Preparation and application in the hydrogenation of dimethyl terephthalate of Ru@G-CS catalyst
王彩丽 浙江大学化学系, 生物质化工教育部重点实验室, 杭州 310058  
叶柏镛 浙江大学化学系, 生物质化工教育部重点实验室, 杭州 310058  
王韩 浙江恒逸石化研究院有限公司, 杭州 311200  
王松林 浙江恒逸石化研究院有限公司, 杭州 311200  
杨磊 浙江恒逸石化研究院有限公司, 杭州 311200  
侯昭胤 浙江大学化学系, 生物质化工教育部重点实验室, 杭州 310058
浙江恒逸石化研究院有限公司, 杭州 311200 
摘要: 采用一步热解法制备了一系列氮掺杂石墨烯包覆的Ru基催化剂(Ru@G-CS),并将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)的反应中。利用粉末X射线衍射、拉曼光谱、N2吸附-脱附、X射线光电子能谱、扫描电子显微镜和透射电子显微镜对催化剂的组成、结构和表面形貌进行了表征。实验发现: Ru@G-CS (1∶4)催化剂具有最高的活性和优异的稳定性,在160℃、2.5 MPa、mDMT/mRu=833的条件下,反应4 h后DMT的转化率可达100%,DMCD的选择性高于98.5%;且该催化剂的活性经10次循环使用后未见明显下降。表征结果表明,氮掺杂石墨烯骨架中的氮原子可以促进Ru的分散,而且与负载的Ru之间存在较强的相互作用,这种电子-结构的协同效应可能是Ru@G-CS (1∶4)催化剂表现出优异的活性和稳定性的主要原因。
关键词: 对苯二甲酸二甲酯  1,4-环己烷二甲酸二甲酯  加氢  石墨烯  Ru
基金项目: 中央高校基本科研业务费专项资金(No.226-2022-00055)资助。
Abstract: A series of nitrogen-doped graphene-coated Ru-based catalysts (Ru@G-CS) were prepared using glucose, melamine, and RuCl3 as raw materials in a facile one-step pyrolysis method at 700℃ with a varied mass ratio of glucose/melamine in feed. The composition, structure, and surface morphology of these catalysts were characterized with powder X-ray diffraction, Raman spectroscopy, N2 adsorption-desorption, X-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscope. Characterization results showed that nitrogen in the graphene skeleton can promote the dispersion of Ru, and there was also a strong interaction between nitrogen and loaded Ru. Ru@G-CS(1:4) catalyst (with the mass ratio of glucose/melamine in feed was 1:4) possesses the highest surface area (429 m2·g-1), biggest pore volume (0.45 cm3·g-1) and highly dispersed Ru particles (about 1 nm) that encapsulated in 1-2 layered graphene film. At the same time, the detected wRu0/wRu4 + (73.6/26.4), ID/IG (1.30) and I2D/IG (0.32) reached their maximum in Ru@G-CS(1:4). These catalysts were tested in dimethyl terephthalate (DMT) hydrogenation to 1,4-cyclohexane dimethyl dicarboxylate (DMCD) under mild conditions and compared with those traditional carriers (HZSM-5, Al2O3, MgO, ZnO) supported Ru catalysts. Ru@G-CS(1:4) exhibited high activity and stability at 160℃, 2.5 MPa H2, mDMT/mRu=833, the detected conversion of DMT reached 100% and the selectivity of DMCD remained higher than 98.5% within 4 h. The calculated turnover frequency of each Ru was 233.4 h-1. More importantly, Ru@G-CS(1:4) could maintain its performance at least in 10 cycles. It was concluded that the electron-structure synergistic effect might be the main reason for the excellent activity and stability of Ru@G-CS(1:4).
Keywords: dimethyl terephthalate  dimethyl 1,4-cyclohexanedicarboxylate  hydrogenation  graphene  Ru
投稿时间:2023-05-20 修订日期:2023-09-17
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