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CN-122012136-A - Method for preparing JP-10 aviation fuel

CN122012136ACN 122012136 ACN122012136 ACN 122012136ACN-122012136-A

Abstract

The invention provides a method for preparing JP-10 aviation fuel, which comprises the following steps of A) preparing cyclopentenone from furfural through rearrangement reaction under the condition of hydrogen and a first catalyst, B) carrying out self dimerization reaction on the cyclopentenone under the condition of ultraviolet light to obtain a C10 quaternary ring oxygen-containing compound, C) carrying out hydrodeoxygenation and rearrangement reaction on the C10 quaternary ring oxygen-containing compound under the action of hydrogen and a second catalyst to obtain the JP-10 aviation fuel, wherein the second catalyst comprises a molecular sieve supported catalyst and/or an active carbon supported catalyst. According to the invention, five-membered carbocycle molecular cyclopentenone is prepared through furfural molecular reconstruction, quaternary tension carbocycle is constructed through green efficient photocatalysis [2+2] cycloaddition, and finally, a skeleton rearrangement hydrodeoxygenation reaction is carried out through a metal-loaded molecular sieve catalyst, so that a cycloalkane product is efficiently prepared, wherein the highest selectivity of the hanging tetrahydrodicyclopentadiene can reach 93%.

Inventors

  • GONG TIANJUN
  • FU YAO
  • ZHANG ZEKUAN
  • LIU XIANHUI

Assignees

  • 中国科学技术大学

Dates

Publication Date
20260512
Application Date
20260130

Claims (10)

  1. 1. A method of preparing JP-10 aviation fuel comprising the steps of: A) Preparing cyclopentenone from furfural through a rearrangement reaction under the condition of hydrogen and a first catalyst; B) Carrying out self dimerization reaction on the cyclopentenone under the ultraviolet light condition to obtain a C10 quaternary epoxy compound; C) Carrying out hydrodeoxygenation and rearrangement reaction on the C10 quaternary epoxy compound under the action of hydrogen and a second catalyst to obtain JP-10 aviation fuel; the second catalyst comprises a molecular sieve supported catalyst and/or an activated carbon supported catalyst; The molecular sieve supported catalyst is a molecular sieve supported metal catalyst, wherein the molecular sieve in the molecular sieve supported catalyst comprises one or more of an HY molecular sieve, laY molecular sieve, ceY molecular sieve, naY molecular sieve, reY molecular sieve, NH 4 Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, beta molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve and ITQ-1 molecular sieve, and the supported metal comprises one or more of Pd, rh, pt and Ru; The active carbon supported catalyst comprises an active carbon supported metal catalyst and an auxiliary agent, wherein the active carbon supported metal catalyst comprises one or more of a Pd/C catalyst, a Rh/C catalyst, a Pt/C catalyst and a Ru/C catalyst, and the auxiliary agent comprises a molecular sieve and/or heteropolyacid.
  2. 2. The method for producing JP-10 aviation fuel according to claim 1, wherein the first catalyst is a pentamethylcyclopentadienyl transition metal complex co-catalyst with a Lewis acid, The transition metal in the pentamethylcyclopentadienyl transition metal complex comprises one or more of iridium, ruthenium and rhodium; the ratio of the dosage of the pentamethyl cyclopentadienyl transition metal complex to the dosage of the Lewis acid is (0.005-0.2) mmol to 1mg; the temperature of the rearrangement reaction is 0-300 ℃, the time of the rearrangement reaction is 0.5-24 hours, and the hydrogen pressure is 0.1-10 MPa.
  3. 3. The method for producing an aviation fuel of JP-10 according to claim 1, wherein in the step B), the temperature of the dimerization reaction is 0 to 80 ℃ and the time of the dimerization reaction is 0.1 to 24 hours.
  4. 4. The method for preparing the JP-10 aviation fuel according to claim 1, wherein the molar ratio of SiO 2 to Al 2 O 3 in the molecular sieve-supported metal catalyst is 10 to 200; The mass of the metal element in the molecular sieve supported metal catalyst is 0.01-50wt% of the mass of the molecular sieve.
  5. 5. The method for producing an aviation fuel of JP-10 according to claim 1, characterized in that the molar ratio of the metal element in the molecular sieve supported metal catalyst to the C10 four-membered ring oxygen-containing compound is (0.0001 to 0.1): 1.
  6. 6. The method for preparing the JP-10 aviation fuel according to claim 1, wherein the molar ratio of SiO 2 to Al 2 O 3 in the molecular sieve in the activated carbon supported catalyst is 10-200; The mass of metal in the activated carbon supported metal catalyst is 0.5-20wt% of the mass of the activated carbon; The molar ratio of the metal in the activated carbon supported metal catalyst to the C10 quaternary ring oxygen-containing compound is (0.0001-0.1): 1.
  7. 7. The method of making JP-10 aviation fuel according to claim 1, wherein the molecular sieve in the adjuvant comprises one or more of HY molecular sieve, laY molecular sieve, ceY molecular sieve, naY molecular sieve, reY molecular sieve, NH 4 Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, beta molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve; the heteropoly acid comprises one or more of trifluoromethanesulfonate, silicotungstic acid, phosphotungstic acid or phosphomolybdic acid; the mass ratio of the active carbon supported metal catalyst to the auxiliary agent is (0.01-10) 1.
  8. 8. The method for producing an aviation fuel of JP-10 according to claim 1, wherein the hydrodeoxygenation and rearrangement reaction in step C) is performed at a temperature of 100 to 350 ℃, for a reaction time of 0.5 to 24 hours, and at a hydrogen pressure of 0.1 to 10mpa.
  9. 9. The method for producing JP-10 aviation fuel according to claim 1, wherein the rearrangement reaction in step a) is performed in a first solvent comprising one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide; The dimerization reaction in the step B) is carried out in a second solvent, wherein the second solvent comprises one or more of water, acetonitrile, ethyl acetate, benzene, toluene, cyclohexane, normal hexane, methylene dichloride and chloroform; the hydrodeoxygenation and rearrangement reaction in step C) is performed in a third solvent comprising one or more of cyclohexane, n-hexane, cyclopentane and n-pentane.
  10. 10. The method for producing JP-10 aviation fuel according to claim 9, wherein the concentration of the C10 quaternary cyclic oxygen-containing compound in the third solvent is 0.05 to 1mol/L.

Description

Method for preparing JP-10 aviation fuel Technical Field The invention belongs to the technical field of organic fuels, and particularly relates to a method for preparing JP-10 aviation fuel. Background The increasingly reduced fossil resources and the environmental problems such as the massive emission of greenhouse gases caused by the combustion of fossil energy are increasingly prominent, and the social demand of energy is continuously increasing, so that the development of new energy capable of replacing fossil resources is imperative. Biomass has become a current hot research in the production of carbon materials, fuels and chemicals as a renewable organic carbon source. Aviation fuel JP-10 is a high density aviation fuel commonly used internationally. According to U.S. military specification MIL-P-87107C-1989, the fuel has a density of 0.935g/cm 3 (16 ℃) and a freezing point of-78 ℃, has a combustion heating value of 42.1 MJ/kg, has a higher energy density than conventional hydrocarbon fuels, and is an aviation fuel with excellent performance. The method is widely applied to aircrafts such as supersonic fighters, cruise missiles, rockets and the like. JP-10 is a single component fuel composed of hanging tetrahydrodicyclopentadiene with a purity of 98.5%. The existing JP-10 synthesis route is that bridge dicyclopentadiene is taken as a raw material, hydrogenated into bridge tetrahydrodicyclopentadiene, and then isomerized into hanging tetrahydrodicyclopentadiene under the catalysis of catalysts such as AlCl 3、H2SO4. The method has the advantages of more byproducts, complex separation process, serious environmental pollution caused by acid catalytic isomerization step and low yield. There are also some other JP-10 aviation fuels synthesized but they all use cyclopentadiene or dicyclopentadiene from fossil energy sources as raw materials, which are highly dependent on non-renewable fossil energy sources. Disclosure of Invention The invention aims to provide a method for preparing JP-10 aviation fuel, wherein the catalyst and the raw materials are simple and easy to obtain, and the reaction has higher yield and selectivity. The invention provides a method for preparing JP-10 aviation fuel, which comprises the following steps: A) Preparing cyclopentenone from furfural through a rearrangement reaction under the condition of hydrogen and a first catalyst; B) Carrying out self dimerization reaction on the cyclopentenone under the ultraviolet light condition to obtain a C10 quaternary epoxy compound; C) Carrying out hydrodeoxygenation and rearrangement reaction on the C10 quaternary epoxy compound under the action of hydrogen and a second catalyst to obtain JP-10 aviation fuel; the second catalyst comprises a molecular sieve supported catalyst and/or an activated carbon supported catalyst; The molecular sieve supported catalyst is a molecular sieve supported metal catalyst, wherein the molecular sieve in the molecular sieve supported catalyst comprises one or more of an HY molecular sieve, laY molecular sieve, ceY molecular sieve, naY molecular sieve, reY molecular sieve, NH 4 Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, beta molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve and ITQ-1 molecular sieve, and the supported metal comprises one or more of Pd, rh, pt and Ru; The active carbon supported catalyst comprises an active carbon supported metal catalyst and an auxiliary agent, wherein the active carbon supported metal catalyst comprises one or more of a Pd/C catalyst, a Rh/C catalyst, a Pt/C catalyst and a Ru/C catalyst, and the auxiliary agent comprises a molecular sieve and/or heteropolyacid. Preferably, the first catalyst is a pentamethyl cyclopentadienyl transition metal complex and Lewis acid co-catalyst, The transition metal in the pentamethylcyclopentadienyl transition metal complex comprises one or more of iridium, ruthenium and rhodium; the ratio of the dosage of the pentamethyl cyclopentadienyl transition metal complex to the dosage of the Lewis acid is (0.005-0.2) mmol to 1mg; the temperature of the rearrangement reaction is 0-300 ℃, the time of the rearrangement reaction is 0.5-24 hours, and the hydrogen pressure is 0.1-10 MPa. Preferably, in the step B), the temperature of the dimerization reaction is 0to 80 ℃ and the time of the dimerization reaction is 0.1 to 24 hours. Preferably, in the molecular sieve supported metal catalyst, the molar ratio of SiO 2 to Al 2O3 is 10-200; The mass of the metal element in the molecular sieve supported metal catalyst is 0.01-50wt% of the mass of the molecular sieve. Preferably, the molar ratio of the metal element in the molecular sieve supported metal catalyst to the C10 four-membered ring oxygen-containing compound is (0.0001-0.1): 1. Preferably, in the molecular sieve in the activated carbon supported catalyst, the molar ratio o