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     

环氧油一步合成的反应机理和动力学研究

研究了环氧油一步合成的反应机理和动力学；结合实验结果和理论分析动力学模型，首次提出：在适当的反应条件下，油脂的一步环氧化反应动力学模型可以表示为过氧酸生成反应动力学模型；其实验动力学模型方程为：ｒ０＝ｋ［Ｈ２Ｏ２］（０．９９）［ＨＯＡｃ］（０．９７），其中ｋ与催化剂用量有关。     

Influence of ZnO and P2O5 Content on Modified HZSM-5 on Aromatization of FCC Gasoline

Catalytic properties of different content of ZnO and P₂O₅ supported on HZSM-5 zeolites were studied in the conversion of FCC gasoline (75°C-120°C) into aromatic hydrocarbons with a temperature of 430°C, a liquid hourly space velocity of 1.0 hr^-1, and a pressure of 0.1 MPa. In the reaction, when the contents of ZnO and P₂O₅ are 2% and 4%, respectively, Zn-P/HZSM-5 showed the highest selectivity and activity to aromatic hydrocarbons and conversion of olefins. The content of aromatics in the liquid product and the yield of aromatics reached as high as 94.53%, 68.87%, and 51.74%, respectively.     

La改性的Ag/TS-1催化剂上丙烯选择氧化制环氧丙烷

在H2 和O2 混合气体存在下 ,在常压固定床、石英反应器上考察了La改性的Ag/TS - 1催化剂催化丙烯环氧化反应。研究结果表明 ,Ag和La负载在TS - 1上的先后顺序对丙烯环氧化反应有影响。H2 在丙烯气相氧化反应体系中起着重要的作用。     

SAPO-34/SiO_2催化甲醇制烯烃

采用水热法合成了SAPO-34分子筛,并用X射线粉末衍射仪和扫描电子显微镜对SAPO-34分子筛的结构进行了表征,同时探讨了黏合剂种类、甲醇分压、催化剂粒径和硅源等对SAPO-34分子筛催化甲醇制烯烃(MTO)反应性能的影响。实验结果表明,在MTO反应中,三烯(乙烯、丙烯和丁烯)选择性在反应初期存在明显的诱导期;以S iO2为黏合剂合成的SAPO-34/S iO2催化剂不但可缩短MTO反应的诱导期,三烯选择性也较未添加黏合剂或以A l2O3为黏合剂时高1~2个百分点;且当催化剂活性明显下降时,三烯选择性下降的幅度较小。催化剂粒径、甲醇分压及硅源对催化剂的诱导期也有明显的作用。在甲醇分压低于19kPa、催化剂粒径0.25~0.38mm、S iO2为黏合剂、硅酸四乙酯为硅源时,SAPO-34/S iO2催化剂的MTO性能明显提高。     

Epoxidation of β-ionone using molecular oxygen over Pt/MCM-41 catalyst under mild conditions

The epoxidation of β-ionone over the Pt/MCM-41 catalyst using molecular oxygen in the liquid phase had been studied. The results indicated that the β-ionone was catalytically oxidized to 5,6-epoxy-β-ionone, 4-oxo-β-ionone, 4-hydroxy-β-ionone and dihydroactinidiolide using molecular oxygen as the sole oxidant. The effects of solvent, content of Pt, reaction temperature and time on the catalytic activity and product selectivity had also been investigated in detail.     

由二氧化碳出发合成有机碳酸酯

对以二氧化碳为原料合成有机碳酸酯的环氧路线、酯交换和直接合成方法作了综合评述 ,认为直接合成是最佳的合成路线。碳酸酯的直接合成可在均相及多相催化体系中进行 ,负载金属、金属甲氧基化合物及碱均可作为催化剂。直接法研究的关键在于高性能催化剂的开发、由二氧化碳对金属 -氧键插入反应导致的催化循环的构筑及耦合反应的应用。     

碳四烷烃催化裂解制低碳烯烃的研究进展

论述了碳四烷烃催化裂解制低碳烯烃的催化剂体系、影响因素及催化裂解方式。该催化剂体系包括硅铝酸盐及锆硫酸盐,氧化铝与碱金属或碱土金属的混合物,负载型催化剂等3种类型。其中分子筛(晶体硅铝酸盐)及其改性催化剂是研究开发的主要方向。除操作条件外,稀释剂、引发和抑制剂和裂解反应方式对催化裂解反应均有影响。催化裂解反应机理与催化剂的种类和反应条件相关。对于酸性分子筛催化剂有2种比较公认的机理:正碳离子机理,自由基与正碳离子机理两种形式。研究表明碳四烷烃,特别是正丁烷催化裂解制低碳烯烃具有良好的低碳烯烃收率,收率可达50%以上。     

Co-LsX催化苯乙烯生成环氧苯乙烷绿色合成工艺研究

采用离子交换法制备Co-LsX催化剂,分子筛经Co2+离子交换后,其骨架结构没有发生变化。考察了反应温度、反应时间、催化剂用量、溶剂加入量及氧气通入速率等因素对苯乙烯环氧化反应的影响。得出最佳工艺条件:反应温度100℃,反应时间6 h,Co-LsX与苯乙烯质量比为0.16,混合溶剂与苯乙烯体积比为5;V(O2)∶V(苯乙烯)=1.3 min-1。在此条件下苯乙烯转化率达到62.5%,环氧苯乙烷的选择性达到57.1%。催化剂经6次循环使用后活性和稳定性都比较好。     

Asymmetric Sharpless epoxidation of 13S‐hydroxy‐ 9Z, 11E‐octadecadienoic acid (13S‐HODE)

The asymmetric Sharpless epoxidation of methyl 13S‐hydroxy‐9Z, 11E‐octadeca‐dienoate (13S‐HODE, 1 ) with tert‐butyl hydroperoxide (TBHP) catalysed by titanium tetraisopropoxide {Ti(ⁱOPr)₄} in the presence of L(+)‐diisopropyl tartrate (L‐DIPT) gave methyl 13S‐hydroxy‐11S, 12S‐epoxy‐9Z‐octadecenoate 2 (erythro isomer) in 84% diastereomeric excess (de). The epoxidation of 1 with TBHP catalysed by Ti(ⁱOPr)₄ in the presence of D(‐)‐DIPT yielded methyl 13S‐hydroxy‐11RR12R‐epoxy‐9Z‐octadecenoate (threo isomer) 3 in 76% de.