钌基催化剂催化苯部分加氢制环己烯的研究进展  

Advances in the Ruthenium Catalysts for Partial Hydrogenation of Benzene to Cyclohexene

作　　者：王红琴[1] 谢继阳[1] 安霓虹 戴云生[1] 唐春[1] 刘俊 沈亚峰[1] 周伟[1] WANG Hongqin;XIE Jiyang;AN Nihong;DAI Yunsheng;TANG Chun;LIU Jun;SHEN Yafeng;ZHOU Wei(State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals,Sino-Platinum Metals Co. Ltd.,Kunming Institute of Precious Metals,Kunming 650106)

机构地区：[1]昆明贵金属研究所贵研铂业股份有限公司稀贵金属综合利用新技术国家重点实验室

出　　处：《材料导报》2019年第23期4016-4024,共9页Materials Reports

基　　金：国家自然科学基金(21763014)~~

摘　　要：环己烯具有活泼的双键,被广泛用于医药、农药、食品及其他高附加值精细化学品的生产中。工业上生产环己烯的方法主要有环己烷脱氢、环己醇脱水、卤代环己烷脱卤化氢、Birch还原和苯部分加氢等。相比于其他方法,苯部分加氢制环己烯工艺由于具有安全可靠、原子经济性强、环境友好等优点,引起了研究者的广泛关注。从热力学角度看,苯加氢生成环己烯的标准Gibbs自由能比生成环己烷的标准Gibbs自由能低75 kJ/mol,极不利于环己烯的生成。另外,苯环共轭大π键的化学性质较环己烯双键更稳定,在催化剂存在下环己烯极易深度加氢生成环己烷,反应难以停留在环己烯阶段。除引入水相外,催化剂是实现苯部分加氢制备环己烯工艺过程的关键,因此开发高活性、高选择性的催化剂显得格外重要。100多年前人们就开始探索苯部分加氢制环己烯工艺。自1957年Anderson在Ni膜催化苯加氢产物中检测到环己烯的存在以来,一些研究者陆续报道了钌催化剂催化的苯加氢反应,在苯转化率较低的情况下能检测到中间产物环己烯,并发现钌催化剂最适合该反应。其中,一项极为重要的研究进展是在含油相、水相、气相和固相的四相反应体系中,以过渡金属盐为添加剂,在剧烈搅拌下反应,环己烯收率可高达60%,提高了技术可行性。1989年日本旭化成公司率先实现了Ru-Zn催化苯部分加氢制环己烯工艺的工业化。1995年,我国神马集团引进日本旭化成苯部分加氢技术。随着技术的引进,国内各大科研院所、高校等的多个课题组相继加入苯选择加氢制环己烯催化剂的研究,研究工作主要集中在优化和完善催化反应条件、研制新催化剂、探索提高环己烯选择性的本质原因。近年来,大量文献报道通过合理设计Ru催化剂来提高环己烯选择性,如采用NaOH溶液对Ru/ZrO2催化剂进行锌刻蚀以增加催Cyclohexene with an active double bond is widely used in the synthesis of pharmaceuticals,pesticides,food and other high value-added fine chemicals.Cyclohexene can be synthesized by several ways,such as dehydrogenation of cyclohexane,dehydration of cyclohexanol,dehydrohalogenation of halogenated cyclohexane,Birch reduction or partial hydrogenation of benzene.Compared with other methods,the technology of partial hydrogenation of benzene to cyclohexene is of the advantage of safety,high atom-economy,environmentally friendly,and has caused a wide range of concerns by different researcher in recent years.The hydrogenation of benzene to cyclohexane is thermodynamically much more favorable since the cyclohexane is at least 75 kJ/mol more stable than cyclohexene in terms of the Gibbs free energy.In addition,cyclohexene is easily hydrogenated to cyclohexane,because the chemical properties of conjugatedπbonds of benzene ring are more stable than that of double bond of cyclohexene.Development of new catalyst is the key to enhance the selectivity to cyclohexene for partial hydrogenation of benzene in the tetra-phase reaction system.The partial hydrogenation of benzene to cyclohexene has been known for more than 100 years.Only in 1957 was the products identified in the hydrogenation of benzene catalyzed by Ni membrane.Since then,the production of cyclohexene in the hydrogenation of benzene at low degrees of conversion has been reported by several researchers,and ruthenium catalysts have been especially suiting for the reaction.One of the most important advances was the adoption of agitated tetra-phase reactors containing an organic phase,an aqueous phase,a gas phase(H 2)and a solid phase(catalysts),to which transition metal salts are added,and can achieve yields as high as 60%.In 1989,the Ru-Zn catalyst for benzene partial hydrogenation was industrialised for the first time in Japan by Asahi-Kasei Chemical Co.,Ltd..The technology was introduced from Japan into Shenma Group Company in 1995.Along with the introduction of adva

关 键 词：钌催化剂 苯 部分加氢 环己烯 

分 类 号：O643.38[理学—物理化学]