杂多酸盐催化乙二醇合成乙二醇乙醚和乙二醇双乙醚的研究  

Synthesis of glycol ether and glycol diethyl ether from ethylene glycol catalyzed by heteropolyacid salt

作　　者：李刚森 付思美[1] 王俊文[1] 章亚东[2] LI Gang-sen;FU Si-mei;WANG Jun-wen;ZHANG Ya-dong(College of Chemistry and Chemical Engineering,Taiyuan University of Technology,Taiyuan 030024,China;School of Chemical Engineering and Energy,Zhengzhou University,Zhengzhou 450001,China)

机构地区：[1]太原理工大学化学化工学院,山西太原030024 [2]郑州大学化工与能源学院,河南郑州450001

出　　处：《应用化工》2019年第9期2070-2073,2080,共5页Applied Chemical Industry

基　　金：国家自然科学基金青年科学基金(21602207);山西省自然科学基金(201801D121058)

摘　　要：以磷钨酸、硅钨酸和磷钼酸及硝酸银、硝酸铁、硝酸铯和碳酸铯为原料,通过共沉淀法制备了系列杂多酸盐催化剂,通过X射线衍射仪(XRD)、电子能谱(EDS)、热重/差热分析仪(TG)对催化剂的晶型结构、表面元素及热重性质进行了表征。结果表明,磷钨酸银铯和磷钨酸银具有Keggin型磷钨酸结构,表面元素分布均匀,煅烧温度在20~220℃时会失去结合水,300~450℃时会失去结晶水和结构水,900℃以上则会分解。通过催化乙二醇和乙醇合成乙二醇乙醚和乙二醇双乙醚的反应考察杂多酸及杂多酸盐催化性能。考察了阳离子种类、取代度和不同煅烧温度对杂多酸盐催化性能的影响,结果表明,磷钨酸及其盐系列催化剂效果最好。通过考察阳离子种类和磷钨酸氢离子的取代度,结果表明,Cs0.66Ag0.33H2PW12O40催化效果最好。在该催化剂存在下,n乙二醇∶n乙醇为1∶4,反应时间4 h,反应温度200℃,乙二醇转化率为98.16%,乙二醇乙醚选择性为49.25%,乙二醇双乙醚选择性为48.59%,乙二醇醚的总产率为96.04%。A series of heteropoly acid salt catalysts were prepared through the coprecipitation method with phosphotungstic acid,silicotungstic acid,phosphomolybdic acid,silver nitrate,ferric nitrate,cesium nitrate and cesium carbonate as raw material.The crystal structure,surface element,were characterized by means of X-ray diffraction(XRD),energy dispersive spectroscopy(EDS) and thermogravimetry(TG).The results show that Cs3PW12O40 and Ag3PW12O40 have the same Keggin structure as H3PW12O40.The elements of Cs0.66Ag0.33H2PW12O40 distributed uniformly at the surface.The bound water and crystal water of catalyst loosed respectively with the calcination temperature range of 20~220 ℃ and 300~450 ℃.The catalyst will decomposition at 900 ℃.The catalytic activity of the catalysts were investigated through catalyzed glycol and ethanol to synthesis the ethylene glycol ethyl ether and ethylene glycol diethyl ether.The effects of cationic species,degree of substitution,and temperature of calcinations on the catalytic properties of heteropoly acid salt were studied.The results indicate that the catalytic activity of phosphotungstic acid and its salt are higher than other heteropoly acid salt.By investigating the degree of substitution and the cationic species,the results showed that the best catalyst was Cs0.66Ag0.33H2PW12O40.In the presence of this catalyst,n(ethanol)∶n(glycol)=1∶4,reaction time 4 h,reaction temperature 200 ℃,the conversion of ethylene glycol was 98.16%,the selectivity of ethylene glycol monoethyl ether and ethylene glycol dimethyl ether were 49.25% and 48.59% respectively,the total yield of ethylene glycol ether was 96.04%.

关 键 词：磷钨酸 硝酸铯 硝酸银 乙二醇乙醚 乙二醇 乙醇 

分 类 号：TQ032.4[化学工程] O643.36[理学—物理化学]