氮修饰Ni2P-Nx/SiO2催化剂设计合成及间甲酚加氢脱氧性能研究
Preparation of N Modified Ni2P-Nx/SiO2 Catalysts and Hydrodeoxygenation Performance of m-Cresol
Received date: 2024-07-15
Online published: 2024-09-06
Supported by
National Natural Science Foundation of China(22278068)
采用浸渍法制备了一系列N修饰的Ni2P-Nx/SiO2催化剂, 通过X射线衍射(XRD)、N2物理吸脱附(BET)、H2-程序升温还原(H2-TPR)、NH3-程序升温脱附(NH3-TPD)、吡啶红外(Py-FTIR)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等表征手段对催化剂的结构进行分析, 系统地研究了Ni/N物质的量比对催化剂理化性质的影响. 以间甲酚为模型化合物, 研究了Ni/N物质的量比、反应温度、反应时间及反应压力对催化剂加氢脱氧(HDO)性能的影响. 结果表明, 适量N修饰可以促进更小活性颗粒的形成, 提高活性组分的分散性, 进而提高催化剂的催化活性. Ni/N比为1时制备的Ni2P-N1.0/SiO2催化剂具有最优异的HDO活性, 在250 ℃、3 MPa、1 h条件下, 间甲酚转化率为93.2%, 目标产物甲基环己烷(MCH)的选择性达到94.2%. Ni2P-Nx/SiO2催化剂上间甲酚HDO主要以加氢-脱氧(HYD)路径为主.
关键词： N修饰; Ni2P-Nx/SiO2催化剂; 间甲酚; 加氢脱氧; 甲基环己烷
王帅 , 宋华 . 氮修饰Ni2P-Nx/SiO2催化剂设计合成及间甲酚加氢脱氧性能研究[J]. 化学学报, 2024 , 82(9) : 979 -986 . DOI: 10.6023/A24070217
The gradual depletion of fossil fuels and increasing environmental pollution problems inspire researchers to seek renewable and clean energy. Lignocellulosic biomass is deemed to be a sustainable and promising resource to produce chemicals and fuels due to its abundant existence in nature. Hydrodeoxygenation (HDO) of phenolic compounds in bio-fuel is a promising technology to convert biomass materials to value-added chemicals and fuels. However, the development of highly efficient catalysts remains a great challenge. In this work, a series of N modified Ni2P-Nx/SiO2 catalysts were prepared by impregnation method. The structure of the catalysts was characterized by X-ray diffraction (XRD), N2 physical adsorption desorption (BET), H2 temperature programmed reduction (H2-TPR), NH3 temperature programmed desorption (NH3-TPD), pyridine infrared (Py-FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and the influence of Ni/N molar ratio on the physicochemical properties of the catalysts was systematically investigated. Using m-cresol as a model compound, the effects of Ni/N molar ratio, reaction temperature, reaction time, and reaction pressure on the HDO performance were studied. It was found that the appropriate introduction of N element can promote the formation of smaller active particles, improve the dispersion of active components, thus enhancing the catalytic activity. The Ni2P-N1.0/SiO2 catalyst with a Ni/N ratio of 1.0 exhibited the best HDO activity. Under the conditions of 250 ℃, 3 MPa, and 1 h, m-cresol conversion reached 93.2%, and the selectivity of the target product methylcyclohexane (MCH) reached 94.2%. Based on the product distribution, it can be inferred HDO of m-cresol over Ni2P-Nx/SiO2 catalyst proceeded mainly via hydrogenation-deoxygenation (HYD) pathway. Furthermore, this series of catalysts also displayed excellent recyclability, m-cresol conversion, as well as the selectivity towards MCH did not decrease obviously even after 5 successive cycles. We believe that this strategy can provide a simple and repeatable route to synthesize high-performance HDO catalysts.
Key words： N modified; Ni2P-Nx/SiO2 catalyst; m-cresol; hydrodeoxygenation; methylcyclohexane
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