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CN-117535075-B - Method for preparing aviation oil component from glycerol and cyclopentadiene

CN117535075BCN 117535075 BCN117535075 BCN 117535075BCN-117535075-B

Abstract

The invention discloses a method for preparing an aviation oil component by using glycerol and cyclopentadiene, which belongs to the technical field of biomass liquid fuels, and comprises the steps of placing the glycerol into a reaction kettle, carrying out liquid phase dehydration reaction under the catalysis of HPW to obtain acrolein, taking olefine aldehyde as a raw material, taking methanol, ethanol or diethyl ether as a solvent, carrying out Diels-Alder reaction with cyclopentadiene under the absence of catalysis in the reaction pipe to obtain 5-norbornene-2-formaldehyde, placing the 5-norbornene-2-formaldehyde into the reaction kettle, adding benzonitrile and RhCl (PPh 3 ) 3 ) for deoxidization decarbonylation reaction to obtain norbornene, placing the norbornene into the reaction kettle, adding a molecular sieve catalyst and methylene dichloride for self polymerization reaction to obtain a mixture composed of nortricycloalkane, norbornene dimer and trimer, placing the mixture composed of nortricycloalkane, norbornene dimer and trimer into the reaction kettle, and adding the catalyst for hydrogenation reaction to obtain the fuel.

Inventors

  • ZHANG XINGHUA
  • FANG ZHENQUAN
  • MA LONGLONG
  • ZHANG QI
  • CHEN LUNGANG
  • LIU JIANGUO

Assignees

  • 东南大学

Dates

Publication Date
20260505
Application Date
20231114

Claims (10)

  1. 1. A method for preparing an aviation oil component by glycerol and cyclopentadiene, which is characterized by comprising the following steps: placing glycerol into a reaction kettle, and carrying out liquid phase dehydration reaction under the catalysis of HPW to obtain acrolein; acrolein is used as a raw material, methanol, ethanol or diethyl ether is used as a solvent, diels-Alder reaction is carried out with cyclopentadiene in a reaction tube under the condition of no catalysis, and 5-norbornene-2-formaldehyde is obtained; putting 5-norbornene-2-formaldehyde into a reaction kettle, and adding benzonitrile and RhCl (PPh 3 ) 3 for deoxidization decarbonylation reaction to obtain norbornene; Putting norbornene into a reaction kettle, adding a molecular sieve catalyst and methylene dichloride for self-polymerization reaction to obtain a mixture consisting of nortricycloalkane, norbornene dimer and trimer; putting a mixture consisting of nortricycloalkane, norbornene dimer and trimer into a reaction kettle, and adding a catalyst for hydrogenation reaction to obtain an aviation oil component; the molecular sieve catalyst is HY, MCM-41 or H beta.
  2. 2. The method of preparing a aviation oil component of claim 1, wherein the molar ratio of glycerin to HPW is 100-600:0.208-0.347.
  3. 3. The method for preparing an aviation oil component by using glycerol and cyclopentadiene according to claim 1 or 2, wherein the reaction time of the liquid phase dehydration reaction is 1-8 hours, the reaction temperature is 180-280 ℃, and the stirring rate is 300 rpm/min.
  4. 4. The method for preparing an aviation oil component by using glycerol and cyclopentadiene according to claim 1, wherein the molar ratio of acrolein to cyclopentadiene is 1:0.5-5.
  5. 5. The method for preparing an aviation oil component by using glycerol and cyclopentadiene according to claim 1 or 4, wherein the reaction time of Diels-Alder reaction is 3-7 h, the reaction temperature is 25-45 ℃, and the stirring rate is 20 rpm.
  6. 6. The method for preparing an aviation oil component by using glycerol and cyclopentadiene according to claim 1, wherein in the deoxidization decarbonylation reaction, the mass ratio of 5-norbornene-2-formaldehyde to RhCl (PPh 3 ) 3 is 1:1-6).
  7. 7. The method for preparing an aviation oil component by using glycerol and cyclopentadiene according to claim 1 or 6, wherein the reaction temperature of the deoxidization decarbonylation reaction is 170-240 ℃ and the reaction time is 4-48 hours.
  8. 8. The method for preparing the aviation oil component by using the glycerin and the cyclopentadiene according to claim 1, wherein the self-polymerization reaction is carried out at a reaction temperature of 40-100 ℃ for 1-3 hours, and the mass ratio of norbornene to molecular sieve catalyst is 10:1.
  9. 9. The method for preparing the aviation oil component by using the glycerol and the cyclopentadiene according to claim 1, wherein in the hydrogenation reaction, the catalyst is Pt/C, pd/C or Ru/C, the reaction temperature is 120-160 ℃, the reaction time is 6-10 h, the H 2 pressure is 2-6 MPa, and the mass ratio of the mixture to the catalyst is 40:1.5-3.
  10. 10. A biomass liquid fuel comprising an aviation oil component prepared using the method of any one of claims 1-9.

Description

Method for preparing aviation oil component from glycerol and cyclopentadiene Technical Field The invention belongs to the technical field of biomass liquid fuels, and particularly relates to a method for preparing an aviation oil component from glycerol and cyclopentadiene. Background High density, high heating value jet fuels can enable modern aircraft to have faster speeds, greater loads, and greater range. At present, the high-density aviation oil component used in various countries in the world is mainly obtained by Diels-Alder, hydrogenation and isomerization reactions of fossil-based (coal and petroleum) derivatives. For example, JP-10 (exo-tetrahydrodicyclopentadiene as a main component with a density of 0.93g/cm 3), RJ-5 (endo-dihydrobis (norbornadiene) as a main component with a density of 1.08g/cm 3), HDF-T1 (exo-tetrahydrodicyclopentadiene as a main component with a density of 1.02g/cm 3) and the like. Fossil resources are nonrenewable and emit large amounts of carbon dioxide during use, thus creating a double crisis for energy and the environment. In addition, since current aviation fuel components are mainly derived from fossil energy sources, their high price (e.g., JP-10, $25 per gallon) limits their wide use in civil aviation. Thus, there is a need to develop new technological routes for synthesizing aviation oil components using renewable biomass. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a method for preparing an aviation oil component by glycerol and cyclopentadiene, which solves the problems in the prior art. The aim of the invention can be achieved by the following technical scheme: A method for preparing an aviation oil component by glycerol and cyclopentadiene, which comprises the following steps: placing glycerol into a reaction kettle, and carrying out liquid phase dehydration reaction under the catalysis of HPW to obtain acrolein; Olefine aldehyde is used as a raw material, methanol, ethanol or diethyl ether is used as a solvent, diels-Alder reaction is carried out with cyclopentadiene in a reaction tube under the condition of no catalysis, and 5-norbornene-2-formaldehyde is obtained; putting 5-norbornene-2-formaldehyde into a reaction kettle, and adding benzonitrile and RhCl (PPh 3)3 for deoxidization decarbonylation reaction to obtain norbornene; putting norbornene into a reaction kettle, adding a molecular sieve catalyst and methylene dichloride for self-polymerization reaction to obtain a mixture consisting of nortricycloalkane, norbornene dimer and trimer; and (3) putting a mixture consisting of nortricycloalkane, norbornene dimer and trimer into a reaction kettle, and adding a catalyst for hydrogenation reaction to obtain the fuel. Further, the molar ratio of the glycerol to the HPW is 100-600:0.208-0.347. Further, the reaction time of the liquid phase dehydration reaction is 1-8 hours, the reaction temperature is 180-280 ℃, and the stirring speed is 300rpm/min. Further, the molar ratio of the acrolein to the cyclopentadiene is 1:0.5-5. Further, the reaction time of the Diels-Alder reaction is 3-7 h, the reaction temperature is 25-45 ℃, and the stirring speed is 20rpm/min. Further, in the deoxidization decarbonylation reaction, the mass ratio of 5-norbornene-2-carbaldehyde and RhCl (PPh 3)3 is 1:1-6. Further, the reaction temperature of the deoxidization decarbonylation reaction is 170-240 ℃ and the reaction time is 4-48 h. Further, the molecular sieve catalyst is HY, MCM-41 or H beta, the reaction temperature of the self-polymerization reaction is 40-100 ℃, the reaction time is 1-3H, and the mass ratio of norbornene to the molecular sieve catalyst is 10:1. Further, in the hydrogenation reaction, the catalyst is Pt/C, pd/C or Ru/C, the reaction temperature is 120-160 ℃, the reaction time is 6-10 h, the H 2 pressure is 2-6 MPa, and the mass ratio of the mixture to the catalyst is 40:1.5-3. A biomass liquid fuel comprising a aviation oil component prepared using the above method. The invention has the beneficial effects that: 1. The raw material glycerin of the invention is a byproduct of preparing biodiesel from animal and vegetable oil, and cyclopentadiene can be prepared by directional conversion of hemicellulose components in agricultural and forestry waste biomass, and belongs to renewable resources. 2. The product of the invention is hydrocarbon fuel composed of norbornene isomer, dimer and trimer, has high density and high heat value, and is an ideal high-performance jet fuel component. 3. The invention realizes the conversion of renewable biomass resources into high-quality jet fuel, and promotes the high-value utilization of low-value agricultural and forestry waste and the reduction of carbon emission. Drawings In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be brief