化工学报 ›› 2019, Vol. 70 ›› Issue (4): 1420-1428.DOI: 10.11949/j.issn.0438-1157.20181006

• 催化、动力学与反应器 • 上一篇    下一篇

Sr改性Cu催化剂的果糖加氢制备甘露醇性能

胡凤腾(),姚建龙,李小青,李思汉,严新焕()   

  1. 浙江工业大学绿色化学合成技术国家重点实验室培育基地,浙江 杭州 310014
  • 收稿日期:2018-09-10 修回日期:2019-01-23 出版日期:2019-04-05 发布日期:2019-04-05
  • 通讯作者: 严新焕
  • 作者简介:<named-content content-type="corresp-name">胡凤腾</named-content>(1992—),男,硕士研究生,<email>1259896575@qq.com</email>|严新焕 (1964—),男,博士,教授,<email>xhyan@zjut.edu.cn</email>

Properties of Sr modified Cu-based catalysts for hydrogenation of fructose to mannitol

Fengteng HU(),Jianlong YAO,Xiaoqing LI,Sihan LI,Xinhuan YAN()   

  1. State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
  • Received:2018-09-10 Revised:2019-01-23 Online:2019-04-05 Published:2019-04-05
  • Contact: Xinhuan YAN

摘要:

使用共沉淀法制备负载Cu催化剂。通过添加碱土金属Sr,对Cu催化剂进行了改性,以提高Cu催化剂在果糖加氢制备甘露醇过程中的活性和选择性。采用ICP-MS、TEM、XRD、H2-TPR、XPS和CO2-TPD等对所制备的催化剂进行了系统表征。结果表明:Sr的添加能增大催化剂的比表面积,促进活性组分Cu的分散,从而提高了催化剂的活性,并且增加了催化剂的碱性,使果糖优先形成β-呋喃糖中间体,从而提高了甘露醇的选择性。在果糖浓度为1.1 mol·L-1、催化剂用量为反应物质量的6%、反应温度为373 K、反应氢压为4.0 MPa、Cu/Sr原子比为7∶1的反应条件下,果糖转化率为99%,甘露醇的选择性为79%。催化剂循环使用了20次,其催化稳定性基本保持不变。

关键词: Sr, 催化剂, 果糖, 加氢, 甘露醇, 活性, 选择性

Abstract:

A supported Cu catalyst was prepared by using a co-precipitation method. The Cu catalyst was modified by adding alkaline earth metal strontium to improve the activity and selectivity for the hydrogenation of fructose to prepare mannitol. Systematic characterizations, with ICP-MS, XRD, TEM, H2-TPR, XPS and CO2-TPD, showed that the increase catalytic activity of the catalyst is due to the fact that the formation of SrCO3 formed on the surface of the support can increase the specific surface area of the catalyst and improve the dispersion of the copper species. In addition, the medium-strong basic sites formed on the surface of SrCO3 can activate the carbonyl group into β-furanose which can be easily hydrogenated into mannitol. Fructose conversion of around 100% and mannitol selectivity of 79% were achieved in the conditions of 1.1 mol·L-1 fructose concentration, catalyst dosage of 6% of reactant quality, reaction temperature of 373 K, hydrogen pressure of 4.0 MPa and Cu/Sr atomic ratio of 7∶1. The excellent stability of the Cu-Sr/SiO2 catalyst remained basically unchanged after recycling for 20 times.

Key words: Sr, catalyst, fructose, hydrogenation, mannitol, activity, selectivity

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