A process for the preparation of a jet fuel component from glycerol and cyclopentadiene
High-density aviation fuel components were prepared through a multi-step chemical reaction between glycerol and cyclopentadiene, solving the problems of non-renewability and high cost of fossil resources and realizing the transformation of renewable biomass resources into high-performance fuels.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SOUTHEAST UNIV
- Filing Date
- 2023-11-14
- Publication Date
- 2026-05-05
AI Technical Summary
The existing high-density aviation fuel components are mainly derived from fossil resources, resulting in non-renewability and high costs, which limits their widespread application in civil aviation.
High-density fuel components are prepared by a series of chemical reactions between glycerol and cyclopentadiene in the presence of a catalyst, including liquid-phase dehydration, Diels-Alder reaction, deoxygenation and decarbonylation, self-polymerization and hydrogenation.
It has enabled the preparation of high-density, high-calorific-value aviation fuel components from renewable biomass resources, promoting the high-value utilization of agricultural and forestry waste and the reduction of carbon emissions.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of biomass liquid fuel technology, specifically relating to a method for preparing aviation fuel components from glycerol and cyclopentadiene. Background Technology
[0002] High-density, high-calorific-value jet fuels enable modern aircraft to achieve higher speeds, greater payloads, and longer ranges. Currently, the high-density jet fuels used worldwide are primarily composed of fossil-based (coal, petroleum) derivatives obtained through Diels-Alder, hydrogenation, and isomerization reactions. For example, JP-10 (with tetrahydrodicyclopentadiene as its main component and a density of 0.93 g / cm³) 3 The main components are RJ-5 (endo-endo-dihydrodi(norbornadiene)) and its density is 1.08 g / cm³. 3 HDF-T1 (with tetrahydrotricyclopentadiene as the main component and a density of 1.02 g / cm³) 3 Fossil resources are non-renewable and emit large amounts of carbon dioxide during use, creating a dual crisis of energy and environment. Furthermore, current aviation fuel components are primarily derived from fossil fuels, making them expensive (e.g., JP-10 at $25 per gallon), limiting their widespread use in civil aviation. Therefore, there is an urgent need to develop new technological routes for synthesizing aviation fuel components using renewable biomass. Summary of the Invention
[0003] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing aviation fuel components from glycerol and cyclopentadiene, thereby solving the problems in the prior art.
[0004] The objective of this invention can be achieved through the following technical solutions:
[0005] A method for preparing aviation fuel components from glycerol and cyclopentadiene includes the following steps:
[0006] Glycerol was placed in a reaction vessel and subjected to a liquid-phase dehydration reaction under the catalysis of HPW to obtain acrolein;
[0007] Using enaldehyde as a raw material and methanol, ethanol or diethyl ether as a solvent, cyclopentadiene is reacted with 5-norbornene-2-carboxaldehyde in a reaction tube without a catalyst to obtain 5-norbornene-2-carboxaldehyde.
[0008] 5-Norbornene-2-carboxaldehyde was placed in a reaction vessel, and benzonitrile and RhCl(PPh3)3 were added to carry out a deoxygenation and decarbonylation reaction to obtain norbornene.
[0009] Norbornene was placed in a reaction vessel, and a molecular sieve catalyst and dichloromethane were added to carry out a self-polymerization reaction to obtain a mixture composed of nortricycloane, norbornene dimer and trimer;
[0010] A mixture of nortricycloane, norbornene dimer and trimer is placed in a reactor, and a catalyst is added to carry out a hydrogenation reaction to obtain fuel.
[0011] Furthermore, the molar ratio of glycerol to HPW is 100-600: 0.208-0.347.
[0012] Furthermore, the reaction time of the liquid-phase dehydration reaction is 1 to 8 hours, the reaction temperature is 180 to 280°C, and the stirring rate is 300 rpm / min.
[0013] Furthermore, the molar ratio of acrolein to cyclopentadiene is 1:0.5 to 5.
[0014] Furthermore, the reaction time of the Diels-Alder reaction is 3 to 7 hours, the reaction temperature is 25 to 45°C, and the stirring rate is 20 rpm / min.
[0015] Furthermore, in the deoxygenation and decarbonylation reaction, the mass ratio of 5-norbornene-2-carboxaldehyde to RhCl(PPh3)3 is 1:1-6.
[0016] Furthermore, the reaction temperature of the deoxygenation and decarbonylation reaction is 170–240°C, and the reaction time is 4–48 h.
[0017] Furthermore, the molecular sieve catalyst is HY, MCM-41 or Hβ; the reaction temperature of the self-polymerization reaction is 40-100℃, and the reaction time is 1-3h; the mass ratio of norbornene to the molecular sieve catalyst is 10:1.
[0018] Furthermore, in the hydrogenation reaction, the catalyst is Pt / C, Pd / C or Ru / C, the reaction temperature is 120-160℃, the reaction time is 6-10h, the H2 pressure is 2-6MPa, and the mass ratio of the mixture to the catalyst is 40:1.5-3.
[0019] A biomass liquid fuel comprising aviation fuel components prepared using the method described above.
[0020] The beneficial effects of this invention are:
[0021] 1. The raw material of this invention, glycerol, is a byproduct of the preparation of biodiesel from animal and vegetable oils, and cyclopentadiene can be prepared by the directional conversion of hemicellulose components in agricultural and forestry waste biomass. Both are renewable resources.
[0022] 2. The product of this invention is a hydrocarbon fuel composed of norbornene isomers, dimers and trimers. It has high density and high calorific value and is an ideal high-performance jet fuel component.
[0023] 3. This invention realizes the conversion of renewable biomass resources into high-quality jet fuel, which will promote the high-value utilization of low-value agricultural and forestry waste and the reduction of carbon emissions. Attached Figure Description
[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0025] Figure 1 This is a schematic diagram of the route for preparing high-density fuel from glycerol and cyclopentadiene in this invention. Detailed Implementation
[0026] The following will be combined with the appendix of this invention. Figure 1 The technical solutions in the embodiments of the present invention are clearly and completely described herein. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0027] It should be noted that the glycerol used in this invention is a byproduct of the preparation of biodiesel from animal and vegetable oils, and cyclopentadiene can be prepared by the directional conversion of hemicellulose components in agricultural and forestry waste biomass. In addition, the high-density fuel described in this invention is mainly composed of polycyclic alkanes.
[0028] Example 1
[0029] The process of preparing acrolein from glycerol includes:
[0030] 0.1 mol of glycerol and 0.0000347 mol of HPW were added to a high-pressure reactor and reacted at 240℃ for 2 h with a stirring rate of 300 rpm / min. After the reaction was completed, the target product acrolein was obtained. Gas chromatography analysis showed that the glycerol conversion rate was 88.4%, the acrolein yield was 86.3%, and the hydroxyacetone yield was 1.3%.
[0031] Example 2
[0032] The steps for preparing acrolein from glycerol include:
[0033] 0.6 mol of glycerol and 0.000208 mol of HPW were added to a high-pressure reactor and reacted at 280℃ for 8 h with a stirring rate of 300 rpm / min. After the reaction, the target product acrolein was obtained. The test analysis showed that the glycerol conversion rate was 75.6%, the acrolein yield was 58.4%, and the hydroxyacetone yield was 7.8%.
[0034] Example 3
[0035] The process of preparing acrolein from glycerol includes:
[0036] 0.1 mol of glycerol and 0.0000347 mol of HPW were added to a high-pressure reactor and reacted at 180 °C for 1 h with a stirring rate of 300 rpm / min. After the reaction, the target product acrolein was obtained. The test analysis showed that the glycerol conversion rate was 64.9%, the acrolein yield was 42.4%, and the hydroxyacetone yield was 6.3%.
[0037] Example 4
[0038] The process of preparing 5-norbornene-2-carboxaldehyde from acrolein includes:
[0039] 5 ml of methanol, 0.01 mol of acrolein, and 0.01 mol of cyclopentadiene were added to a reaction tube equipped with a magnetic stir bar. The mixture was stirred at 35 °C (20 rpm / min) and subjected to a Diels-Alder reaction for 5 h. After the reaction was completed, the product 5-norbornene-2-carboxaldehyde was obtained by separation. The conversion rate of acrolein was 98.2%, and the yield of 5-norbornene-2-carboxaldehyde was 96.2%.
[0040] Example 5
[0041] The process of preparing 5-norbornene-2-carboxaldehyde from acrolein includes:
[0042] 5 ml of diethyl ether, 0.01 mol of acrolein, and 0.01 mol of cyclopentadiene were added to a reaction tube equipped with a magnetic stir bar. The mixture was stirred at 35 °C (20 rpm / min) and subjected to a Diels-Alder reaction for 5 h. After the reaction was completed, the product 5-norbornene-2-carboxaldehyde was obtained by separation. The conversion rate of acrolein was 75.6%, and the yield of 5-norbornene-2-carboxaldehyde was 58.3%.
[0043] Example 6
[0044] The process of preparing 5-norbornene-2-carboxaldehyde from acrolein includes:
[0045] 5 ml of ethanol, 0.01 mol of acrolein, and 0.01 mol of cyclopentadiene were added to a reaction tube equipped with a magnetic stir bar. The mixture was stirred at 35 °C (20 rpm / min) and subjected to a Diels-Alder reaction for 5 h. After the reaction was completed, the product 5-norbornene-2-carboxaldehyde was obtained by separation. The conversion rate of acrolein was 89.2%, and the yield of 5-norbornene-2-carboxaldehyde was 87.3%.
[0046] Example 7
[0047] The process of preparing 5-norbornene-2-carboxaldehyde from acrolein includes:
[0048] 5 ml of methanol, 0.01 mol of acrolein, and 0.01 mol of cyclopentadiene were added to a reaction tube equipped with a magnetic stir bar. The mixture was stirred at 25 °C (20 rpm / min) and subjected to a Diels-Alder reaction for 5 h. After the reaction was completed, the product 5-norbornene-2-carboxaldehyde was obtained by separation. The conversion rate of acrolein was 82.5%, and the yield of 5-norbornene-2-carboxaldehyde was 80.6%.
[0049] Example 8
[0050] The process of preparing 5-norbornene-2-carboxaldehyde from acrolein includes:
[0051] 5 ml of methanol, 0.01 mol of acrolein, and 0.01 mol of cyclopentadiene were added to a reaction tube equipped with a magnetic stir bar. The mixture was stirred at 45 °C (20 rpm / min) and subjected to a Diels-Alder reaction for 5 h. After the reaction was completed, the product 5-norbornene-2-carboxaldehyde was obtained by separation. The conversion rate of acrolein was 92.5%, and the yield of 5-norbornene-2-carboxaldehyde was 90.3%.
[0052] Example 9
[0053] The process of preparing 5-norbornene-2-carboxaldehyde from acrolein includes:
[0054] 5 ml of methanol, 0.01 mol of acrolein, and 0.005 mol of cyclopentadiene were added to a reaction tube equipped with a magnetic stir bar. The mixture was stirred at 45 °C (20 rpm / min) and subjected to a Diels-Alder reaction for 3 h. After the reaction was completed, the product 5-norbornene-2-carboxaldehyde was obtained by separation. The conversion rate of acrolein was 80.6%, and the yield of 5-norbornene-2-carboxaldehyde was 75.4%.
[0055] Example 10
[0056] The process of preparing 5-norbornene-2-carboxaldehyde from acrolein includes:
[0057] 5 ml of methanol, 0.01 mol of acrolein, and 0.05 mol of cyclopentadiene were added to a reaction tube equipped with a magnetic stir bar. The mixture was stirred at 45 °C (20 rpm / min) and subjected to a Diels-Alder reaction for 7 h. After the reaction was completed, the product 5-norbornene-2-carboxaldehyde was obtained by separation. The conversion rate of acrolein was 76.3%, and the yield of 5-norbornene-2-carboxaldehyde was 63.8%.
[0058] Example 11
[0059] The process of preparing norbornene involves a deoxygenation and decarbonylation reaction of 5-norbornene-2-carboxaldehyde in a high-pressure reactor, including:
[0060] 0.1 g of 5-norbornene-2-carboxaldehyde, 0.2 g of rhodium tris(triphenylphosphine) chloride (RhCl(PPh3)3), and 30 ml of benzonitrile were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 190 °C for 6 h. After the reaction was completed, the conversion rate of 5-norbornene-2-carboxaldehyde was 60.3%, and the yield of norbornene was 40.2%.
[0061] Example 12
[0062] The process of preparing norbornene involves a deoxygenation and decarbonylation reaction of 5-norbornene-2-carboxaldehyde in a high-pressure reactor, including:
[0063] 0.1 g of 5-norbornene-2-carboxaldehyde, 0.1 g of rhodium tris(triphenylphosphine) chloride (RhCl(PPh3)3), and 30 ml of benzonitrile were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 170 °C for 4 h. After the reaction was completed, the conversion rate of 5-norbornene-2-carboxaldehyde was 20.6%, and the yield of norbornene was 5.4%.
[0064] Example 13
[0065] The process of preparing norbornene involves a deoxygenation and decarbonylation reaction of 5-norbornene-2-carboxaldehyde in a high-pressure reactor, including:
[0066] 0.1 g of 5-norbornene-2-carboxaldehyde, 0.6 g of rhodium tris(triphenylphosphine) chloride (RhCl(PPh3)3), and 30 ml of benzonitrile were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 240 °C for 48 h. After the reaction was completed, the conversion rate of 5-norbornene-2-carboxaldehyde was 40.8%, and the yield of norbornene was 15.6%.
[0067] Example 14
[0068] Norbornene undergoes a self-polymerization reaction catalyzed by a molecular sieve catalyst to obtain a mixture composed of: norbornene isomerization product nortricycloane, norbornene dimer and trimer. The specific process includes:
[0069] 10g norbornene, 1g Hβ and 30ml dichloromethane were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 80℃ for 1h. After the reaction, the conversion rate of norbornene was 98.7%, the yield of norbornene isomer (nortricycloane) was 55.7%, the yield of norbornene dimer was 41.0%, and the yield of norbornene trimer was 0.94%.
[0070] Example 15
[0071] Norbornene undergoes a self-polymerization reaction catalyzed by molecular sieves to obtain a mixture consisting of: norbornene isomerization product nortricycloane, norbornene dimer and trimer. The specific process includes:
[0072] 10g norbornene, 1g HY and 30ml dichloromethane were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 80℃ for 1h. After the reaction was completed, the conversion rate of norbornene was 96.5%, the yield of norbornene isomer (norbornene tricycloane) was 50.5%, the yield of norbornene dimer was 43.8%, and the yield of norbornene trimer was 1.8%.
[0073] Example 16
[0074] Norbornene undergoes a self-polymerization reaction catalyzed by molecular sieves to obtain a mixture consisting of: norbornene isomerization product nortricycloane, norbornene dimer and trimer. The specific process includes:
[0075] 10g norbornene, 1g MCM-41 and 30ml dichloromethane were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 80℃ for 1h. After the reaction, the conversion rate of norbornene was 99.7%, the yield of norbornene isomer (norbornene tricycloane) was 47.9%, the yield of norbornene dimer was 45%, and the yield of norbornene trimer was 6.2%.
[0076] Example 17
[0077] Norbornene undergoes a self-polymerization reaction catalyzed by molecular sieves to obtain a mixture consisting of: norbornene isomerization product nortricycloane, norbornene dimer and trimer. The specific process includes:
[0078] 10g norbornene, 1g Hβ and 30ml dichloromethane were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 100℃ for 1h. After the reaction, the conversion rate of norbornene was 97.3%, the yield of norbornene isomer (norbornene tricycloane) was 55.3%, the yield of norbornene dimer was 39.4%, and the yield of norbornene trimer was 1.2%.
[0079] Example 18
[0080] Norbornene undergoes a self-polymerization reaction catalyzed by molecular sieves to obtain a mixture consisting of: norbornene isomerization product nortricycloane, norbornene dimer and trimer. The specific process includes:
[0081] 10g norbornene, 1g Hβ and 30ml dichloromethane were added to a high-pressure reactor equipped with mechanical stirring, and the reaction was carried out at 40℃ for 3h. After the reaction was completed, the conversion rate of norbornene was 60.3%, the yield of norbornene isomer (nortricycloane) was 23.4%, the yield of norbornene dimer was 26.9%, and the yield of norbornene trimer was 2.3%.
[0082] Example 19
[0083] Using a mixture of norbornene isomerization product nortricycloane, norbornene dimer, and trimer as raw materials, a hydrogenation reaction is carried out to prepare a high-density fuel composed of norbornene isomerization product norbornene dimer and trimer; the specific steps include:
[0084] 40g of the mixture obtained in Example 14 and 1.5g of 5% Pd / C were added to a high-pressure reactor equipped with mechanical stirring for hydrogenation reaction; the reaction temperature was 150℃, the reaction time was 10h, and the H2 pressure was 5MPa. After the reaction, the conversion rate of the reactants was 100%, and the yield of the target product was 99.6%; the density and calorific value of the prepared fuel were measured to be 0.936g / cm³. 3 37.98 MJ / L.
[0085] Example 20
[0086] 40g of the mixture obtained in Example 14 and 2g of 5% Pt / C were added to a high-pressure reactor equipped with mechanical stirring for hydrogenation reaction; the reaction temperature was 120℃, the reaction time was 6h, and the H2 pressure was 2MPa. After the reaction, the conversion rate of the reactants was 90.2%, and the yield of the target product was 84.7%.
[0087] Example 21
[0088] 40g of the mixture obtained in Example 14 and 3g of 5% Ru / C were added to a high-pressure reactor equipped with mechanical stirring for hydrogenation reaction; the reaction temperature was 160℃, the reaction time was 6h, and the H2 pressure was 6MPa. After the reaction, the conversion rate of the reactants was 94.3%, and the yield of the target product was 85.2%.
[0089] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0090] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.
Claims
1. A method for preparing aviation fuel components from glycerol and cyclopentadiene, characterized in that, Includes the following steps: Glycerol was placed in a reaction vessel and subjected to a liquid-phase dehydration reaction under the catalysis of HPW to obtain acrolein; Using acrolein as a raw material and methanol, ethanol or diethyl ether as a solvent, a Diels-Alder reaction is carried out with cyclopentadiene in a reaction tube without catalysis to obtain 5-norbornene-2-carboxaldehyde. 5-Norbornene-2-carboxaldehyde was placed in a reaction vessel, and benzonitrile and RhCl(PPh3)3 were added to carry out a deoxygenation and decarbonylation reaction to obtain norbornene. Norbornene was placed in a reaction vessel, and a molecular sieve catalyst and dichloromethane were added to carry out a self-polymerization reaction to obtain a mixture composed of nortricycloane, norbornene dimer and trimer; A mixture consisting of nortricycloane, norbornene dimer and trimer is placed in a reactor, and a catalyst is added to carry out a hydrogenation reaction to obtain aviation fuel components. The molecular sieve catalyst is HY, MCM-41, or Hβ.
2. The method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1, characterized in that, The molar ratio of glycerol to HPW is 100-600: 0.208-0.
347.
3. The method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1 or 2, characterized in that, The reaction time for the liquid-phase dehydration reaction is 1-8 h, the reaction temperature is 180-280℃, and the stirring rate is 300 rpm / min.
4. The method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1, characterized in that, The molar ratio of acrolein to cyclopentadiene is 1:0.5~5.
5. A method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1 or 4, characterized in that, The Diels-Alder reaction takes 3 to 7 hours, is carried out at a temperature of 25 to 45°C, and is stirred at a speed of 20 rpm.
6. The method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1, characterized in that, In the deoxygenation and decarbonylation reaction, the mass ratio of 5-norbornen-2-carboxaldehyde to RhCl(PPh3)3 is 1:1-6.
7. A method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1 or 6, characterized in that, The deoxygenation and decarbonylation reaction is carried out at a temperature of 170~240℃ for 4~48 h.
8. The method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1, characterized in that, The self-polymerization reaction is carried out at a temperature of 40-100℃ and for a time of 1-3 h; the mass ratio of norbornene to molecular sieve catalyst is 10:
1.
9. The method for preparing aviation fuel components from glycerol and cyclopentadiene according to claim 1, characterized in that, 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 H2 pressure is 2-6 MPa, and the mass ratio of the mixture to the catalyst is 40:1.5-3.
10. A biomass liquid fuel, characterized in that, Includes aviation fuel components prepared using the method described in any one of claims 1-9.
Citation Information
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