磷化镍催化异丁烷临氢脱氢制异丁烯

摘要

以SiO₂为载体,结合浸渍法和程序升温还原法制备磷化镍催化剂,考察了不同n(Ni)/n(P)和不同Ni负载量等对催化剂的结构及异丁烷脱氢性能的影响。运用透射电镜(TEM),X射线衍射(XRD),程序升温还原(H₂-TPR),氢气程序升温脱附(H₂-TPD)等表征手段考察催化剂的组成与结构、还原性能及氢吸附性能。研究结果表明:Ni/P比对催化剂表面的物相有较大影响,n(Ni)/n(P)为1.0和0.5时,形成Ni₂P相;n(Ni)/n(P)为1.5时,形成Ni₁₂P₅。随着Ni负载量的增加,活性组分Ni₂P粒子尺寸变大,但分散度降低。磷化镍能够催化异丁烷脱氢制异丁烯,但Ni₂P的催化活性要比Ni₁₂P₅高,经实验研究发现,当Ni/P比为1.0、负载量为10%、n(H₂)/n(i-C₄H₁₀)=1.0、空速为800 h^-1时,在460 ℃反应时,对异丁烯的选择性可达到80%。

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	许燕丽
	王希涛

关键词：磷化镍异丁烷异丁烯脱氢

Abstract：

Nickle phosphide catalysts were prepared by combining the method of incipient wetness impregnation and temperature-programmed reduction, using silica as the support. The effects of different Ni/P molar ratios and different loadings on catalysts structure and isobutane dehydrogenation performance were investigated. The structure and constitute, reducing property and hydrogen adsorption performance were characterized by TEM, XRD, H₂-TPR and H₂-TPD. The results prove that Ni/P molar ratios make great effect on the surface material, that catalysts contained phase-pure Ni₂P on the silica when Ni/P molar ratios were 1.0 and 0.5, and when Ni/P molar ratio was 1.5 to yield Ni₁₂P₅. Ni₂P particles with low loading were well distributed, but the particles become larger and uniformly with the increase of loading. Nickel phosphide catalysts have dehydrogenation activities and Ni₂P have a better performance than Ni₁₂P₅, the catalyst have the best performance for isobutene selectivity higher than 80% when n(Ni)/n(P)=1.0, loading 10%, n(H₂)/n(i-C₄H₁₀)=1.0, 800 h^-1, 460 ℃.

Keywords： nickel phoside； isobutane； isobutene； dehydrogenation

Received 2014-03-03;

Corresponding Authors: 王希涛,E-mail:wangxt@tju.edu.cn。 Email: wangxt@tju.edu.cn

About author: 许燕丽(1987-),女,主要研究方向为异丁烷临氢脱氢制异丁烯。

引用本文:

许燕丽, 王希涛.磷化镍催化异丁烷临氢脱氢制异丁烯[J]. 化学工业与工程, 2016,33(2): 17-22

Xu Yanli, Wang Xitao.Dehydrogenation of Isobutane to Isobutene over Nickel Phosphide Catalyst in the Presence of Hydrogen[J]. Chemcial Industry and Engineering, 2016,33(2): 17-22

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