还原温度对Ni<sub>2</sub>P/SiO<sub>2</sub>催化月桂酸甲酯脱氧性能的影响

摘要

分别以NH₄H₂PO₄和H₃PO₂作为磷源,采用等体积浸渍-程序升温还原法制备了Ni₂P/SiO₂催化剂,采用H₂-TPR、XRD、CO化学吸附、NH₃-TPD和H₂-TPD等表征手段并结合月桂酸甲酯加氢脱氧反应评价,研究了还原温度对H₃PO₂作为磷源制备Ni₂P/SiO₂催化剂的结构及催化月桂酸甲酯脱氧性能的影响,并与以NH₄H₂PO₄作为磷源制备的催化剂进行了比较。研究表明,随还原温度提高,以H₃PO₂为磷源制备的Ni₂P/SiO₂催化剂中Ni₂P晶粒尺寸及CO吸附量增加,但催化剂表面磷含量及酸量减少;其催化月桂酸甲酯脱氧反应的性能呈提高趋势,这与其表面Ni位增多及表面P含量逐渐减少密切有关。与以NH₄H₂PO₄为磷源所制备的Ni₂P/SiO₂催化剂相比,以H₃PO₂为磷源所制备的Ni₂P/SiO₂更有利于催化月桂酸甲酯的加氢脱氧路径,可能与其表面具有较强的酸性有关。

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	唐明晓
	陈吉祥

关键词：磷化镍催化剂；次磷酸；加氢脱氧；脱羰

Abstract：

A series of Ni₂P/SiO₂ catalysts were prepared by the temperature-programmed reduction method from the precursors derived from different P sources (ammonium dihydrogen phosphate(ADP) and hypophosphorous acid(HA)). The effect of reduction temperature on the structure and performance of the catalysts prepared with HA as phosphrous source for the deoxygenation of methyl laurate was studied by means of H₂-TPR, XRD, CO chemisorption, NH₃-TPD, H₂-TPD and activity test. For the precursor with HA as phosphrous source, as the reduction temperature increased, the crystallite size of Ni₂P and CO uptake of the prepared catalyst increased, while the content of phosphrous and acid amount on the catalyst surface decreased. Moreover, the activities of the prepared catalysts for the deoxygenation of methyl laurate tended to increase. This is closely related to the increase of the amount of Ni sites and the decrease of the phosphrous content. Compared with that with ADPas phosphrous source, the Ni₂P/SiO₂ catalyst with HAas phosphrous source preferably catalyzed the hydrodeoxygenation pathway, which may result from its stronger acidity.

Keywords： nickel phosphide catalyst； hypophosphorous acid； hydrodeoxygenation； decarbonylation

Received 2014-04-09;

Fund:

国家自然科学基金(21176177);天津市自然科学基金(12JCYBJC13200)。

Corresponding Authors: 陈吉祥,E-mail:jxchen@tju.edu.cn。 Email: jxchen@tju.edu.cn

About author: 唐明晓(1989-),女,硕士研究生,主要从事加氢催化剂的研究。

引用本文:

唐明晓, 陈吉祥.还原温度对Ni₂P/SiO₂催化月桂酸甲酯脱氧性能的影响[J]. 化学工业与工程, 2016,33(3): 1-7

Tang Mingxiao, Chen Jixiang.Effect of Reduction Temperature on Performance of Ni₂P/SiO₂ for Deoxygenation of Methyl Laurate[J]. Chemcial Industry and Engineering, 2016,33(3): 1-7

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