乙酸镁改性ZSM-5分子筛上甲苯与碳酸二甲酯的择形烷基化.pdfVIP

学兔兔 化 工 进 展 ·1498· CHEMICAL INDUSTRY AND ENGINEERING PROGRESS 201 1年第30卷第7期 乙酸镁改性ZSM．5分子筛上甲苯与碳酸二甲酯的择形烷基化 王永飞，薛 冰，许 杰，李永昕 (常州大学石油化工学院，江苏 常州 213164) 摘 要：以乙酸镁为前体，采用等体积浸渍法制备不同负载量的MgO／ZSM一5催化剂，在气相连续流动固定床反 应器上对甲苯与碳酸二甲酯(DMC)择形烷基化合成对二甲苯进行了研究。采用XRD、NH3一TPD、吡啶吸附红 外和2,4一二甲基喹啉吸附红外等手段对催化剂进行了表征。结果表明：B酸中心是甲苯与DMC烷基化反应的活 性中心；随着MgO负载量的增加，甲苯转化率下降，对二甲苯的选择性上升；当MgO负载量大于9％时，甲苯 转化率和对二甲苯选择性基本保持不变。2，4一二甲基喹啉吸附红外表征结果表明，乙酸镁在改性过程中未进入 ZSM一5孔道内，焙烧分解生成的MgO主要分布在分子筛的外表面，分子筛孔内酸位并未受到影响。随着MgO 负载量的增加，催化剂外表面的B酸位数量下降，当负载量大于9％时，外表面的B酸位基本消失。 关键词：ZSM一5分子筛；MgO氧化镁；碳酸二甲酯；烷基化；对二甲苯 中图分类号：TQ 243．1 文献标志码：A 文章编号：1000—6613(2011)07—1498—05 Selective synthesis ofp-xylene by alkylation of toluene with dimethyl carbonate over magnesium acetate--modified ZSM--5 WANG Yongfei，XUEBing，XUJie，LI Yongxin (School ofPetrochemical Technology，Changzhou University，Changzhou 213164，Jiangsu，China) Abstract：MgO—modified ZSM一5 was prepared by impregnation of ZSM一5 with an aqueous solution of magnesium nitrate．Selective synthesis of P—xylene by alkylation of toluene with dimethyl carbonate (DMC)was carried out in a continuous flOW fixed—bed rector over MgO—modified ZSM．5 zeolite． Physico—chemical properties of MgO／ZSM一5 catalysts were characterized by means of XRD， NH3一TPD， 2，4一dimethylquinoline—IR and pyridine—IR．The results of experiments indicated that alkylation of toluene with DMC occu~ed mainly on BrCnsted acid sites．With increasing Mg0 content，there was a decrease in toluene conversion and increase in selectivity for P—xylene．With further increase in MgO content