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【摘要】:综述了分子氧氧化环己烷制取环己酮的催化剂的研究进展,重点介绍了光催化剂、纳米催化剂、仿生催化剂、分子筛催化剂和复合催化剂在环己烷催化氧化方面的应用,其中,负载在分子筛上的纳米金催化剂具有较高的催化活性、选择性及稳定性。

【关键词】:环己烷氧化,环己酮,催化剂的认识。

环己酮是重要的有机化工原料和工业溶剂,广泛应用于医药、油漆、涂料、橡胶、农药行业、印刷和塑料回收方面。目前,工业上制取环己醇和环己酮的方法主要为苯酚加氢法、苯部分加氢法和环己烷液相氧化法,环己烷氧化法的应用最为普遍,占90%以上。

由于环己醇和环己酮比环己烷更易于被氧化,为获得适宜的环已醇和环已酮的选择性,工业上环己烷氧化转化率通常控制在3.5%~5.0%,氧化选择性为90%左右。

但环己烷的大量循环造成能耗上的巨大浪费。目前,环己烷氧化工艺研究的热点主要集中在对传统工艺的改造优化、氧化剂的选择及高效催化剂的开发。开发高性能和环境友好的催化剂成为研究热点,近年来开发的一些氧化催化剂在改善环己烷转化率和产物选择性方面表现出较好的性能。

本文主要综述分子氧氧化环己烷制环己酮催化剂的研究进展。

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Lolita1015

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家装工装

发表学术论文90余篇,其中SCI收录70余篇,SCI他人引用1200余次;EI收录42篇;ISTP收录5篇;撰写/翻译5部专著中6章;应邀在国内外研究机构和学术会议上作报告20多次。代表性期刊论文69. Xiaojuan Ni, Chuang Li, Min Pang, Bingsen Zhang, Dangsheng Su, Changhai Liang*, A solvent-less and fast route to highly dispersed Ru/CNT catalysts by microwave-assisted MOCVD, 2011, submitted68. Xin Jin, Yanjiao Yi, Qiumin Zhang, Changhai Liang*, A novel route to MoS2/MCM-41 by in-situ formation and decomposition of molecular precursor , 2011, submitted67. Xiao Chen, Bingsen Zhang, Zhengfeng Shao, Wenzhen Li, Dangsheng Su, Changhai Liang*, Magnetic, Electrochemical and Catalytic Properties of Nickel Silicides Prepared by Direct Silification Method, 2011, submitted66. Chuang Li, Zhengfeng Shao, Min Pang, Christopher T. Williams, Xiongfu Zhang, Changhai Liang*, Carbon Nanotubes Supported Pt-Ru Core-Shell , Alloy and Monometallic Catalysts for Hydrogenation of Phenylacetylene, 2011, submitted65. Yanjiao Yi, Xin Jin, Bingsen Zhang, Qiumin Zhang, Dangsheng Su and Changhai Liang*, Preparation and Characterization of Unsupported Ni-Mo-W Sulfide Catalysts for Hydrodesulfurization of Dibenzothiophene, 2011, submitted64. Bingsen Zhang, Yanjiao Yi, Wei Zhang, Changhai Liang, Dangsheng Su*, Unsupported Ni-Mo-W Sulfide Catalysts: A Structure Investigation, 2011, submitted63. Anqi Zhao, Xiao Chen, Jingchao Guan, Christopher T. Williams, Changhai Liang*, Formation mechanism of cobalt silicide on silica by chemical vapor deposition of Co(SiCl3)(CO)4, PCCP, 2011, revised62. Yanjiao Yi, Xin Jin, Lei Wang, Qiumin Zhang, Guang Xiong, and Changhai Liang*, Preparation of Unsupported Ni-Mo-S Catalysts for Hydrodesulfurization of Dibenzothiophene by Thermal Decomposition of Tetramethylammonium Thiomolybdates, Catal. Today, 2011, revised61. Zihui Xiao, Zhiqiang Ma, Xinkui Wang, Christopher T. Williams, Changhai Liang*, Effect of Preparative Parameters on Structure and catalytic performance of Cu-Cr Catalysts in Non-alkoxide Sol-gel Route, Ind. Eng. Chem. Res., 2010, 2010, 50, 2031-203960. Xiao Chen, Anqi Zhao, Zhengfeng Shao, Chuang Li, Christopher T. Williams, Changhai Liang*, Silicide Overlayers on Nickel Surfaces for Selective Hydrogenation of Phenylacetylene, J. Phys. Chem. C, 2010, 114 (39), 16525-1653359. Zhengfeng Shao, Chuang Li, Xiao Chen, Xinkui Wang, Changhai Liang*, A facile and controlled route to prepare eggshell Pd catalyst for selective hydrogenation of Phenylacetylene, ChemCatChem, 2010, 2, 1555-155858. 张小菲,邵正锋,毛国强,何德民,张秋民*,梁长海*,萘在贵金属Pd﹑Pt及Pd-Pt催化剂上的加氢活性及耐硫性能研究,物理化学学报,2010,26,2691-269857. Xiaofei Zhang, Qiumin Zhang*, Anqi Zhao, Jun Guan, Demin He, Haoquan Hu, Changhai Liang*, Hydrogenation of naphthalene over nickel phosphide supported on silica for in the absence and presence of quinoline and its hydrogenated intermediates, Energy & Fuel, 2010, 24, 3796-380356. 张奇,刘春艳,梁长海*,何德民,关珺,张秋民*,H2S和喹啉对NiWS/γ-Al2O3催化剂上吲哚加氢脱氮反应的影响,燃料化学学报,2010, 印刷中55. Min Pang, Ling Ding, Chuang Li, Changhai Liang*, Microwave-assisted preparation of Mo2C/CNTs nanocomposites as an efficient support for electrocatalysts towards oxygen reduction reaction, Stud. Surf. Sci. Catal., 2010, 175, 275-27854. Jingchao Guan, Anqi Zhao, Xiao Chen, Mingming Zhang, Changhai Liang*, Chemical vapor deposition of Fe(CO)4(SiCl3)2 for the synthesis of hydrogenation catalyst made of highly dispersed iron silicide particles on silica , Stud. Surf. Sci. & Catal., 2010, 175, 259-26253. Xiao Chen, Anqi Zhao, Zhengfeng Shao, Zhiqiang Ma, Changhai Liang*, A Novel Approach to Synthesize Highly Selective Nickel Silicide Catalysts for Phenylacetylene Semihydrogenation, Stud. Surf. Sci. Catal., 2010, 175, 77-8452. Changhai Liang*, Ling Ding, Chuang Li, Min Pang, Dangsheng Su, Yuemin Wang, and Wenzhen Li, Nanostructured WCx/CNTs as highly efficient support of electrocatalysts with low Pt loading for oxygen reduction reaction, Energy Environ. Sci., 2010, 3, 1121-112751. Min Pang, Chuang Li, Ling Ding, Jian Zhang, Dangsheng Su, Wenzhen Li, Changhai Liang*, Microwave-assisted preparation of Mo2C/CNTs nanocomposites as efficient electrocatalyst supports for oxygen reduction reaction, Ind. Eng. Chem. Res., 2010, 49, 4169-417450. Olumide Winjobi, Zhiyong Wang, Changhai Liang, Wenzhen Li*, Carbon nanotube (CNT) supported platinum-palladium nanoparticles for formic acid oxidation, Electrochimica Acta, 2010, 55(13), 4217-42249. Xin Jin, Chongle Ma, Yanjiao Yi, Qiumin Zhang, Jieshan Qiu, Changhai Liang*, Controlled Preparation of Unsupported Binary and Ternary Sulfides with High Surface Area from Tetraalkylammonium Thiosalts, J. Phys. Chem. Solids, 2010, 71, 642-64648. Anqi Zhao, Xiaofei Zhang, Xiao Chen, Jingchao Guan, and Changhai Liang*, Cobalt Silicide Nanoparticles in Mesoporous Silica as Efficient Naphthalene Hydrogenation Catalysts by Chemical Vapor Deposition of of Co(SiCl3)(CO)4 Precursor , J. Phys. Chem. C, 2010, 114, 3962-396747. Zhiqiang Ma, Zihui Xiao, Jeroen A. van Bokhoven,Changhai Liang*, A Non-alkoxide Sol-gel Route to Highly Active and selective Cu-Cr Catalysts for Glycerol Hydrogenolysis,J. Mater. Chem., 2010, 20, 755-76046. Yezhi Luan, Qiumin Zhang*, Demin He, Jun Guan, Changhai Liang, Hydrodenitrogenation of quinoline and its intermediates over sulfided NiW/Al2O3 in the absence and presence of H2S , Asia-Pacific J. Chem. Eng., 2009, 4, 704-71045. Xiaofei Zhang, Qiumin Zhang*, Jun Guan, Demin He, Haoquan Hu, Changhai Liang*, Hydrogenation of naphthalene on nickel phosphide supported on silica, Asia-Pacific J. Chem. Eng., 2009, 4, 574-58044. Changhai Liang*, Wei Xia, Maurits van den Berg, Yuemin Wang, Hamideh Soltani-Ahmadi, Oliver Schlüter, Roland A. Fischer and Martin Muhler*,Synthesis and Catalytic Performance of Pd Nanoparticle / Functionalized CNF Composites by a Two-step Chemical Vapor Deposition of Pd(allyl)(Cp) Precursor, Chem. Mater.,2009, 21(12), 2360-236643. Tonghua Wang, Suxia Tan, Changhai Liang*, Preparation and characterization of activated carbon from wood by microwave–induced ZnCl2 activation, Carbon, 2009, 47, 1880-188342. Qingling Liu, Tonghua Wang, Hongchen Guo, Changhai Liang, Shili Liu, Zhiguo Zhang, Yiming Cao, Dangsheng Su and Jieshan Qiu, Controlled Synthesis of High Performance Carbon/Zeolite T Composite Membrane Materials for Gas Separation, Micro.& Meso. Mater. 2009, 120, 460-46641. Changhai Liang*, Anqi Zhao, Xiaofei Zhang,Zhiqiang Ma,Roel Prins, CoSi particles on silica support as a highly active and selective catalyst for naphthalene hydrogenation, Chem. Commun., 2009, 2047-204940. Changhai Liang*, Ling Ding, Aiqin Wang, Zhiqiang Ma, Jieshan Qiu, Tao Zhang, Microwave-Assisted Preparation and Hydrazine Decomposition Properties of Nanostructured Tungsten Carbides on Carbon Nanotubes, Ind. Eng. Chem. Res., 2009, 48(6), 3244-324839. Changhai Liang*, Zhiqiang Ma, Ling Ding, Jieshan Qiu, Template Preparation of a Highly Active and selective Cu-Cr Catalyst with High Surface Area for Glycerol Hydrogenolysis, Catal. Lett., 2009, 130, 169-17638. 马崇乐,金鑫,丁玲,张秋民,邱介山,梁长海*,高比表面积二硫化钼的制备及其对喹啉选择加氢反应的催化性能,催化学报,2009,30 (1), 78-8237. Changhai Liang*, Zhiqiang Ma, Hongyan Lin, Ling Ding, Jieshan Qiu,Wiebke Frandsen and Dangsheng Su, Structure and Catalytic Properties of Nanoscale CexFe1-xO2 Solid Solution by Template Route, J. Mater. Chem., 2009, 19, 1417-1424教材和专著中章节6. 梁长海,辛勤,“氨合成化学”,现代催化化学 (辛勤等主编), 科学出版社,2010,第三章5. 梁长海,“多相催化反应动力学”,现代催化研究方法 (辛勤,罗孟飞 主编),科学出版社,2009,第十章, pp429-4884.Changhai Liang*, Preparation and characterization of Nanostructured Carbides on Carbon Material by Carbothermal Hydrogen Reduction, Focus on Nanomaterials Research, Chapter 1, Nova Science Publishers, Inc., 2006, pp1-143.辛勤,梁长海,“红外光谱技术在多相催化中的应用”,固体催化剂研究方法 (辛勤主编), 科学出版社,2004,第七章,pp320-3852.梁长海,李文震,辛勤,“催化发展简史 (译自Catalysis Letters 67卷第一期)”,固体催化剂研究方法 (辛勤主编), 科学出版社,2004,附录,pp860-9081.Changhai Liang*, Zhonglai Li, Jieshan Qiu, Zhaobin Wei, Qin Xin, Can Li, Graphitic Nanofilaments: A Superior Support of Ru-Ba Catalyst for Ammonia Synthesis in Nanotechnology in Catalysis (Eds. B. Zhou, S. Hermans and G. A. Somorjai ), Kluwer Academic/Plenum Publishers, 2003, volume II, Chapter 25, pp543-555

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