钌催化苯选择加氢制环己烯的研究进展

介绍了钌催化苯选择加氢制环己烯这一经济、安全、高效的环己烯制备新工艺的研究进展,着重介绍了液相法苯选择加氢制环己烯钌系催化剂的研究及其对苯液相选择加氢制环己烯反应的各种影响。指出钌催化剂应用于苯相选择国氢制环己烯一般选择反应温度为150℃-190℃,压力为4MPa-5MPa,加入助催化剂及添加剂可以提高环己烯的收率,钌催化苯液相选择加氢制环己烯的反应是一个非常复杂的四相（水、气、油、固）反应体系,对这个四相复杂反应体系的深入研究,有助于找出加快环己烯从催化剂表面脱附的方法,进一步提高环己烯的收率。     

苯选择加氢制环己烯在钌基催化体系中的技术进展

环己烯是一种非常重要的有机化工原料,苯选择加氢制环己烯是获取高产量环己烯的最佳途径。长期以来科研工作者们都致力于开发出具有高选择性高收率制环己烯的钌基催化反应体系,然而环境因素使其在工业上大规模应用受到了限制,因此有必要对该领域进一步的深入研究。绿色催化是当下研究的热点之一,开发具有负载少钌且无需反应添加剂的高亲水性催化剂的这一趋势在今后的绿色化学发展中势必加强,因此苯选择加氢制环己烯的技术开发是一项极富有经济意义与科研挑战性的课题。本文从苯选择加氢的反应工艺技术、发展历程、钌基催化剂的反应体系组成以及反应机理等方面,系统介绍了苯选择性加氢制备环己烯的技术进展。     

苯选择加氢制环己烯催化剂研究进展

目前苯选择加氢制环己烯催化剂已广泛应用于合成纤维工业及其它领域中。本文综述了国内外苯选择加氢制环已烯催化剂的研究现状,重点介绍了活性组分、载体、助剂、制备方法及添加剂对催化剂活性及选择性的影响,分析了其影响原因,并指出了提高环己烯选择性的关键因素,最后在此基础上展望了苯选择加氢催化剂的发展方向。     

用催化剂表面修饰以进行苯选择加氢制环己烯的研究

1 前言常规的气相苯催化加氢反应,苯环大π键一经打开就全部加氢到底,产物中只能获得环己烷而极难得到选择加氢产物环己烯。生成环己烷的反应从热力学上看远比生成环己烯的反应容易进行很多,并且环己烯也非常容易进一步加氢生成环己烷。但催化剂的表面经修饰剂作用后可根本改变其性能,从而改进催化活性及选择性,或实现常规方法不可能实现的反应,获得不易得到的产物。在经表面修饰的催化剂上进行苯加氢反应可获得选择加氢产物环     

钌催化苯选择加氢制环己烯的研究进展

介绍了钌催化苯选择加氢制环己烯这一经济、安全、高效的环己烯制备新工艺的研究进展,着重介绍了液相法苯选择加氢制环己烯钌系催化剂的研究及其对苯液相选择加氢制环己烯反应的各种影响,指出钌催化刘应用于苯液相选择加氢制环己烯一般选择反应温度为150℃～190℃,压力4MPa～5MPa,加入助催化剂及添加剂可以提高环己烯的收率．钌催化苯液相选择加氢制环己烯的反应是一个非常复杂的四相(水、气、油、固)反应体系,对这个四相复杂反应体系的深入研究,有助于找出加快环己烯从催化剂表面脱附的方法,进一步提高环己烯的收率．     

助剂对苯加氢Ru系催化剂催化性能的影响

以三氯化钌(RuCl3)、硫酸锌(ZnSO4)和硫酸亚铁(FeSO4)为原料,采用共沉淀法制备Ru-Zn及Ru-Fe-Zn催化剂,研究了苯选择加氢制环己烯过程中助剂Zn和Zn/Fe对Ru系催化剂催化加氢性能的影响,并利用透射电镜等对催化剂进行表征。结果表明:Ru-Zn催化剂粒子清晰较为分散,Ru-Fe-Zn催化剂粒径变大,比表面积变小;Ru系催化剂中加入助剂Zn,Ru/Zn摩尔比为7时,环己烯选择性较高,加入第三组分Fe,Zn/Fe摩尔比为10,环己烯选择性进一步提高;Ru-Fe-Zn催化剂具有很好的催化活性和稳定性,苯转化率达54.9%,环己烯选择性达81.8%。     

苯选择性加氢技术的研究进展

对苯选择性加氢反应特性、催化剂的研究现状及进展、影响催化剂性能的主要反应条件等方面作了细致的探讨 ,在此基础上提出了提高苯选择性加氢制环己烯收率的可能途径。     

苯部分加氢工艺生产环己醇

以旭化成工艺为基础，概述了苯部分加氢反应机理、相关催化剂的研究开发、反应影响因素及后续工艺过程，比较了旭化成工艺与传统工艺。     

葡萄糖加氢制山梨醇Ru/C催化剂的开发

针对葡萄糖加氢制山梨醇反应,研究了以水合RuCl3为前驱体制备高活性Ru/C催化剂的方法。考察了活性组分负载方式、活性炭载体的预处理、钌负载量、以及氯离子的洗涤脱除对催化活性的影响。结果表明,尿素均匀沉淀法可得到高分散的钌晶粒;活性炭载体经双氧水处理效果最好;经洗涤脱氯,钌晶粒的分散度增加,催化剂活性显著提高。在120℃,氢压4 MPa下,测得用优选条件制备的含钌3.79%质量分率的Ru/C催化剂活性,即拟一级反应速率常数,为0.533 L/(s.g-cat),比两种糖加氢商用催化剂,即Raney-Ni的0.285 L/(s.g-cat)和含钌5%质量分率商业Ru/C催化剂的0.422 L/(s.g-cat)均有明显提高。     

钌催化剂上苯加氢制环己烯的影响因素

综述了钌催化剂上苯选择性加氢的反应机理、催化剂制备过程中前躯体、制备方法、载体、添加剂(水,有机添加剂,无机添加剂)对催化剂催化性能的影响和反应过程中温度、压力、搅拌速率、催化剂用量及反应时间等对苯转化率、环己烯选择性和环己烯收率的影响。     

苯选择加氢制环己烯在钌基催化体系中的技术进展

苯选择加氢是获取高产量环己烯的最佳途径,但该反应极易导致苯的过度加氢生成副产物环己烷,使得环己烯的选择性普遍不高。钌(Ru)是苯选择加氢的高效催化活性中心,Ru活性位的活泼程度及其在载体上的分散性与稳定性很大程度决定了环己烯的选择性和收率。同时,在反应过程中各种添加剂,如酸、碱、盐体系所带来的环境污染和强腐蚀性问题严重地限制了Ru基催化剂在工业上的大规模应用。因此,研究Ru基催化剂上选择加氢活性中心形成机制与制备参数之间的关系,以及在不损失反应性能的前提下寻找更简单、更绿色的催化体系代替传统工艺颇为关键。该文介绍了苯选择加氢合成环己烯的发展历程、反应工艺技术、Ru基催化剂的反应体系组成以及反应机理。最后,指出苯选择加氢制备环己烯研究重点。     

NaOH浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响

用共沉淀法制备了纳米Ru-Zn催化剂,考察了不同浓度NaOH同时作沉淀剂和还原介质对苯选择加氢制环己烯Ru-Zn催化剂性能的影响,并用X射线衍射(XRD)、N₂物理吸附(BET)、X射线荧光光谱(XRF)和透射电镜(TEM)手段等对催化剂进行了表征。结果表明,NaOH浓度可以调变Ru-Zn催化剂的Zn含量、粒径和孔径,进而影响Ru-Zn催化剂的苯选择加氢制环己烯性能。NaOH含量为15%时制备的Ru-Zn催化剂在优化的反应条件下获得了61.5%的环己烯收率,而且该催化剂具有良好的重复使用性能。     

合成方法对Ru-Zn/ZrO2苯部分加氢催化剂的影响

分别采用水热-共沉淀法和机械混合法制备Ru-Zn/ZrO2催化剂,并用于苯部分加氢制环己烯反应体系.通过XRD、SEM、TEM等对催化剂的组成、结构和形貌进行表征,对比不同方法合成的催化剂对苯部分加氢反应的影响.结果表明,水热-共沉淀法制备的Ru-Zn/ZrO2催化剂上的Ru分散度高,晶粒尺寸小,催化剂表面苯加氢位点多...     

Partial hydrogenation of benzene with ruthenium catalysts prepared by a chemical mixing procedure: Preparation and properties of the catalysts

Ruthenium catalysts were prepared in different alcohols by a chemical mixing technique, characterised by the preparation of a homogeneous solution containing catalyst components, and the uniform coagulation of the solution through hydrolysis. The technique has the potential for controlling the surface area of the catalysts and for making them porous. The ruthenium catalysts were much more effective for the partial hydrogenation of benzene to cyclohexene (maximum cyclohexene yield, 31.4%) in the absence of any poison such as alkali metal hydroxide or transitional metal sulphate in the reaction solution.     

Partial hydrogenation of benzene to cyclohexene in a continuously operated slurry reactor

A method has been developed for direct measurement of reaction rates in a continuously operated slurry (CST-) reactor. In contrast to the usual procedure in a two-liquid-phase system the reactor contains only one liquid phase, an aqueous zinc chloride solution in which a ruthenium lanthanoxide catalyst is suspended. The selectivity of benzene hydrogenation with respect to cyclohexene is higher when the new one-liquid-phase procedure is applied. With decreasing degree of benzene conversion the selectivity with respect to cyclohexene approaches 100%. The conclusion is that cyclohexane is formed only by consecutive hydrogenation of cyclohexene.     

Sugar hydrogenation over a Ru/C catalyst

BACKGROUND: In recent years, exploitation of renewable resources has gained considerable attention. In this respect, polyols derived from the hydrogenation of sugar molecules are versatile molecules with a variety of uses, such as low‐caloric sweeteners. The hydrogenation of D‐maltose, D‐galactose, L‐rhamnose and L‐arabinose was carried out on a finely dispersed Ru/activated carbon catalyst with the objective of studying the kinetics of the production of the corresponding polyols. The reactions were carried out in a stirred tank reactor at temperatures ranging from 90 to 130 °C and hydrogen pressures from 40 to 60 bar. RESULTS: Sugar conversions up to 100% were achieved. Some by‐product formation affecting the quality of the selectivity was also observed at elevated operating conditions. The catalyst was characterized by scanning electron microcopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectrometry (ICP‐OES) and nitrogen physisorption. Kinetic models based on the Langmuir Hinshelwood assumptions were proposed for the reactions and a nonlinear regression was performed to obtain the numerical values of the kinetic parameters. CONCLUSIONS: The kinetic models predicted well the sugar hydrogenation process and the kinetic parameters were established. The model can be used to predict the behaviour of batchwise operating slurry reactors. Copyright © 2011 Society of Chemical Industry     

Liquid phase hydrogenation of benzene to cyclohexene on ruthenium catalysts supported on zinc oxide‐based binary oxides

A series of binary oxide‐supported ruthenium catalysts with zinc oxide as a component of the support was prepared. Zinc oxide was a major component of the support, the other component was lanthanum oxide, zirconium oxide, chromium oxide, barium oxide, gallium oxide, strontium oxide, calcium oxide or magnesium oxide. Liquid phase hydrogenation of benzene to cyclohexene was studied on these catalysts in a stirred tank reactor at a hydrogen pressure of 2.5–6.0 MPa and 448 K. The reaction was operated in a kinetic‐controlled regime. In order to have high selectivity to cyclohexene, a large amount of water should be present. In addition, the reaction medium should be an alkaline solution. The yield of cyclohexene was in the order: Ru/Ga₂O₃–ZnO > Ru/La₂O₃–ZnO > Ru/Cr₂O₃–ZnO > Ru/ZrO₂–ZnO > Ru/MgO–ZnO = Ru/CaO–ZnO = Ru/SrO–ZnO = Ru/BaO–ZnO.Ru/Ga₂O₃–ZnO demonstrated the highest selectivity and yield of cyclohexene. A model of the low solubilities of reactants in the water film surrounding the catalyst can explain the reaction behavior of the catalyst. © 2001 Society of Chemical Industry