereas the presence of the chiral ligands led to leaching of the active species in the liquid phase.     

多相催化加氢动力学方程的建立与推导

在化学实验放大到生产装置过程中,催化反应动力学的研究具有十分重要的意义。详细介绍了多相催化加氢动力学方程的建立与推导过程,通过可能存在的反应机理,按照Langmuir吸附等温方程和决速步假设,建立并推导可能存在的反应方程,以便于按照这些方程对反应数据进行回归分析,得到可能的反应方程以推测出可能的反应机理。同时,还列举了一些已被证实的反应速率模型。     

Heterogeneous Catalytic Hydrogenation of Ethyl Acetate to Produce Ethanol

The hydrogenation of ethyl acetate to produce ethanol has been studied, first in scoping runs with a commercial catalyst and then with a Degussa H10167 copper chromite catalyst. Both catalysts exhibit good stability with the Degussa catalyst maintaining constant conversion levels for over 3,000 h; however, some as yet unidentified factor impacts the aging character of the catalyst. Acetic acid is a catalyst poison so that each 1 % vol. of acid in the liquid feed decreased the conversion of ethyl acetate by 8 %. This decrease appears to be due to the acid being hydrogenated more slowly than the ester since, at lower concentrations, the acid is completely converted. Even at high (90 %) total conversion, the selectivity for ethanol is 93 % or higher.     

催化加氢制备含卤芳胺化合物工艺研究

采用BCA为防脱氯剂,甲醇为溶剂,用自制催化剂进行加氢还原2,5-二氯硝基苯制备了2,5-二氯苯胺。最佳工艺条件为:反应温度70~75℃,氢气压力0·7~0·8MPa,w(2,5-二氯硝基苯)∶w(自制催化剂)=63·4∶1·0。在此最佳工艺条件下,得到的产品含量(气相色谱外标法)99·3%,产品收率达96·2%。     

多相贵金属催化剂对芳香化合物催化加氢研究进展

综述了近年来多相贵金属催化剂对芳香化合物加氢的研究；揭示了负载型铂、钯、钌、铑以及二元金属催化剂各自在加氢反应中的特点，以及载体、助催化剂对其活性和选择性的重要作用；同时介绍了TCSM和Raney型贵金属催化剂的概况。     

Combination of Reaction and Separation in Heterogeneous Catalytic Hydrogenation of Ethylformate

Continuous hydrogenation reaction of ethyl benzoylformate was studied over a (–)‐cinchonidine (CD)‐modified Pt/Al₂O₃ catalyst. The catalyst showed a good stability, and high enantioselectivity was achieved in the fixed‐bed reactor. Chromatographic separation of (R)‐ and (S)‐ethyl mandelate originating from a post‐continuous hydrogenation reaction of ethyl benzoylformate over the (–)‐CD‐modified Pt/Al₂O₃ catalyst was investigated in the same reaction mixture. A commercial column filled with a chiral selector resin was chosen as a perspective preparative‐scale adsorbent. Since adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post‐reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug‐flow model with linear driving force approximation.     

Catalytic Friedel–Crafts Acylation and Benzoylation of Aromatic Compounds Using Activated Hematite as a Novel Heterogeneous Catalyst

Catalytic Friedel–Crafts acylation of benzene and unactivated benzenes such as chlorobenzene and nitrobenzene have been successfully carried out using activated hematite (α‐Fe₂O₃) as a new, heterogeneous and green catalyst. Sonication of neat α‐Fe₂O₃ in a water bath under air atmosphere at room temperature followed by heating at 200 °C, dramatically increase the activity of α‐Fe₂O₃. With the catalyst loading as low as 5.0 mol%, a wide variety of benzene derivatives were easily converted into the corresponding acylated products in a clean and high‐yielding acylation reaction. It was found that the activated α‐Fe₂O₃ could be efficiently recycled and reused several times by simple washing with ethyl acetate, this cannot be attained with most of the traditional catalysts.     

芳硝基物的水合肼催化还原研究进展

综述了芳硝基物水合肼催化还原反应中溶剂、催化剂、硝基物分子结构对还原反应的影响。有12篇参考文献。     

Thermo-responsive Ruthenium Dendrimer-based Catalysts for Hydrogenation of the Aromatic Compounds and Phenols

In this work thermo-responsive ruthenium catalysts, based on the poly(propylene imine) dendrimers cross-linked with the poly(ethylene glycol) diglycidyl ether, have been prepared for the first time. The materials obtained were characterized by X-ray photoelectron spectroscopy and transmission electron microscopy, and tested in the phenol and benzene hydrogenation. Conditions for the metal impregnation into the polymeric matrix were demonstrated to have a great influence both on physical chemical properties of the synthesized catalysts (metal loading, mean particles size, surface structure etc.), and, as a consequence, on their hydrogenation activity and thermo-responsive properties.     

芳香族硝基化合物的水合肼催化还原反应的研究

研究了以８０％水合肼为还原剂,在ＦｅＣｌ３·６Ｈ２Ｏ／Ｃ存在下,回流３～８ｈ,将芳香族硝基化合物转变成芳香族氨基化合物的还原反应。相应的氨基化合物的产率达到８５％～９８％。     

液相催化加氢法制取芳胺的研究进展

对近年来以硝基芳烃为原料,用液相催化加氢还原方法制取芳胺的应用及其进展进行了归纳总结。对液相催化加氢法的主要影响因素和工艺条件进行了探讨。说明了该项技术具有很好的推广应用前景。     

催化CO/H2O还原芳香硝基化合物制芳胺的研究进展

CO／H2O还原芳香硝基化合物制芳胺是1978年首次被发现。所使用的催化剂为过滤金属羰基化合物有些可以在常温常压下完成反应，并具有很好的选择性，在反应完成后可将催化剂从反应产物中分离这项技术可以做为加氢还原重要补充。反应过程的常压化、催化剂的分离将成为这项技术研究重点。这项新技术将有广阔的工业前景、有24篇参考文献。     

Diastereoselective Hydrogenation in the Preparation of Fine Chemicals

Heterogeneous catalytic diastereoselective hydrogenation is reviewed with a special emphasis on its application in the preparation of fine chemicals.     

含低价硫芳硝基化合物催化氢转移还原制备芳香胺

在自制耐低价硫催化剂存在下,以水合肼为氢给体,对5种含硫芳硝基化合物的催化氢转移还原进行了研究.结果表明,催化剂表现出极高的活性,反应在20-50min完成,仅消耗理论量的水合肼,产率97%～99%.     

含氟芳香族化合物的合成

介绍了含氟芳香族化合物的几种合成方法,叙述了卤交换氟代中的几个关键技术。叙述了一些重要的含氟芳香族化合物医药中间体的合成路线、方法。     

Aromatic Hydrogenation Catalysis: A Review

High aromatic content in diesel fuel has been recognized both to lower the fuel quality and to contribute significantly to the formation of undesired emissions in exhaust gases [1, 2]. Because of the health hazards associated with these emissions, environmental regulations governing the composition of diesel fuels are being tightened in both Europe and the United States, leading to limitations on aromatics [3, 4].