Ru/CN催化对苯二甲酸二甲酯加氢制备1,4-环己烷二甲酸二甲酯  

Catalytic hydrogenation of dimethyl terephthalate to dimethyl 1,4-cyclohexanedicarboxylate over Ru/CN catalyst

作　　者：苏佳娜 郭秀枝 王公应[1,3] 邓志勇 SU Jiana;GUO Xiuzhi;WANG Gongying;DENG Zhiyong(Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610041,Sichuan,China;China-Serbia"the Belt and Road"Joint Laboratory on Environment and Energy,College of Resources and Environment,Chengdu University of Information Technology,Chengdu 610225,Sichuan,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院成都有机化学研究所,四川成都610041 [2]成都信息工程大学资源环境学院,中-塞环境与能源“一带一路”联合实验室,四川成都610225 [3]中国科学院大学,北京100049

出　　处：《精细化工》2021年第7期1505-1512,共8页Fine Chemicals

基　　金：四川省科技计划资助(2021YFG0225,2021ZHZY0006)。

摘　　要：通过超声辅助NaBH_(4)还原法制备了3%Ru/CN(3%为Ru的负载量,以CN的质量计,下同),其中,CN为介孔结构的氮掺杂碳材料,该催化剂用于对苯二甲酸二甲酯(DMT)加氢制备1,4-环己烷二甲酸二甲酯(DMCD)。采用Raman、SEM、TEM、N_(2)吸附-脱附、XRD、XPS对载体和催化剂的组成、表面性能进行了表征。考察了催化剂用量、反应温度、H_(2)压力、反应时间对催化剂加氢性能的影响。结果表明,氮元素成功掺入碳骨架中且氮掺杂碳材料为介孔结构。在DMT 1.00 g,催化剂0.05 g、反应温度140℃、反应压力5.0 MPa、反应时间1.0h的最优反应条件下,DMT转化率为100%,DMCD选择性为99.3%。以1000℃下炭化制备的CN-1000为载体,得到的3%Ru/CN-1000催化剂循环使用4次后,催化性能未见明显下降,DMT转化率可达98.8%,DMCD选择性为99.7%。3% Ru/CN catalyst(3% being the loading amount of Ru,calculated by the mass of CN,the same below)was prepared via a simple ultrasound-assisted NaBH_(4) reduction method.In which,CN was a nitrogen doped carbon material with mesoporous structure.Then the catalyst was used for the hydrogenation of dimethyl terephthalate(DMT)to dimethyl 1,4-cyclohexanedicarboxylate(DMCD).The composition and surface properties of the support and catalyst were characterized by Raman spectrum,SEM,TEM,N_(2) adsorption-desorption isotherms,XRD and XPS.The effects of catalyst dosage,reaction temperature,H_(2) pressure and reaction time on the hydrogenation properties were investigated.The results showed that nitrogen was successfully incorporated into the carbon framework and the N-doped carbon material had a mesoporous structure.Under optimal reaction conditions of DMT 1.00 g,catalyst 0.05 g,reaction temperature 140℃,reaction pressure 5.0 MPa and reaction time 1.0 h,the conversion rate of DMT was 100% and the selectivity of DMCD was 99.3%.After recycled for 4 times,the catalytic performance of 3% Ru/CN-1000 catalyst(CN-1000 being the support which was prepared by carbonization at 1000℃)did not decrease obviously,the conversion rate of DMT and the DMCD selectivity was 98.8% and 99.7%,respectively.

关 键 词：对苯二甲酸二甲酯 1 4-环己烷二甲酸二甲酯 催化加氢 Ru/CN催化剂 精细化工中间体 

分 类 号：TQ235[化学工程—有机化工] TQ426