碳酸乙烯酯选择加氢合成甲醇与乙二醇高效稳定Cu/SiO2催化剂研究

doi:10.1016/S1872-2067(18)63032-3

催化学报 ›› 2018, Vol. 39 ›› Issue (8): 1283-1293.DOI: 10.1016/S1872-2067(18)63032-3

• 第十五届国际二氧化碳利用会议专栏 • 上一篇下一篇

碳酸乙烯酯选择加氢合成甲醇与乙二醇高效稳定Cu/SiO₂催化剂研究

刘佳驹^a,c, 贺鹏^a, 王利国^a,b,d, 刘辉^c, 曹妍^a, 李会泉^a,d

a 中国科学院过程工程研究所中国科学院绿色过程与工程重点实验室, 北京 100190;
b 盐城工学院, 江苏省生态建材与环保装备协同创新中心, 江苏盐城 224051;
c 北京化工大学, 北京 100029;
d 中国科学院大学中丹学院, 北京 100049

收稿日期:2017-11-15 修回日期:2018-01-11 出版日期:2018-08-18 发布日期:2018-07-04
通讯作者: 王利国, 李会泉
基金资助:
国家自然科学基金（21576272，21406245）；江苏省生态建材与环保装备协同创新中心专项（YCXT201607）；中国科学院洁净能源先导科技专项资助（XDA21030600）.

An efficient and stable Cu/SiO₂ catalyst for the syntheses of ethylene glycol and methanol via chemoselective hydrogenation of ethylene carbonate

Jiaju Liu^a,c, Peng He^a, Liguo Wang^a,b,d, Hui Liu^c, Yan Cao^a, Huiquan Li^a,d

a National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
b Jiangsu Collaborative Innovation Center for Ecological Building Materials and Environmental Protection Equipments, Yancheng Institute of Technology, Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province, Yancheng 224051, Jiangsu, China;
c Beijing University of Chemical Technology, Beijing 100029, China;
d Sino-Danish College, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2017-11-15 Revised:2018-01-11 Online:2018-08-18 Published:2018-07-04
Contact: 10.1016/S1872-2067(18)63032-3
Supported by:
This work was supported by the National Natural Science Foundation of China (21576272, 21406245), the project from Jiangsu Collaborative Innovation Center for Ecological Building Materials and Environmental Protection Equipments (YCXT201607), and the "Transformational Technologies for Clean Energy and Demonstration", Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21030600).

摘要/Abstract

摘要：

CO₂作为重要的碳氧资源，具有来源丰富、价格低廉、安全等突出优点.近年来，由于蕴含的巨大利用潜力，CO₂间接利用制备基础化学品、能源燃料对于可持续制备大宗化工品中具有重要研究意义，日益受到研究者和工业界的广泛重视.甲醇与乙二醇是化学工业中的两种重要大宗原料.甲醇不仅是重要的有机化工原料、清洁环保的液体燃料，同时也是氢气和能量储存的良好载体.乙二醇作为一种重要的有机化工原料，在聚酯等领域具有广泛应用.CO₂经碳酸乙烯酯氢解制备甲醇/乙二醇是典型的原子经济反应，对资源、能源和环境的可持续发展具有重要意义.需要指出的是，CO₂与环氧乙烷环加成制备碳酸乙烯酯已具备成熟的工业化技术.因此，该路线研究重点在于发展碳酸乙烯酯选择加氢联产甲醇和乙二醇高效稳定的催化体系.近年来，铜基多相催化剂催化碳酸乙烯酯加氢联产甲醇乙二醇得到了广泛重视.由于铜基催化剂存在活性较低、高温易失活等问题，开发高效且具有良好稳定性的铜基催化剂是目前碳酸乙烯酯加氢研究重点.
本文针对碳酸乙烯酯选择氢解合成甲醇乙二醇新型铜基催化体系构建和构效关系研究，采用硅溶胶蒸氨法制备高分散Cu/SiO₂过程中引入多羟基β-环糊精修饰催化剂前驱体的合成策略，并通过惰性气体中煅烧后的积碳有效抑制活性铜物种的团聚，获得了β-环糊精改性的Cu/SiO₂催化剂.通过N₂吸脱附、XRD、N₂O滴定、H₂-TPR、TEM和XPS等系统表征，发现β-环糊精可有效调控催化剂结构和表面不同价态活性铜物种分布.碳酸乙烯酯加氢性能评价结果表明引入适量β-环糊精的5β-25%Cu/SiO₂具有较优催化活性，乙二醇选择性98.8%和甲醇选择性71.6%，且相应的催化活性可达1178mg_EC g_cat^-1 h^-1.高活性的原因很可能归因于不同价态Cu⁰与Cu⁺物种协同催化作用及适宜的Cu⁺/（Cu⁰+Cu⁺）比例.结合密度泛函理论模拟计算，我们提出了Cu⁰促进氢气解离、Cu⁺吸附活化碳酸乙烯酯分子中酯羰基的反应机理.催化剂重复使用和表征结果表明，5β-25%Cu/SiO₂具有良好的稳定性，使用前后铜粒子大小和铜物种分布几乎未发生明显变化.本文为解决铜基催化剂高温易烧结等难题提供了简单有效的活性铜物种稳定化方法，并为CO₂经碳酸乙烯酯绿色合成甲醇、乙二醇高效稳定铜基催化新体系的构筑提供了有益借鉴.

关键词: 碳酸乙烯酯, 加氢, β-环糊精, Cu/SiO₂, 甲醇, 乙二醇

Abstract:

The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate (EC) is important for the sustainable utilization of CO₂ to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO₂ catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N₂ physisorption, XRD, N₂O titration, H₂-TPR, TEM, and XPS/XAES. Compared with the unmodified 25Cu/SiO₂catalyst, the involvement of β-cyclodextrin in 5β-25Cu/SiO₂ could remarkably increase the catalytic activity-excellent activity of 1178 mg_EC g_cat^-1 h^-1 with 98.8% ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu⁺/(Cu⁰+Cu⁺). Furthermore, the DFT calculation results demonstrated that metallic Cu⁰ dissociated adsorbed H₂, while Cu⁺ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts-this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO₂.

Key words: Ethylene carbonate, Hydrogenation, β-Cyclodextrin, Cu/SiO₂, Methanol, Ethylene glycol

刘佳驹, 贺鹏, 王利国, 刘辉, 曹妍, 李会泉. 碳酸乙烯酯选择加氢合成甲醇与乙二醇高效稳定Cu/SiO₂催化剂研究[J]. 催化学报, 2018, 39(8): 1283-1293.

Jiaju Liu, Peng He, Liguo Wang, Hui Liu, Yan Cao, Huiquan Li. An efficient and stable Cu/SiO₂ catalyst for the syntheses of ethylene glycol and methanol via chemoselective hydrogenation of ethylene carbonate[J]. Chinese Journal of Catalysis, 2018, 39(8): 1283-1293.

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碳酸乙烯酯选择加氢合成甲醇与乙二醇高效稳定Cu/SiO₂催化剂研究

An efficient and stable Cu/SiO₂ catalyst for the syntheses of ethylene glycol and methanol via chemoselective hydrogenation of ethylene carbonate

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