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用于在温和条件下将生物质相关化合物直接加氢脱氧转化为液态烷烃的钯/五氧化二铌/二氧化硅催化剂。

Pd/Nb2O5/SiO2 catalyst for the direct hydrodeoxygenation of biomass-related compounds to liquid alkanes under mild conditions.

作者信息

Shao Yi, Xia Qineng, Liu Xiaohui, Lu Guanzhong, Wang Yanqin

机构信息

Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, East China University of Science and Technology, No. 130 Meilong Road, Shanghai (PR China), Fax: (+86) 21-64253824.

出版信息

ChemSusChem. 2015 May 22;8(10):1761-7. doi: 10.1002/cssc.201500053. Epub 2015 Apr 15.

DOI:10.1002/cssc.201500053
PMID:25876904
Abstract

A simple Pd-loaded Nb2 O5 /SiO2 catalyst was prepared for the hydrodeoxygenation of biomass-related compounds to alkanes under mild conditions. Niobium oxide dispersed in silica (Nb2 O5 /SiO2 ) as the support was prepared by the sol-gel method and characterized by various techniques, including N2 adsorption, XRD, NH3 temperature-programmed desorption (TPD), TEM, and energy-dispersive X-ray spectroscopy (EDAX) atomic mapping. The characterization results showed that the niobium oxide species were amorphous and well dispersed in silica. Compared to commercial Nb2 O5 , Nb2 O5 /SiO2 has significantly more active niobium oxide species exposed on the surface. Under mild conditions (170 °C, 2.5 MPa), Pd/10 %Nb2 O5 /SiO2 was effective for the hydrodeoxygenation reactions of 4-(2-furyl)-3-buten-2-one (aldol adduct of furfural with acetone), palmitic acid, tristearin, and diphenyl ether (model compounds of microalgae oils, vegetable oils, and lignin), which gave high yields (>94 %) of alkanes with little CC bond cleavage. More importantly, owing to the significant promotion effect of NbOx species on CO bond cleavage and the mild reaction conditions, the CC cleavage was considerably restrained, and the catalyst showed an excellent activity and stability for the hydrodeoxygenation of palmitic acid with almost no decrease in hexadecane yield (94-95 %) in a 150 h time-on-stream test.

摘要

制备了一种简单的负载钯的Nb₂O₅/SiO₂催化剂,用于在温和条件下将生物质相关化合物加氢脱氧转化为烷烃。通过溶胶-凝胶法制备了分散在二氧化硅中的氧化铌(Nb₂O₅/SiO₂)作为载体,并采用多种技术对其进行了表征,包括N₂吸附、XRD、NH₃程序升温脱附(TPD)、TEM和能量色散X射线光谱(EDAX)原子映射。表征结果表明,氧化铌物种为无定形且在二氧化硅中分散良好。与市售Nb₂O₅相比,Nb₂O₅/SiO₂表面暴露的活性氧化铌物种明显更多。在温和条件(170 °C,2.5 MPa)下,Pd/10 %Nb₂O₅/SiO₂对4-(2-呋喃基)-3-丁烯-2-酮(糠醛与丙酮的缩合产物)、棕榈酸、三硬脂酸甘油酯和二苯醚(微藻油、植物油和木质素的模型化合物)的加氢脱氧反应有效,能以高收率(>94 %)生成烷烃,且几乎没有CC键断裂。更重要的是,由于NbOx物种对CO键断裂具有显著的促进作用以及温和的反应条件,CC键断裂受到了相当程度的抑制,该催化剂在棕榈酸加氢脱氧反应中表现出优异的活性和稳定性,在150 h的连续流动测试中十六烷收率几乎没有下降(94 - 95 %)。

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