Cu-Zr复合氧化物催化耦合甘油和CO_(2)合成碳酸甘油酯  

Synthesis of glycerol carbonate from glycerol and CO_(2) over Cu-Zr complex oxide

作　　者：徐换换 柯义虎 XU Huanhuan;KE Yihu(Key Laboratory of Chemical Engineering and Technology,State Ethnic Affairs Commission,North Minzu University,Yinchuan,750021,China;Ningxia Key Laboratory of Solar Chemical Conversion Technology,North Minzu University,Yinchuan 750021,China)

机构地区：[1]北方民族大学国家民委化工技术基础重点实验室,宁夏银川750021 [2]北方民族大学宁夏太阳能化学转化技术重点实验室,宁夏银川750021

出　　处：《燃料化学学报（中英文）》2024年第2期171-183,共13页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(21862001);宁夏餐厨废油资源化利用技术研发创新团队(2022QCXTD03);宁夏低品质资源高值化利用技术研发人才小高地资助。

摘　　要：采用水热法合成了一系列不同Cu-Zr物质的量比的Cu1-xZrxO_(2)双金属氧化物,以此为催化剂,将生物柴油生产过程副产物甘油与温室气体CO_(2)耦合反应制备精细化工产品碳酸甘油酯。结果表明,Zr掺杂量不同,催化剂对甘油羰基化反应效果呈现明显差距,最佳反应条件下,Cu0.99Zr0.01O_(2)催化剂具有最佳催化性能,甘油转化率和碳酸甘油酯选择性分别达到64.1%和85.9%。并且发现与纯CuO和纯ZrO_(2)相比,Cu1-xZrxO_(2)复合氧化物在甘油与CO_(2)耦合反应体系中表现出更强的催化活性,结合X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、N2吸附-脱附、程序升温还原(H2-TPR)、程序升温脱附(TPD)、傅里叶变换红外光谱(FT-IR)等表征手段,推测高活性与Zr在CuO表面的分散程度、催化剂表面氧物种含量及酸碱性位点数量有关。此外,为了研究催化剂的稳定性,以Cu0.99Zr0.01O_(2)催化剂作为基准进行了循环性能测试,结果表明,经过六次循环后,甘油的转化率和碳酸甘油酯的选择性未发生明显变化,说明该催化剂稳定性良好。A series of Cu1−xZrxO_(2) bimetallic oxides with different Cu-Zr molar ratios for glycerol carbonate synthesis from glycerol and CO_(2) were prepared by hydrothermal method.The results found that the performance was significantly affected by the Zr doping amounts.Under the optimal reaction conditions,the Cu0.99Zr0.01O_(2) catalyst had the best catalytic performance.The conversion of glycerol and the selectivity of glycerol carbonate reached 64.1%and 85.9%,respectively.Cu1−xZrxO_(2) complex oxide exhibited better activity than pure CuO and pure ZrO_(2).The structures,morphologies and surface properties of the catalysts were characterized by X-ray powder diffraction(XRD),Scanning electron microscopy(SEM),Transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),N2 adsorption and desorption,Temperature programmed reduction(H2-TPR),Temperature programmed desorption(TPD)and Fourier Transform Infrared Spectroscopy(FT-IR).It is speculated that the high activity is related to the degree of dispersion of Zr on the surface of CuO,the surface content of oxygen species and the number of acidic-basic sites.In addition,catalytic activity did not change significantly after six cycles,indicating the excellent stability of the catalyst.

关 键 词：甘油 碳酸甘油酯 二氧化碳 复合氧化物 2-氰基吡啶 

分 类 号：O643.36[理学—物理化学]