Efficient Synthesis of Furfuryl Alcohol and 2‐Methylfuran from Furfural over Mineral‐Derived Cu/ZnO Catalysts
Efficient Synthesis of Furfuryl Alcohol and 2‐Methylfuran from Furfural over Mineral‐Derived Cu/ZnO Catalysts
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DOI：
10.1002/cctc.201700279
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发表时间：
2017-08
期刊：
影响因子：
4.5
通讯作者：
Xiaohai Yang;Xiaomin Xiang;Hongmei Chen;Hongyan Zheng;Yong-wang Li;Yulei Zhu
中科院分区：
文献类型：
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作者：
Xiaohai Yang;Xiaomin Xiang;Hongmei Chen;Hongyan Zheng;Yong-wang Li;Yulei Zhu
在固定床反应器中，考察了两种典型矿物铜/氧化锌（Cu/ZnO）催化剂对糠醛加氢制糠醇（FOL）和2-甲基呋喃（2-MF）的催化性能。在适当的反应条件下，以铜绿铜矿Cu/ZnO为催化剂（AC-CZ）可以获得较高的FOL（99%以上）和2-MF（94.5%）收率，而以锌孔雀石Cu/ZnO为催化剂（ZM-CZ）的2-MF收率最高仅为76.9%（0.5 h-1）。对于AC-CZ和ZM-CZ，2-MF的归一化生产率分别为43.5 mol kgCu−1 h−1和17.4 mol kgCu−1 h−1（LHSV=1.5 h−1）。通过XRD分析、拉曼光谱、CO IR光谱、H2程序升温还原、N2 O滴定、NH3程序升温脱附和X射线光电子能谱对催化剂进行表征。AC-CZ在糠醛加氢中的更好的性能归因于其更高的铜物种分散度、上级铜表面积、更好的表面酸性分布和更强的Cu 0-ZnO协同作用。此外，催化剂的表面酸性似乎比Cu表面积对2-MF生产的影响更大，但这两个因素的最佳平衡仍然需要系统地研究。
Two kinds of typical mineral‐derived Cu/ZnO catalysts consisting of aurichalcite and zincian malachite were introduced for furfural hydrogenation to furfuryl alcohol (FOL) and 2‐methylfuran (2‐MF) in a fixed‐bed reactor. Under proper reaction conditions, high yields of FOL (above 99 %) and 2‐MF (94.5 %) could be obtained over the aurichalcite Cu/ZnO catalyst (AC‐CZ), whereas the best yield of 2‐MF was only 76.9 % (0.5 h−1) over the zincian malachite Cu/ZnO catalyst (ZM‐CZ). The normalized productivity of 2‐MF was 43.5 mol kgCu−1 h−1 and 17.4 mol kgCu−1 h−1 for AC‐CZ and ZM‐CZ, respectively (LHSV=1.5 h−1). The catalysts were characterized by XRD analysis, Raman spectra, CO IR spectroscopy, H2 temperature‐programmed reduction, N2O titration, NH3 temperature‐programmed desorption, and X‐ray photoelectron spectroscopy. The far better performance of AC‐CZ in furfural hydrogenation was ascribed to its higher dispersion of copper species, superior copper surface area, better surface acidity distribution, and stronger Cu0–ZnO synergy. In addition, the surface acidity of the catalysts seemed to have a higher influence on 2‐MF production than the Cu surface area, but the optimal balance of both factors still needs to be investigated systematically.