Study On Synthesis Of High Density Fuel Components From Biomass And Non-biomass Derived Compounds

High-Energy-Density fuels are widely applied to the aerocrafts such as the rockets,missiles and fighter crafts,because of their properties of high density,high volumetric net heat of combustion.With the depletion of fossil resources and the increasing environmental problems,the synthesis of high-energy-density fuels through renewable and environmentally friendly biomass-derived resources has become the research hotspot.In this dissertation,the co-transformation of lignocellulosic platform compounds?4-ethylphenol,cyclopentanone?with non-biomass compounds?benzyl alcohol,cyclopentadiene?was carried out by alkylation reaction,Mannich reaction,Diels-Alder reaction and hydrodeoxygenation?HDO?.Two high density fuels were prepared with alkyl-substituted bicycloalkanes and bicyclic naphthene including the spiro and bridge structure as the main components,respectively.The alkylation of 4-ethylphenol with phenylmethanol was studied and the route of this reaction was explored.The conversion of reactants and the total selectivity of alkylated target products?2-benzyl-4-ethylphenol and 3-benzyl-4-ethylphenol?were explored under different commercial catalysts,reaction temperature,ratio of reactants and amount of catalysts,respectively.With HPW as the catalyst and the 4-ethylphenol/phenylmethanol ratio of 2,the conversion of phenylmethanol was up to100%and the selectivity of total alkylated target products reached 71%under the condition of 110?for 2h.Following the HDO of fuel precursor and vacuum distillation,a high-density fuel was obtained,with a density of 0.873 g/mL and a freezing point of-42?,demonstrating that the introduction of alkyl branches could have some effect on reducing the freezing point of hydrocarbon fuels.The Mannich reaction of cyclopentanone with formaldehyde and dimethylamine hydrochloride was studied.The influence on the conversion of cyclopentanone and the selectivity of the target product Mannich base were investigated under different temperature,reaction time and molar equivalents of cyclopentanone,respectively.The solvent used in the Diels-Alder reaction also explored for the influence on the yield of fuel precursor.When the system was reluxed at the boiling point of 90?for 2h,the conversion of cyclopentanone could reach 95%and the selectivity of Mannich base could reach 75%.With n-butanol as the solvent of Diels-Alder reaction,the yield of fuel precursor reached 62.8%.Fuel precursor was dealt with through NaBH₄ under the molar equivalents of 1:1 for 12h,and the product yield reached 99.5%.Further HDO by Pd/C and HZSM-5 under high temperature and high H₂ pressure,and the vacuum distillation,a spiro-bridge-structure fuel with high density?0.952 g/mL?and high volumetric net heat of combustion?40.2 MJ/L?was obtained.