Keggin型磷钼矾杂多化合物在氧化羰基化合成碳酸二苯酯中的应用

Application of Keggin type molybdovanadophosphoric compounds in synthesis of diphenyl carbonate by oxidative carbonylation with phenol

采用酸化乙醚萃取法制备了Keggin型磷钼矾杂多酸及其盐,并采用FT-IR和BET对磷钼矾杂多酸进行了表征。考察了磷钼矾杂多化合物在苯酚氧化羰基化合成碳酸二苯酯反应中的性能。结果表明,高含钒量的杂多酸具有更好的催化活性,它们的活性顺序为:H6PMo9V3O40>H5PMo10V2O40>H4PMo11VO40。用不同价态的金属阳离子取代H6PMo9V3O40中的氢离子后,CeH3PMo9V3O40表现出了最好的性能,DPC的收率达6.7%;当进一步用VO2+取代了CeH3PMo9V3O40中的氢离子后,Ce[VO]1.5PMo9V3O40的性能更好,碳酸二苯酯的收率达10.2%。

A series of vanadium-containing H3＋xPMo12-xVxO40 （x = 1,2 and 3） Keggin HPA were prepared for use in the oxidative carbonylation of phenol to DPC. The co-catalysts were characterized by FT- IR,BET, and their activities were test, too. The catalytic performance exhibited that the activity of the H3＋xPMo12-xVxO40 decreased in order of H6PMo9V3O40 〉 H5PMo10V2O40 〉 H4PMo11VO40. When the hydrogen atoms of the H6PMo9V3O40 were replaced by different valence metal cation to obtain the salt of the Keggin structure of molybdovanadophosphoric heteropoly acid, the Ce substituted salt CeH3PMo9V3O40 gave the highest activity,and the yield of DPC reached 6.7% ;when a further substitution of the hydrogen atoms of the Ce salt was carried by VO^2＋ , Ce [ VO ] 3/2 PMo9 V3 O40 showed the higher activity, and the yield of DPC was up to 10.2%.