Xiang Mei, Wu Dongfang
Department of Chemical Engineering, School of Chemistry and Chemical Engineering, Southeast University Jiangning District Nanjing 211189 China
RSC Adv. 2018 Oct 1;8(58):33473-33486. doi: 10.1039/c8ra06811a. eCollection 2018 Sep 24.
A transesterification reaction has been carried out over a transition metal modified hierarchical ETS-10 (METS-10) catalyst to synthesize glycerol carbonate (GC) from glycerol. The inherent Lewis basicity of ETS-10 favors oriented conversion of glycerol, and the hierarchical structure benefits exposure of more active sites, shortens the molecular diffusion path, suppresses the formation of coke in the micropores, and then enhances the catalytic reactivity and stability. Furthermore, the influence of transition metals (Fe, Co, Ni, Cu, Zn and Mn) on the basic sites of supports has been investigated in detail. It is found that basicity change of the catalyst depends on not only the cation size, nature and composition of the transition metal but also the zeolite structure and pore topology. Besides, the presence of a certain amount of Ni species from catalyst reduction has proved to play a critical role in strengthening the interaction of Lewis basic sites (TiO ) with active glycerol hydroxyl groups. Finally, a 97.7% glycerol conversion and 97.1% GC yield have been obtained over Ni/METS-10, of which the high catalytic performance can be maintained after 8 runs.
在过渡金属改性的分级ETS-10(METS-10)催化剂上进行了酯交换反应,以由甘油合成碳酸甘油酯(GC)。ETS-10固有的Lewis碱性有利于甘油的定向转化,分级结构有利于更多活性位点的暴露,缩短了分子扩散路径,抑制了微孔中焦炭的形成,进而提高了催化反应活性和稳定性。此外,还详细研究了过渡金属(Fe、Co、Ni、Cu、Zn和Mn)对载体碱性位点的影响。发现催化剂的碱性变化不仅取决于过渡金属的阳离子尺寸、性质和组成,还取决于沸石结构和孔拓扑结构。此外,催化剂还原产生的一定量Ni物种的存在已证明在增强Lewis碱性位点(TiO)与活性甘油羟基的相互作用中起关键作用。最后,在Ni/METS-10上获得了97.7%的甘油转化率和97.1%的GC产率,其中高催化性能在8次运行后仍可保持。