Zr改性Ni2P/SBA-15催化剂的制备及其加氢脱氧性能

Preparation of Zr modified Ni2P/SBA-15 catalysts and its hydrodeoxygenation performance

  • 摘要: 以正丙醇锆(n)和Zr(SO42(m)为锆源制备了Zr改性的Ni2P/ZrO2-SBA-15(n)和Ni2P/ZrO2-SBA-15(m)催化剂,并采用XRD、BET、CO吸附、XPS、NH3程序升温脱附等手段对催化剂进行了表征。以苯并呋喃(BF)为模型化合物,研究了催化剂加氢脱氧(HDO)性能。结果表明,Zr改性后,形成了新的层状结构的ZrP;Zr的引入有助于生成更多、更小粒径的Ni2P活性相,催化剂的酸强度和酸量均提高。与正丙醇锆相比,Zr(SO42为锆源能够获得比表面积大、酸性强、酸量大的催化剂,得到更多的ZrP相、更小粒径的Ni2P晶粒,暴露更多的Ni活性位点。Ni2P/ZrO2-SBA-15(n)和Ni2P/ZrO2-SBA-15(m)的BF HDO产率分别为71.5%和85.9%,较Ni2P/SBA-15分别提高了14.0%和28.4%。催化剂HDO活性、脱氧产物选择性和产率大小顺序为:Ni2P/ZrO2-SBA-15(m)> Ni2P/ZrO2-SBA-15(n)> Ni2P/SBA-15。

     

    Abstract: Ni2P/ZrO2-SBA-15(n) and Ni2P/ZrO2-SBA-15(m) catalysts were prepared from n-propoxide zirconium (n) and Zr(SO4)2(m) as zirconium sources. The catalysts were characterized by X-ray diffraction (XRD), N2 adsorption specific surface area measurements (BET), CO uptake, X-ray photoelectron spectroscopy (XPS) and NH3 temperature programmed desorption (NH3-TPD). The results show that after Zr modification, a new layered structure of ZrP is formed. The introduction of Zr helps to generate more Ni2P active phase with smaller crystal size, and increase both the acid strength and acid amount of the catalyst. Compared with zirconium n-propoxide, the catalyst prepared from Zr(SO4)2 has larger specific surface area, more acid amount, stronger acidity, more ZrP phases, smaller Ni2P crystal grains and more Ni active sites. The product yields of benzofuran hydrodeoxygenation (BF HDO) given by Ni2P/ZrO2-SBA-15(n) and Ni2P/ZrO2-SBA-15(m) were 71.5% and 85.9% respectively, which were increased by 14.0% and 28.4% respectively compared with Ni2P/SBA-15. The BF HDO activity, selectivity and yield of the BF HDO products decreased in the order of Ni2P/ZrO2-SBA-15(m) > Ni2P/ZrO2-SBA-15(n) > Ni2P/SBA-15.

     

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