Two‐phase production of cyclohexene and cyclooctene oxides in water as an approach to pollution prevention

Liquid–liquid two‐phase epoxidation from cyclohexene and cyclooctene in aqueous potassium peroxymonosulfate (commercially available as Oxone^®) solution was studied as an application in pollution prevention. To avoid potential emissions of volatile organic compounds an aqueous solution was employed to replace the usual chlorinated solvents used in epoxide production. A droplet column reactor and stirred tank reactor were used to investigate two‐phase synthesis of epoxide. An aqueous Oxone^® solution was used to oxidize a dispersion of alkene droplets and form epoxide. The study of aqueous epoxidation in both reactors showed that the epoxidation of alkenes can be represented as a first order reaction with respect to alkene. The salting out effect of Oxone^® concentration was studied in both reactors and found to be very similar at optimal conditions. In comparing the two reactors, it was found that the droplet column reactor produces larger quantities of product per unit reactor volume for the same reaction time. The objective of this study is to provide an alternative reactor design and synthesis route that can meet pollution prevention goals. Copyright © 2004 Society of Chemical Industry     

A new synthesis procedure for titanium-containing zeolites under strong alkaline conditions and the catalytic activity for partial oxidation and photocatalytic decomposition

A new synthesis procedure for titanium-containing aluminosilicate zeolites has been obtained using a clear colloidal dispersion (sol) which was prepared with titanium isopropoxide, water, hydrochloric acid and colloidal silica, Ludox. When NaY, KL, offretite, mordenite and ZSM-5 zeolites were crystallized from the sol following conventional hydrothermal crystallization procedures, all the aluminosilicate zeolites showed the same X-ray absorption fine structure at the Ti K edge indicating framework Ti. The zeolites showed remarkable catalytic activity for the partial oxidation of cyclohexene using H₂O₂ as an oxidant and the photocatalytic decomposition of trichloroethene using water.     

微波辐射活性炭负载磷钨酸催化环己醇脱水制环己烯

研究了在微波辐射条件下，活性炭负载磷钨酸脱水制环己烯的反应。考察了催化剂的负载量、催化剂用量、微波辐射时间和功率对反应的影响。结果表明：在催化剂负载量为25．4％，催化剂用量为3g，环己醇用量为20mL，微波辐射功率为600W，辐射时间为6min时，环己烯收率达84．3％，催化剂可重复使用。     

Towards an Environmentally Acceptable Heterogeneous Catalytic Method of Producing Adipic Acid by the Oxidation of Hydrocarbons in Air

A survey is given of the catalytic methods potentially available for the production of adipic acid by the oxidation of readily available hydrocarbon precursors under environmentally benign conditions. Encouraging results are reported using H₂O₂ as oxidant and microporous FeAlPO-5 as catalyst at moderate temperatures.     

4-乙烯基环己烯环氧化反应研究

分别以单过氧马来酸、单过氧邻苯二甲酸、过氧三氯乙酸以及过氧乙酸作环氧化试剂，对４－乙烯基环己烯环氧化反应作了研究，并从分子结构的角度，阐明了４－乙烯基环己烯在环氧化反应中所表现出的选择性     

环己烯水合生产环己醇工艺条件优化

从有机化工反应热力学和动力学的角度研究分析了我公司环己烯水合反应生产环己醇的工艺条件，并初步讨论了该反应工艺的理论和实践间的影响与关系。     

三氧化钨催化氧化环己烯合成己二酸

无需有机溶剂、酸性配体及相转移剂,以30%H2O2为氧源,单独使用三氧化钨作催化剂催化氧化环己烯合成己二酸即可达到较高的产率和纯度。当三氧化钨用量为5.0m m ol,W O3:环己烯:H2O2的摩尔比为1:40:176时,在回流温度下反应6h,己二酸分离产率为75.4%,己二酸纯度99.8%。三氧化钨催化剂重复使用4次,己二酸的分离产率仍可达到70%以上。结合FTIR和XRD分析证明了三氧化钨催化氧化环己烯反应过程中催化剂的结构稳定性和重复使用性。     

双金属Mo-Ti-SBA-15材料的制备及其环己烯环氧化性能

采用一步法分别制备了一系列单金属介孔催化剂Ti-SBA-15-36,Mo-SBA-15-(180/28)和双金属介孔催化剂Mo-Ti-SBA-15-(X)。考察了双金属催化剂Mo-Ti-SBA-15-(X)的Mo含量,对催化剂的结构和催化性能的影响。分析了催化剂活性差异的原因以及探讨了双金属催化剂的催化协同机理。考察了催化环氧化反应中的主要影响因素。结果表明,最佳的双金属催化剂Mo-Ti-SBA-15-(180/28)的催化效果均优于单金属催化剂的环氧化效果。当反应时间为8 h,反应温度为80 ℃,催化剂剂量为25 mg,以环己烯作为底物,TBHP作为氧源,1,2-二氯乙烷作为溶剂时,Ti-SBA-15-36,Mo-SBA-15-(180/28)和Mo-Ti-SBA-15-(180/28)的转化率分别为41.07%、46.44%和98.33%,选择性分别为97.56%、93.19%和98.86%。同时Mo-Ti-SBA-15-(180/28)也具有很好的可循环利用性。     

TiO_2-ZrO_2二元复合氧化物作分散剂的苯部分加氢制环己烯研究

采用共沉淀法制备了一系列不同TiO2/ZrO2质量比的TiO2-ZrO2复合氧化物试样。考察了其作为分散剂时Ru-Zn催化剂上苯部分加氢制环己烯的反应性能,并采用N2物理吸附和X射线衍射等手段对TiO2-ZrO2试样进行了表征。结果表明:TiO2在ZrO2表面高度分散,改变了其孔径分布及其晶粒的大小,从而提高了环己烯的选择性;当TiO2/ZrO2质量比为10/90时,环己烯选择性达到最高。催化剂重复使用6次,环己烯选择性仍保持在79%左右。     

MoO3/TiO2纳米复合催化剂的合成及催化脱氢性能

采用溶胶-凝胶法合成MoO3/TiO2、K2O-MoO3/TiO2、V2O5-MoO3/TiO2、Al2O3-MoO3/TiO2、K2O-V2O5-MoO3/TiO2系列纳米催化剂。借助TEM、XRD、IR等技术对催化剂进行了表征,并利用环己烷催化氧化脱氢成环己烯的反应进行活性测试。结果表明,MoO3在载体TiO2呈单层和多层分布,单层分布时发生了Mo与O—Ti的键合作用,同时使TiO2表面水分子发生解离反应,活化时脱去—OH产生Mo6+和Mo—O-活性中心;多层分布时以Mo[FY=,1]O、Mo—O-活性物种为主。脱氢中心和供氧中心之间存在协同作用,K、Al、V均能影响其协同作用。