Synthesis Of High-density Fuels Based On Turpentine And Lignocellulose Platform Chemicals

High-density hydrocarbon fuel is a kind of valuable liquid space propellant.It can significantly increase the flight and load of aircraft,and usually synthesized from fossil materials.With the consumption of fossil resource,synthesis of high-density fuel from biomass gradually draws attention of people.Turpentine and lignocellulose platform compounds are rich and renewable sources from nature.Regarding to the synthesis of fuel precursors and hydrogenation,this work gives a research on the technologies of synthesis of high-density polycyclic fuels using them.Technology of synthesis of turpentine based high-density fuel was studied.High activity catalyst of HPW(H₃PW₁₂O₄₀)/MCM-41 was made and the product distribution in isomerization and dimerization of turpentine by this catalyst was analyzed.In terms of the products development process,a reaction pathway is elaborated.It is found that the pinene and oxy-terpenes in the turpentine are firstly isomerized to camphene,limonene,terpinene etc and then these terpenes are dimerized to produce fuel precursors by Diels-Alder reaction and oligomerization reaction with 71%yield.Technology of synthesis of connected naphthenes was studied.Fuel precursors of mono-naphthenic phenols were synthesized from the alkylation of lignin-derived phenols?phenol,anisole,guaiacol?and the lignocellulose cyclols?cyclohexanol,cyclopentanol?catalyzed by zeolites.The selectivity of mono-naphthenic phenols was more than 76.7%by reducing the concentration of intermediates?cycloalkene ect?in the reaction.Bicyclohexane and cyclopentyl cyclohexane can be obtained from the hydrodeoxygenation of mono-naphthenic phenols.Regarding to reducing the high freezing point of bicyclohexane,hydroisomerization was introduced to the hydrodeoxygenation of mono-naphthenic phenols to optimize the fuel molecular structure.?Cyclopentylmethyl?cyclohexane was produced and the freezing point of fuel was reduced.The density of fuels produced by this technology is from 0.87 g/m L to 0.88 g/mL.Technology of synthesis of perhydrofluorene was studied.Substituted diphenylmethane fuel precursors were synthesized from alkylation of phenols with benzyl ether by super acid catalyst and so on.Judging from the product distribution of the alkylation,MMT-K10?H₀=-8.2?can inhibit self-alkylation of benzyl ether with selectivity of substituted diphenylmethanes more than 80.6%.In the hydrodeoxygenation of substitution of diphenylmethanes,Pd/C is favorable to intramolecular cyclization with perhydrofluorene formation finally,while increasing the dosage of zeolite can accelerate dehydroxy process in the single ring with dicyclohexylmethane formation.The density of fuels produced by this technology is around at 0.88⁰.96 g/mL.Technology of naphthas synthesis was studied.Super acid was used to catalyze the reaction of cyclic alcohols?cyclohexanol etc?and cycloalkanes?methylcyclohexane etc?.In this process,hydride transfer induced by super acid is used to initiate the alkylation and hydrogenate the alkylated products.The combination of the alkylation and hydride transfer completes the synthesis of naphthas precursors and hydrogenation of the precursors in one step.The selectivity of naphthas is up to 86.5%and the fuel density is more than 0.88 g/m L by this technology.