Co掺杂诱导CoxP-Ni2P双金属位点与酸协同作用实现高效加氢脱氧

Co doping induces CoxP-Ni2P bimetallic site and acid synergistic effect to achieve efficient hydrodeoxidation

  • 摘要: 高效加氢脱氧催化剂的开发是生物油提质升级的关键。以介孔SiO2为载体,在Ni2P活性相基础上,通过Co掺杂制备了CoxP-Ni2P双金属位点与酸性位点并存的CoxP-Ni2P/SiO2-y催化剂(y为初始P/(Ni+Co)物质的量比),采用XRD、BET、XPS、H2-TPR、NH3-TPD、Py-FTIR和TEM技术表征了催化剂的结构和化学性质,并以间甲酚为模型化合物,考察了Co掺杂以及P/M物质的量比对Ni2P/SiO2催化剂加氢脱氧性能的影响。结果表明,Co的掺杂不仅新增了活性位点CoxP,还优化了Ni2P的电子结构,进而提高了催化剂的加氢脱氧(HDO)活性。在CoxP-Ni2P/SiO2-y催化剂中,P/M物质的量比为0.5的CoxP-Ni2P/SiO2-0.5催化性能最好,在275 ℃,2 MPa,1 h的反应条件下,间甲酚转化率达到98.7%,对脱氧产物甲基环己烷(MCH)的选择性达到95.6%,且CoxP-Ni2P/SiO2-y催化剂上的HDO反应过程以先加氢后脱氧(HYD)路径为主。

     

    Abstract: The development of highly efficient hydrodeoxidation (HDO) catalyst is the key to upgrad the quality of bio-oil. CoxP-Ni2P/SiO2-y catalysts (y is the initial P/(Ni+Co) molar ratio) comprised of CoxP-Ni2P bimetallic sites and acidic site were prepared by doping Co into Ni2P active phase using mesoporous SiO2 as the support. The structure and chemical properties of the catalyst were characterized by XRD, BET, XPS, H2-TPR, NH3-TPD, Py-FTIR and TEM methods. The effects of Co doping and P/M molar ratio on the hydrodeoxidation performance of Ni2P/SiO2 catalyst were investigated taking m-cresol as the model compound. The results show that Co doping not only creates new CoxP active sites, but also optimizes the electronic structure of Ni2P, thus improving the HDO activity of the catalyst. Among the CoxP-Ni2P/SiO2-y catalysts, CoxP-Ni2P/SiO2-0.5 with P/M molar ratio of 0.5 exhibits the best catalytic performance, with the m-cresol conversion of 98.7% and selectivity to the deoxidized product methylcyclohexane (MCH) of 95.6% at 275 ℃ , 2 MPa and 1 h. The HDO of m-cresol over the CoxP-Ni2P/SiO2-y catalyst mainly proceeded through HYD pathway.

     

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