碳碳双键催化加氢的研究进展

综述了近年来碳碳双键催化加氢的研究进展;分别针对以氢气为氢源的催化加氢反应和以非氢气为氢源的催化转移加氢反应进行了分析概括;指出其中催化转移加氢(包括光照下转移加氢)具有反应条件温和且操作安全简便的优势,应用前景广阔.     

油脂加氢催化剂研究进展

油脂加氢可增加油的氧化稳定性和保存期限,是改变油脂物理、化学性质的常用方法,也是油脂工业中非常重要的一个催化过程.我们从催化剂的种类以及加氢反应机理等方面综述了油脂加氢催化剂的研究进展,并对新型加氢催化剂及工艺进行了概述,最后对未来催化剂改进和工艺发展提出了看法.     

抗硫性芳烃加氢催化剂研究进展

因环保立法限制,芳烃加氢日益受到重视.本文简述了芳烃加氢的热力学及动力学行为,归纳总结了不同的抗硫性芳烃加氢催化剂类型及其加氢机理.鉴于硫中毒对过渡金属催化剂性质的复杂影响,对过渡金属催化剂的硫中毒做了较为详尽的阐述.     

廉价金属铁、钴、锰配合物催化的加氢/脱氢反应研究进展

催化加氢和脱氢反应是现代化学工业的发展核心.从毫克级有机化学反应探索到吨级化学品的生产,均存在催化加氢和脱氢反应的广泛应用.长期以来,贵金属催化剂是实现含氮及含氧化合物催化加氢和脱氢反应的关键所在.从绿色环保及可持续发展的角度出发,近年来廉价金属催化的加氢和脱氢反应取得了重要的研究进展,本文主要介绍在非贵金属催化的加氢...     

羧酸加氢反应机理及催化剂的研究进展

生物质衍生羧酸化合物的加氢反应是生产生物质化学品的重要过程之一.我们从羧酸分子加氢反应机理与加氢催化剂两个方面进行概述,着重介绍了第VIII族金属,尤其贵金属作为活性金属的羧酸加氢反应机理,以及不同催化剂对羧酸加氢反应途径的影响.此外,还介绍了羧酸水相加氢反应中Ru基催化剂的研究进展.     

氢解还原法进行环境污染控制

化学氢解法具有脱卤、脱氮、脱硫、脱芳构化等作用,目前的研究表明该方法对环境中的许多重要污染物都具有还原去除效果,包括卤代化合物、硝基芳香化合物、有机硫化合物、多环芳烃等有机污染物,以及硝酸盐、硫酸盐、氮氧化物、二氧化硫、重金属等无机污染物。为此,本文综述了氢解还原方法降解各类污染物的研究现状,分别介绍了上述各种污染物氢解还原的脱除机理以及影响因素的作用机制,基于绿色化学的要求分析了氢解还原方法的技术优势,从提高氢解效率和节能的角度提出了今后的研究方向。     

Über die Hydrierung α-cyanoäthylierter Aldimine

The catalytic hydrogenation of α-mono- and bis-cyanoethylated aldimines The catalytic hydrogenation of α-mono- and -bis-cyanoethylated aldimines using nickel catalysts was studied. Piperidine derivatives are formed in intramolecular cyclization reactions. The hydrogenation products of α-bis-cyanoethylated ketones, the decahydro-1, 8-naphthyridines, are observed here only as by-products.     

First-Principles Microkinetic Study of Methanol Synthesis on Cu(221) and ZnCu(221) Surfaces

First-principle based microkinetic simulations are performed to investigate methanol synthesis from CO and CO₂ on Cu(221) and CuZn(221) surfaces. It is found that regardless of surface structure, the carbon consumption rate follows the order:CO hydrogenation > CO/CO₂ hydrogenation > CO₂ hydrogenation. The superior CO hydrogenation activity mainly arises from the lower barriers of elementary reactions than CO₂ hydrogenation. Compared to Cu(221), the introduction of Zn greatly lowers the activity of methanol synthesis, in particularly for CO hydrogenation. For a mixed CO/CO₂ hydrogenation, CO acts as the carbon source on Cu(221) while both CO and CO₂ contribute to carbon conversion on CuZn(221). The degree of rate control studies show that the key steps that determine the reaction activity of CO/CO₂ hydrogenation are HCO and HCOO hydrogenation on Cu(221), instead of HCOOH hydrogenation on CuZn(221). The present work highlights the effect of the Zn doping and feed gas composition on methanol synthesis.     

A novel liquid system of catalytic hydrogenation

On the basis that endothermic aqueous-phase reforming of oxygenated hydrocarbons for H2 produc- tion and exothermic liquid phase hydrogenation of organic compounds are carried out under extremely close conditions of temperature and pressure over the same type of catalyst, a novel liquid system of catalytic hydrogenation has been proposed, in which hydrogen produced from aqueous-phase re- forming of oxygenated hydrocarbons is in situ used for liquid phase hydrogenation of organic com- pounds. The usage of active hydrogen generated from aqueous-phase reforming of oxygenated hy- drocarbons for liquid catalytic hydrogenation of organic compounds could lead to increasing the se- lectivity to H2 in the aqueous-phase reforming due to the prompt removal of hydrogen on the active centers of the catalyst. Meanwhile, this novel liquid system of catalytic hydrogenation might be a po- tential method to improve the selectivity to the desired product in liquid phase catalytic hydrogenation of organic compounds. On the other hand, for this novel liquid system of catalytic hydrogenation, some special facilities for H2 generation, storage and transportation in traditional liquid phase hydrogenation industry process are yet not needed. Thus, it would simplify the working process of liquid phase hy- drogenation and increase the energy usage and hydrogen productivity.     

苯甲酸甲酯促进茂金属催化剂催化SBS加氢反应研究

以苯甲酸甲酯为促进剂,用茂金属催化剂制备了活性丁苯嵌段共聚物(SBS)的选择性催化加氢产物,讨论了苯甲酸甲酯、SBS的数均分子量等因素在几种实验条件下对产物加氢度的影响.结果表明,每百克干胶使用0.15～0.3mmol Ti催化条件下,苯甲酸甲酯在特定添加方式下能较大程度地提高茂金属催化剂的活性.在不加入苯甲酸甲酯的情况下,Mn=6.5×104和Mn=5.5×104两种SBS基础胶加氢反应180min时加氢度均97.0%;加入酯以后,反应60～120min时,基础胶的加氢度≥98%;与已报道的研究结果相比,将加氢反应时间缩短了60～120min.在每百克干胶使用0.15～0.3mmolTi催化条件下,数均分子量的大小也对SBS基础胶的加氢度有影响,反应30min时,Mn=5.5×104的加氢度≥97%,Mn=6.5×104的加氢度90%;随着反应时间的延长,这种差距在逐渐缩小;反应180min时,两者已无明显差距,此时两种基础胶的加氢度都≥98%.对影响的加氢度的机理进行了解释.     

Ionic liquids for the sustainable transformation of levulinic acid to gamma-valerolactone (GVL)

This short review is focused on recent findings on the role of ionic liquids (ILs) in catalysing the hydrogenation of levulinic acid (LA) to gamma valerolactone (GVL), which is a cascade reaction involving more than one type of reaction. A brief introduction on green aspects of IL as a catalyst followed by various types of ILs being used for hydrogenation of LA to GVL are discussed. The unique characteristics of ILs responsible for hydrogenation reaction are also explained along with the current and upcoming scenario of IL catalysed hydrogenation of LA to GVL.     

聚N—乙烯基吡咯烷酮分散钯催化剂加氢性能的研究

制备了聚N-乙烯基吡咯烷酮分散钯催化剂,考察了它对不同底物的加氢活性和在不同介质中对丙烯酸甲酯的加氢活性。结果表明,不同底物的加氢活性和反应级数都有很大的差别,且反应介质对丙烯酸甲酯的加氢速率也有很大影响。还得到了丙烯酸甲酯加氢反应的速率方程。     

常温常压下吡咯及其衍生物的镍催化加氢反应考察

为进一步研究常温常压下吡咯及其衍生物的镍催化加氢反应,我们对试剂吡咯、吡咯烷和吡咯烷酮做了相应的催化加氢实验。并采用电镜（TEM-HREM）、X射线衍射（XRD）对Ni基催化剂的形貌、结构、加氢活性和超声波对其影响进行了检测,同时还用紫外吸收光谱、气相色谱等对加氢产物进行了分析考察。结果表明超声波能促进镍基催化剂活性,使镍微晶(111)晶面间距增大1.5%、并保持高分散态。常温常压下纳米镍基催化剂对吡咯、吡咯烷和吡咯烷酮的加氢反应显示一定的催化活性;吡咯加氢首先生成吡咯烷,进而使环打开生成低碳烃、氨等产物,总反应为零级,符合表面接触反应特征。     

Morphological and chemical influences on alumina-supported palladium catalysts active for the gas phase hydrogenation of crotonaldehyde

A series of five alumina-supported palladium catalysts have previously been prepared and characterised by a combination of CO chemisorption and infrared spectroscopy. The reactive attributes of these catalysts are examined using the hydrogenation of crotonaldehyde as a test reaction, using a modified infrared gas cell as a batch reactor. Periodic scanning of the infrared spectrum of the gaseous phase present over the Pd/Al(2)O(3) catalysts was used to construct reaction profiles. Four of the catalysts were able to facilitate a 2-stage hydrogenation process (crotonaldehyde → butanal → butanol), whilst one catalyst was totally selective for the first stage hydrogenation process (crotonaldehyde → butanal). Rate coefficients for the first and second stage hydrogenation processes are normalised to the number of surface palladium atoms for the particular catalyst. Correlation of these kinetic parameters as a function of mean particle size indicates the first stage process to be structure insensitive, whilst the second stage hydrogenation is structure sensitive. Chlorine residues associated with the preparative process of one of the catalysts is seen to selectively poison the second stage hydrogenation process for that catalyst. Structure/activity relationships are considered to explain the observed trends.     

Preparation of Hydrogenated Nitrile Rubber

Hydrogenated nitrile rubber is an oil and solvent resistant rubber and particularly give more resistant to heat, ozone, light. It is generally prepared from nitrile rubber by selective hydrogenation using a suitable catalyst system. In the present work a prepared method was adapted for the hydrogenation reaction of nitrile rubber using homogeneous tris(tri-phenlphosphine)chlorhodium(I) catalyst (RhCl(PPh3)) system. The hydrogenation reaction was carriedout at different temperature, pressure, time and catalyst concentration, the concentration, the conditions of hydrogenation are stated in table 1.     

Ziegler-type hydrogenation catalysts made from group 8–10 transition metal precatalysts and AlR3 cocatalysts: A critical review of the literature

Ziegler-type hydrogenation catalysts (group 8–10 transition metal precatalysts plus AlR₃ cocatalysts) are one of the most important families of industrial hydrogenation catalysts, especially for polymer hydrogenation. Despite their ～40 year history of industrial use, there is a need for improved fundamental understanding in order to make further, rationally directed improvements in these catalysts. This review examines the existing literature on Ziegler-type hydrogenation catalysts, specifically: (i) the variables important to catalyst synthesis, (ii) the catalyst formation reaction mechanism, (iii) the compositional and structural nature of the active catalyst species, and (iv) the mechanism of catalytic hydrogenation. This review also (v) discusses the current approaches to the homogeneous versus heterogeneous catalysis question, with the goal of identifying if Ziegler-type hydrogenation catalysts are homogeneous (e.g., monometallic) versus heterogeneous (e.g., nanoclusters) as the true catalyst(s). A summary of the main insights from each section of the review is also given.     

Enantioselective Hydrogenation and Transfer Hydrogenation of Bulky Ketones Catalysed by a Ruthenium Complex of a Chiral Tridentate Ligand

A study on the enantioselective hydrogenation of tertiary alkyl ketones catalysed by a novel class of tridentate–Ru complex is reported. In contrast to the extensively studied [RuCl₂(diphos)(di-primary amine)] complexes, this new class of hydrogenation catalyst smoothly reduces these less reactive bulky ketones with up to 94 % ee. The same catalyst system can also selectively reduce other potentially problematic substrates such as bulky heterocyclic ketones. Unusually for a pressure hydrogenation catalyst, similar enantioselectivity can be obtained under transfer hydrogenation conditions. The transfer hydrogenations are somewhat slower than the pressure hydrogenations, but this drawback is readily overcome, since we have discovered that a microwave accelerated transfer hydrogenation of the above ketones occurs within 20 min at about 90 °C with similar selectivity to that obtained in the pressure hydrogenation system.     

芳香氨基酮选择性还原反应的研究

非均相催化剂(钯碳催化剂)一般会将芳香酮彻底还原至亚甲基产物,而不易得到苄醇类的中间还原产物.本文报道一系列氨基酮用钯碳催化剂催化氢化的结果,随酮底物含有不同种类的氨基而得到不同的氢化产物(亚甲基产物或二级醇产物),部分则不发生还原反应;分析讨论了底物所含氨基对产物的影响及其机理.结果表明,这是一个制备胺基芳香仲醇的有效方法.     

合成气制低碳烯烃K－Fe－MnO／MgO催化剂的研究Ⅰ．MnO助剂的作用

采用ＣＯ加氢反应、ＣＯ－ＴＰＤ、ＣＯ／Ｈ＿２－ＴＰＳＲ及Ｃ＿２Ｈ＿４／Ｈ＿２－ＴＰＳＲ等手段，研究合成气制低碳烯烃反应Ｋ－Ｆｅ－ＭｎＯ／ＭｇＯ催化剂中ＭｎＯ的助剂作用。结果表明ＭｎＯ能大幅度提高低碳烯烃的选择性，尤其是乙烯的选择性；ＭｎＯ能抑制催化剂表面的乙烯加氢，因而有利于提高低碳烯烃的选择性及烯／烷的比值。     

温和条件下稀土氯化物-萘催化的碱金属氢化物的合成

本文研究了稀土氯化物对碱金属氢化反应的催化作用。金属钠在稀土氯化物LnCl~3(Ln=La,Nd,Sm,Dy,Yb)和萘的催化下,在常压、40℃下能与氢气反应,生成氢化钠;稀土氯化物的催化活性顺序为LaCl~3>NdCl~3>SmCl~3>DyCl~3>YbCl~3。金属锂可发生类似反应,生成LiH;但其反应动力学曲线与金属钠相比明显不同。稀土氯化物对金属钾的氢化反应不显示催化作用。对反应机理的初步探索表明:碱金属与萘反应生成的阴离子自由基型物种可能是氢化反应的中间体,稀土氯化物的作用是催化该中间体的氢化反应。该反应的产物是一类大比表面积(NaH的比表面积为83m^2/g)、多孔性固体粉末,在空气中可自燃。它们具有比一般市售碱金属氢化物高得多的反应活性,并能与过渡金属配合物组成高活性烯烃加氢催化。