新型钨基催化剂上环己烯环氧化反应（英文）

烯烃环氧化在现代化学中具有重要的学术和工业价值,但采用绿色氧化剂过氧化氢仍面临传质的挑战。采用过氧缩合法制备了一种新型钨基催化剂,用于过氧化氢与环己烯环氧化研究,环己烯的转化率为51.2%,环氧环己烷的选择性为69.2%。结果显示该催化剂催化活性高,环氧环己烷的选择性好,反应条件温和,工艺无溶剂且绿色环保。     

微波辐射下过氧化氢氧化环己烯制环氧环己烷的研究

研究了微波辐射下30%过氧化氢氧化环己烯为环氧环己烷中反应时间、溶剂和催化剂等因素对环氧环己烷的选择性和转化率的影响。微波辐射50minWO42-/PO43-/cetyl催化环氧化选择性为93.1%转化率为75.2%,与常规条件相比反应时间明显缩短且环氧环己烷的选择性和转化率有所提高。     

环己烯环氧化制备环氧环己烷的方法

本本发明提供一种环己烯环氧化制备环氧环己烷的方法,主要解决现有技术中存在催化剂活性低、环氧环己烷选择性低的问题。该方法以环己烯为底物,乙腈为反应溶剂,叔丁基过氧化氢溶液为氧化剂,在片层厚度不超过20nm、骨架钛摩尔含量不低于2%的薄层、高骨架钛含量的Ti-MWW分子筛催化剂上进行烯烃环氧化反应,反应结束后将反应液精馏处理,取130℃～135℃的馏分,得到环氧环己烷。本发明的方法环己烯转化率高、目标产物环氧环己烷的选择性高,可用于环氧环己烷的工业生产。     

环己烯催化环氧化反应的研究新进展

综述了环己烯催化氧化法合成环氧环己烷的最新研究进展。近年来,催化环己烯环氧化越来越受到关注,因为它采用了来源方便和具有环保性质的氧化剂。介绍了环己烯催化环氧化的一些新进展。反应中采用了各种氧化剂如过氧化氢(双氧水),叔丁基过氧化氢(TBHP)和分子氧(O2),以及各种含有各种配体(如席夫碱、卟啉、酞菁和杂多酸)的过渡金属催化剂。对有关反应的机理进行了讨论。     

环己烯液相环氧化催化剂的研究进展

烯烃环氧化是一类重要的有机合成反应 ,其中环己烯经催化环氧化制得的环氧环己烷可广泛用作合成精细化学品的原料。阐述了Mo(Ⅵ )、V(Ⅴ )、Ti(Ⅳ )络合物、过渡金属卟啉络合物等环氧化用催化剂以及无机过氧酸盐、过氧化氢、分子氧、有机过氧酸及烷基过氧化氢等常用氧化剂在环己烯液相环氧化中的应用研究进展。还介绍了无机固体负载催化剂和高分子负载催化剂的负载化方法。最后展望了烯烃环氧化的研究开发趋势。     

环己烯催化环氧化合成环氧环己烷的的优化实验研究

实验选用绿色环保且原子经济性高的分子氧或H2O2为氧化剂,以自制的固载型过氧化磷钨杂多酸季铵盐相转移催化剂,对环己烯催化环氧化合成环氧环己烷研合成工艺条件进行了研究。得出在不使用任何溶剂时的优化条件为:反应物料物质的量配比n环己烯∶nH2O2=1.75∶1(摩尔数),wH2O2水溶液(w=30%)∶w催化剂=7.08∶1(质量比),wH2O2水溶液(w=30%)∶w助剂A=21.24∶1(质量比);反应温度55℃,反应时间5.5 h。在此条件下环己烯的平均当量转化率为84.89%,目的产物环氧环己烷的选择性平均值达94.53%。     

离子热合成CdMoP复合氧化物及其催化性能研究

采用离子液体热合成法制备了新型镉钼磷（CdMoP）系列复合氧化物催化剂,并通过FT-IR、XRD、SEM、TEM及XPS等表征手段对催化剂物化性质进行表征。由表征结果可知离子液体不仅能够进入CdPMo-80催化剂骨架,同时还能将P元素固定于催化剂中,从而呈现出有序增长的层状结构且拥有较多强酸中心。将以环己烯氧化制备环氧环己烷为探针反应,考察了CdMoP-80复合金属氧化物催化剂的催化性能。结果表明,在催化剂用量0.2 g,质量分数为30%的过氧化氢4 mL,环己烯2 mL,乙腈4 mL,55 oC条件下反应4 h后定性定量分析,环己烯的转化率为99.2%,环氧环己烷的选择性为97.0%。     

金属多氧酸盐杂化催化剂上环己烯分子氧环氧化

针对分子氧环己烯催化环氧化反应转化率和环氧化选择性低、需要大量溶剂的加入等缺点,现以金属多氧酸盐(POMs)和纳米金作为催化活性中心,采用混合甲醛还原法、水合肼甲醛还原法、氢气甲醛还原法等3种方式分别添加二元金属Co、Bi制备以ZSM-5分子筛作为载体的负载型金属多氧酸盐杂化催化剂,考察了二元金属种类及负载方法、POMs种类、反应条件等对催化剂在无溶剂条件下催化分子氧环己烯环氧化性能的影响。实验结果表明,以混合甲醛还原法负载二元金属Bi的催化剂性能比负载Co的催化剂更好,其中Bi较合适的表观负载量为0.5%;金属多氧酸盐选择PMo_(11)和BMo_(11)混合负载效果略优,总负载量w为6.67%,二者质量比为1:1,以此制备的催化剂1%Au-0.5%Bi/PMo_(11)-BMo_(11)/ZSM-5-m催化环氧化性能较佳,在反应压力0.5 MPa、反应温度80℃、环己烯2.0 g、3滴(约0.04 g)叔丁基过氧化氢(TBHP)、催化剂0.02 g的条件下反应18 h,环己烯的转化率可达39.3%,环氧环己烷的选择性可达到40.9%。     

Mn saloph/ZSM-5催化环己烯环氧化性能的研究

采用柔性配体法以ZSM-5型分子筛为载体,固载Schiff碱锰配合物,制备了分子氧环氧化环己烯的催化剂Mn saloph/ZSM-5,并用FT IR、ICP、TG-DTA以及BET等技术对其进行表征。对其催化分子氧环氧化环己烯制备环氧环己烷的工艺条件进行探索,结果表明,在35℃,环己烯2 mL,乙腈20 mL,异丁醛5 mL,催化剂40 mg的条件下,,环氧环己烷的单程收率可达78.73%,且催化剂易于分离回收。     

相转移催化H2O2环氧化环己烯合成环氧环己烷

对反应控制相转移催化剂制备方法进行了改进,催化剂产率可达94%,并用红外光谱(IR)和元素分析对催化剂进行了表征;将催化剂用于以w(H2O2)=34.5%为氧化剂,以质量分数76.7%的工业粗环己烯为原料合成环氧环己烷;探讨了反应时间、反应温度、环己烯与H2O2的摩尔比、催化剂用量、溶剂用量等因素对反应的影响。获得的较佳合成条件(以0.08 mol H2O2计)为:反应温度40℃,反应时间90 m in,催化剂用量0.6 g,n(C6H10)∶n(H2O2)=2.5∶1,溶剂1,2-二氯乙烷70 mL。该条件下环氧环己烷平均选择性为96.1%,环氧环己烷的平均收率达91.7%。将回收的催化剂用于反应,环氧环己烷的平均选择性和平均收率分别为95.3%和90.9%。     

丙烯环氧化合成环氧丙烷新技术的研究进展

评述了以分子氧和双氧水为氧源的丙烯环氧化催化剂体系的最新研究进展。其中包括金属Ag催化剂。金属熔盐混合物，钛硅沸石TS-1和过渡金属络合物催化剂体系，根据氧转移机理。金属Ag催化剂和熔盐体系是以分子氧为直接氧源，而TS-1和最近报道的反应相转移含钨催化剂本质上是以过氧化氢为直接氧源。TS-1和反应相转移含钨催化剂和优点是反应条件较温和，生成环氧丙烷的选择性和产率较高。如一种负载成“蛋壳醇作为溶剂），环氧丙烷选择性和产率（以双氧水计）分别可达92%和90%以上。催化剂运转1000h以上性能稳定，今后的一个重要发展方向是开发以分子氧为起始氧源，简单高效的原位双氧水工艺。     

Heterogeneous catalysts obtained by incorporation of polymer-supported phosphonates into silica used in oxidation reactions

Summary The synthesis of copolymers functionalized with phosphonate groups, incorporation of them into ordered meso-macroporous silica, characterization and evaluation of the obtained materials as catalysts in oxidation of cyclohexene are presented. The catalysts obtained are very active and selective in epoxidation of cyclohexene using hydrogen peroxide as an environmentally friendly oxidant.     

C02＋离子取代Keggin型磷钼酸催化剂催化环己烯制备环氧环己烷的工艺研究

以固载型过渡金属Co2＋离子取代的Keg舀n型磷钼酸为催化剂,分子氧为氧化剂,在管式微分反应器中进行了催化氧化环己烯合成环氧环己烷的工艺研究,结果表明,在反应温度260℃、反应压力1．7MPa、环己烯流量0．05mL／min、氧气流量9mL／min和催化剂1．5g的条件下,单程环己烯转化率和环氧环己烷的选择性分别为11．4％和75．1％,环氧环己烷单程收率可迭85．6％。     

超声内环流气升式反应器中环己烯环氧化反应的研究

Epoxidation of cyclohexene to cyclohexene oxide was studied in a new type reactor-the ultrasound airlift loop reactor. The influences of ultrasound intensity, molar ratio of isobutyraldehyde to cyclohexene and oxygen gas flow rate on the conversion of cyclohexene and selectivity of cyclohexene oxide were investigated and discussed, and the optimal operation condition was found, under which 95.2% conversion of cyclohexene and 90.7% selectivity of cyclohexene oxide were achieved. The ultrasonic airlift loop reactor utilizes the synergistic effect of sonochemsitry and higher oxygen transfer rate. Possible reaction mechanisms were outlined and the reason of ultrasound promotion of epoxidation reactionwas analyzed.     

Grafting polyethylene glycols molybdenum(VI) complexes on ZSPP and their catalytic epoxidation of cyclohexene

A new type of inorganic–organic hybrid materials – zirconium oligo-styrenyl phosphonate hydrogen phosphate (ZSPP) was used to prepare heterogeneous catalysts for olefin epoxidation by grafting polyethylene glycols on ZSPP and subsequently coordinating with MoO₂(acac)₂. The catalysts were characterized by IR, Raman, XPS, XRD, TG, BET and elemental analysis. The catalytic activities of the prepared catalysts were evaluated through the epoxidation of cyclohexene using TBHP as oxidant. The results indicated that conversion and selectivity increased at first and then decreased with increasing numbers of O atoms in the ligands, and the catalyst 2b gave the best catalytic results that the conversion and selectivity was up to 98.9% and 97.4%, respectively.     

Epoxidation of allyl alcohol to glycidol using titanium silicalite TS-1: effect of the reaction conditions and catalyst acidity

The epoxidation of allyl alcohol to glycidol using the titanium silicalite TS-1 with hydrogen peroxide as the oxidant is described and discussed in detail. The reaction conditions (alcohol, solvent, temperature) required to obtain 100% selectivity to glycidol are described and this selectivity has been observed at conversions of allyl alcohol of up to 20%. Addition of excess hydrogen peroxide enhances conversion but does not appear to affect selectivity to glycidol deleteriously, whereas addition of hydrogen peroxide over an extended time period is not particularly beneficial. The major side reactions are the oxidation of the alcohol solvent and the ring opening solvolysis of the glycidol that leads to the formation of alkoxy diols. Base treatment of the TS-1 using sodium azide enhances the glycidol selectivity, whereas the incorporation of Brønsted acid sites by addition of aluminium into the framework structure of TS-1 enhances the selectivity to the products of solvolysis ring opening reactions.     

Alumina‐Catalyzed Epoxidation with Hydrogen Peroxide: Recycling Experiments and Activity of Sol‐Gel Alumina

Commercial alumina looses some activity after the first epoxidation reaction of (S)‐limonene with hydrogen peroxide, but maintains a good activity and a very high selectivity in the subsequent three reactions. After this its activity is strongly reduced, probably due to structural modifications. Aluminas obtained by sol‐gel methods are normally less active than the commercial alumina. However, the use of monomeric aluminum sec‐butoxide and of oxalic acid to form stable alumina mesophases allows a very active alumina to be obtained, which catalyses the epoxidation of the less reactive cyclohexene with hydrogen peroxide in 98% yield. Close to 50% of the active oxygen is used up in the formation of molecular oxygen.