异山梨醇焦油还原制备Co-Mo_(2)C催化合成2,5-二羟基对苯二甲酸二甲酯  

Preparation of Co-Mo_(2)C with isosorbitol-tar reduction for catalytic synthesis of dimethyl 2,5-dihydroxyterephthalate

作　　者：赵世丽 单玉华[1,2] 胡林玲 蔡志祥 李焱叶 刘平 ZHAO Shili;SHAN Yuhua;HU Linling;CAI Zhixiang;LI Yanye;LIU Ping(School of Petrochemical Engineering,Changzhou University,Changzhou 213164,Jiangsu,China;Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,Changzhou 213164,Jiangsu,China)

机构地区：[1]常州大学石油化工学院,江苏常州213164 [2]江苏省先进催化与绿色制造协同创新中心,江苏常州213164

出　　处：《精细化工》2023年第10期2257-2263,共7页Fine Chemicals

摘　　要：异山梨醇焦油在无水K_(2)CO3催化下高温原位还原四水合钼酸铵和六水合硝酸钴制备了钴杂化碳化钼(Co-Mo_(2)C),采用XRD、N_(2)吸附-脱附、SEM、XPS对所制备样品进行了表征。将制备的Co-Mo_(2)C用于催化O_(2)氧化丁二酰丁二酸二甲酯(DMSS)合成2,5-二羟基对苯二甲酸二甲酯(DMDHT)。考察了煅烧温度、n(Co)︰n(Mo)、氧化反应条件对DMDHT HPLC纯度和收率的影响。结果表明,异山梨醇焦油在850℃原位还原四水合钼酸铵和六水合硝酸钴4 h制得了比表面积为134 m^(2)/g的Co-5Mo_(2)C-4(其中,5为Mo和Co物质的量比值,4为煅烧时间,h),其较好的催化性能归因于Co与Mo_(2)C的协同作用。在2.00 g Co-5Mo_(2)C-4催化作用下,DMSS在110℃、1.00 MPa O_(2)气氛中反应4 h,可得到收率为88.22%、HPLC纯度为99.98%的DMDHT。Co-5Mo_(2)C-4具有良好的循环性能,循环使用6次后,DMDHT的收率仅下降1.7%;循环使用9次后,DMDHT的收率下降了7.3%。Cobalt-hybrid molybdenum carbide(Co-Mo_(2)C)was prepared by in situ reduction of ammonium molybdate tetrahydrate and cobalt nitrate hexahydrate with isosorbitol-tar in the presence of anhydrous K_(2)CO_(3)at high temperature and characterized by XRD,N_(2)adsorption-desorption,SEM and XPS.The Co-Mo_(2)C obtained was then used to catalyze the oxidation of dimethyl succinate(DMSS)by O_(2)to form dimethyl 2,5-dihydroxyterephthalate(DMDHT).The effects of calcination temperature,molar ratio of Co to Mo and oxidation conditions on HPLC purity and yield of DMDHT were investigated.The results showed that Co-5Mo_(2)C-4(Where,5 is the molar ratio of Mo to Co,and 4 is the calcined time,h)with a specific surface area of 134 m^(2)/g could be successfully synthesized by in situ reduction of ammonium molybdate tetrahydrate and cobalt nitrate hexahydrate at 850℃for 4 h with isosorbitol-tar,and exhibited good catalytic property due to the synergistic effect of Co and Mo_(2)C.Under the conditions of 2.00 g Co-5Mo_(2)C-4 as catalyst,1.00 MPa O_(2),reaction temperature of 110℃,and reaction time of 4 h,DMDHT with a yield of 88.22%and HPLC purity of 99.98%was obtained.Meanwhile,Co-5Mo_(2)C-4 showed good cycling performance.The yield of DMDHT decreased by only 1.7%after 6 recycles,and 7.3%after 9 recycles.

关 键 词：异山梨醇焦油 原位还原 钴杂化碳化钼 催化氧化 二羟基对苯二甲酸二甲酯 

分 类 号：TQ[化学工程]