HKUST-1负载磷钨酸选择性合成乙二醇单叔丁基醚  

Selective synthesis of ethylene glycol mono-tert-butyl ether with HKUST-1 supported phosphotungstic acid

作　　者：马德亮 蒙旭雯 汤吉海 张竹修[1,2] 崔咪芬 乔旭 MA Deliang;MENG Xuwen;TANG Jihai;ZHANG Zhuxiu;CUI Mifen;QIAO Xu(College of Chemical Engineering,Nanjing Tech University,Nanjing 211800 Jiangsu,China;State Key Laboratory of Materials-Oriented Chemical Engineering,Nanjing Tech University,Nanjing 211800 Jiangsu,China)

机构地区：[1]南京工业大学化工学院,江苏南京211800 [2]南京工业大学材料化学工程国家重点实验室,江苏南京211800

出　　处：《精细化工》2022年第7期1411-1418,共8页Fine Chemicals

基　　金：国家自然科学基金(21676141,21808104);国家重点研发计划项目(2017YFB0307304);江苏省重点研发计划重大科技示范项目(BE2021710);江苏高校“青蓝工程”项目。

摘　　要：采用一锅法制备了HKUST-1负载磷钨酸(HPW)(HPW@HKUST-1),采用XRD、SEM、EDS、BET、ICP、吡啶红外(Py-IR)、酸碱滴定对其进行了表征。评价了HPW@HKUST-1作为催化剂用于异丁烯(IB)与乙二醇(EG)选择性醚化合成乙二醇单叔丁基醚(EGME)的催化性能。结果表明,HPW负载量的提高增加了催化剂Bronsted酸活性位点,有利于提高反应物转化率,同时HPW负载量与催化剂平均孔径呈负相关性,平均孔径减小有利于提高EGME选择性。HPW负载量为10%(以HKUST-1物质的量为基准,下同)的HPW@HKUST-1催化剂活性较优,其催化IB和EG合成EGME最优的反应条件为:反应温度100℃,n(IB)/n(EG)=6,催化剂用量为EG质量(11.13 g)的10%,反应时间4 h。在该反应条件下,EG转化率为97%,EGME选择性为85%。此外,该催化剂具有良好的循环稳定性,使用5次后,EG转化率为91%,EGME选择性为78%。HKUST-1 supported phosphotungstic acid(HPW)(HPW@HKUST-1),prepared by one-pot method and characterized by XRD,SEM,EDS,BET and ICP,pyridine infrared(Py-IR)and acid-base titration,was used as a catalyst for selective etherification of isobutene(IB)and ethylene glycol(EG)to ethylene glycol monobutyl ether(EGME)to evaluate its catalytic activity.The results showed that elevated HPW loading increased the Bronsted acid active site of catalyst,which was conducive to high efficiency conversion of reactants.Meanwhile,increased HPW loading led to catalyst pore size reduction which contributed to selectivity enhancement of EGME.HPW@HKUST-1 catalyst with 10% of HPW loading(molecular ratio to HKUST-1,the same below)exhibited better catalytic activity.The reactant EG conversion rate and product EGME selectivity reached 97% and 85% respectively under the optimal reaction conditions of reaction temperature 100℃,n(IB)/n(EG)=6,dosage of 10% HPW@HKUST-1 catalyst being 10% of EG mass(11.13 g)and reaction time of 4 h.In addition,EG conversion rate and EGME selectivity remained as high as 91% and 78% respectively with catalyst recycled 5 times,which indicated good cyclic stability.

关 键 词：HKUST-1 负载 磷钨酸 选择性醚化 乙二醇单叔丁基醚 催化技术 

分 类 号：TQ426[化学工程]