Study On The Construction And Performance Of A Catalyst For The Catalytic Conversion Of Cyclopentanone To High-density Fuel

Recently,the conversion of abundant and renewable biomass into fuels and useful chemicals is a promising way to reduce dependence on petroleum and alleviate environmental issues.The biomass derivatives could be further converted into liquid fuels by combining the aldol condensation reaction and hydrodeoxygenation reaction,and the research of synthesizing high density fuel from biomass platform compounds is getting more and more attention.Biomass liquid fuel was prepared from cyclopentanone in this paper.Different high-efficiency catalysts were constructed according to the characteristics of the aldol condensation and the hydrodeoxygenation reaction,and the catalytic properties were also investigated.The major research contents were shown as follows:（1）A series of CeO₂-Al₂O₃catalysts with different molar ratios of Ce/Al were synthesized by co-precipitation method.The catalyst properties were examined by XRD,N₂adsorption-desorption,TEM,NH₃-TPD and XPS.The CeO₂-Al₂O₃（Ce/Al=3/7）exhibited better catalytic performance in the self-condensation of cyclopentanone,under the optimal reaction conditions,the yield of dimer reached68%.This was attributed to its suitable acidity and abundant oxygen vacancy.（2）TiO₂-ZrO₂composite oxides TZ-SG and TZ-ST were synthesized by sol-gel method and solvothermal method,respectively.The physicochemical properties of the catalysts were characterized by XRD,N₂adsorption-desorption,TEM,XPS,CO₂/NH₃-TPD and Py-FTIR.Compared with TZ-SG,TZ-ST exhibited higher catalytic activity in cyclopentanone self-condensation,which was due to its high specific surface area and plentiful acid-base sites.Under the optimum reaction conditions,the yield of dimer reached 76%.In addition to its basicity,the acidity of TiO₂-ZrO₂also has an important influence on its catalytic activity for cyclopentanone self-condensation.（3）In order to explore the influence of different acidic properties of catalysts on cyclopentanone self-condensation,calcined and uncalcined TiO₂-ZrO₂were synthesised for the self-condensation of cyclopentanone.The catalyst properties were examined by XRD,N₂adsorption-desorption,SEM,XPS,TG and Py-FTIR.Compared with calcined TiO₂-ZrO₂,uncalcined TiO₂-ZrO₂showed higher catalytic activity,which might be because calcined TiO₂-ZrO₂has only Lewis acids,while calcined TiO₂-ZrO₂contains both Lewis and Br（?）nsted acids,and the coexistence of the two acids promoted the cyclopentanone self-condensation.Furthermore,the influence of the cooperation between Lewis and Br（?）nsted acids on the kinetics of cyclopentanone self-condensation were investigated.（4）A series of NiM/TiO₂-ZrO₂（M=Co,Cu,Mo）catalysts were prepared using TiO₂-ZrO₂as the catalyst support,and their catalytic performance in the hydrodeoxygenation reaction were investigated.The effect of metal promoters（Co,Cu,Mo）on the physicochemical properties of the reduced Ni-based catalysts were examined by XRD,N₂adsorption-desorption,SEM,HRTEM,XPS,H₂-TPR and NH3-TPD.Among these catalysts,Ni Cu/TiO₂-ZrO₂exhibited higher catalytic activity,which was because that the addition of Cu improved the dispersion of the active site of the metal and Cu has a strong ability to activate the C=O bond.