Co掺杂诱导Co_(x)P-Ni_(2)P双金属位点与酸协同作用实现高效加氢脱氧  

Co doping induces Co_(x)P-Ni_(2)P bimetallic site and acid synergistic effect to achieve efficient hydrodeoxidation

作　　者：司明浩 王帅 苟晓梅 宋华[1] SI Minghao;WANG Shuai;GOU Xiaomei;SONG Hua(College of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing 163318,China)

机构地区：[1]东北石油大学化学化工学院,黑龙江大庆163318

出　　处：《燃料化学学报（中英文）》2024年第9期1327-1335,共9页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(22278068)资助。

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SiO_(2)为载体,在Ni_(2)P活性相基础上,通过Co掺杂制备了Co_(x)P-Ni_(2)P双金属位点与酸性位点并存的Co_(x)P-Ni_(2)P/SiO_(2)-y催化剂(y为初始P/(Ni+Co)物质的量比),采用XRD、BET、XPS、H_(2)-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/SiO_(2)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Co_(x)P,还优化了Ni_(2)P的电子结构,进而提高了催化剂的加氢脱氧(HDO)活性。在Co_(x)P-Ni_(2)P/SiO_(2)-y催化剂中,P/M物质的量比为0.5的Co_(x)P-Ni_(2)P/SiO_(2)-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Co_(x)P-Ni_(2)P/SiO_(2)-y催化剂上的HDO反应过程以先加氢后脱氧(HYD)路径为主。The development of highly efficient hydrodeoxidation(HDO)catalyst is the key to upgrad the quality of bio-oil.Co_(x)P-Ni_(2)P/SiO_(2)-y catalysts(y is the initial P/(Ni+Co)molar ratio)comprised of Co_(x)P-Ni_(2)P bimetallic sites and acidic site were prepared by doping Co into Ni_(2)P active phase using mesoporous SiO_(2) as the support.The structure and chemical properties of the catalyst were characterized by XRD,BET,XPS,H_(2)-TPR,NH_(3)-TPD,Py-FTIR and TEM methods.The effects of Co doping and P/M molar ratio on the hydrodeoxidation performance of Ni_(2)P/SiO_(2) catalyst were investigated taking m-cresol as the model compound.The results show that Co doping not only creates new Co_(x)P active sites,but also optimizes the electronic structure of Ni_(2)P,thus improving the HDO activity of the catalyst.Among the Co_(x)P-Ni_(2)P/SiO_(2)-y catalysts,Co_(x)P-Ni_(2)P/SiO_(2)-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 Co_(x)PNi_(2)P/SiO_(2)-y catalyst mainly proceeded through HYD pathway.

关 键 词：生物油 加氢脱氧 磷化镍 CO掺杂 间甲酚 

分 类 号：O643.361[理学—物理化学]