A one-pot method for synthesizing polycycloalkane high-density aviation fuel

Abstract

The present invention discloses a one-pot method for synthesizing polycycloalkane high-density aviation fuel, comprising: catalyzing an alkylation reaction of biomass phenols and cyclic alcohols with a metal-supported molecular sieve catalyst X / Y in the absence of solvents to produce an intermediate compound; and catalyzing the intermediate compound with a hydrogenation deoxygenation reaction under the metal-supported molecular sieve catalyst X / Y in a hydrogen atmosphere to produce the polycycloalkane high-density aviation fuel. The present invention prepares a high-density aviation fuel of methyl-substituted polycycloalkanes with carbon numbers of 12, 13, 17, and 19 via the one-pot method. The high-density fuel obtained by the present invention has a density exceeding 0.90 g / mL and exhibits excellent fuel performance. The present invention does not require purification and separation of intermediates, thereby reducing production costs and improving production efficiency. The present invention provides a new route for the synthesis of biomass high-density aviation fuel.

Description

Technical Field

[0001] The present invention belongs to the field of aviation and aerospace technology, and more particularly, the present invention relates to a one-pot method for synthesizing polycycloalkane high-density aviation fuel. Background Art

[0002] High-density aviation fuel is artificially synthesized with a density greater than 0.80 g·mL -1 Aviation fuel, a type of fuel with both military and commercial applications, is widely used in aerospace vehicles such as aircraft, rockets, missiles, spacecraft, and satellites. The performance of a spacecraft depends largely on the density and volumetric calorific value of the fuel used. Given a given fuel tank volume, the higher the fuel density, the greater its volumetric calorific value, effectively improving the aircraft's flight performance, including range, speed, and payload. Given a given thrust, the higher the fuel density, the smaller the fuel tank volume it occupies, effectively reducing the aircraft's volumetric capacity. Currently, high-density aviation fuel is primarily produced from petroleum raw materials through processes such as distillation, cracking, and reforming, or through artificial synthesis, making it non-renewable. With the gradual depletion of fossil energy and the increasing greenhouse effect, the production of liquid fuels from renewable resources, particularly biomass resources, is gaining increasing attention to protect the global environment and achieve sustainable development.

[0003] Biomass is a complex of naturally occurring macromolecular compounds. The total amount of biomass produced annually by photosynthesis on Earth exceeds 200 billion tons. Lignocellulose, represented by crop straw and forestry waste, is the most widespread biomass resource, with an annual production of approximately 170 billion tons. Lignocellulose is composed of three basic structures: cellulose (40-50%), hemicellulose (25-35%), and lignin (15-20%) (Angew. Chem. Int. Ed., 2010, 47, 9200-9211; Ind. Eng. Chem. Res., 2009, 48, 3713-3729). Small biomass compounds, such as cyclic alcohols and biophenols (phenol, catechol, 2-methylphenol, 3-methylphenol, and 4-methylphenol), can be obtained through rapid catalytic cracking (Chem. Rev., 2007, 107, 2411-2502; Polym. Chem., 2015, 6, 4497-4559; ChemSusChem, 2012, 5, 1602-1609). From a fuel structure perspective, fuel density increases with increasing ring structure, and so does the volumetric calorific value. Furthermore, methyl substituents in the ring structure significantly lower the freezing point of the compound (Energy Fuels, 2021, 35, 6691-6699). Biophenols possess both a ring structure and a methyl group. Alkylation with biophenols (cyclopentanol and cyclohexanol) allows for further ring and carbon addition. Finally, through hydrogenation and deoxygenation, they can be used to produce high-density fuels containing methyl-substituted polycycloalkanes. These fuels possess the advantages of high density and a low freezing point. Considering the raw material source, biophenols can be produced directly from biomass on a large scale, offering enormous potential for application. Summary of the Invention

[0004] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0005] In order to achieve these objects and other advantages according to the present invention, a method for synthesizing polycycloalkane high-density aviation fuel in one pot is provided, comprising the following steps:

[0006] Step 1: Under solvent-free conditions, metal-supported molecular sieve catalyst X / Y catalyzes the alkylation reaction of biomass phenol and cyclic alcohol to prepare an intermediate compound;

[0007] Step 2: Under a hydrogen atmosphere, the intermediate compound is subjected to a hydrogenation deoxygenation reaction catalyzed by a molecular sieve catalyst X / Y to prepare a polycycloalkane high-density aviation fuel.

[0008] Preferably, the metal-supported molecular sieve catalyst X / Y comprises an active component X and a carrier Y, wherein the active component X is one or a mixture of two or more of Fe, Ni, Pd, Pt, and Ru; the carrier Y is one or a mixture of two or more of ZSM-5, MCM-41, SBA-15, Hβ, HY, and MCM-22; and the metal-supported molecular sieve catalyst X / Y is prepared by an equal volume impregnation method and a deposition precipitation method.

[0009] Preferably, the equal volume impregnation method includes: the carrier Y needs to be pretreated at 100-300°C for 1-24h before impregnation, the impregnation liquid is a soluble salt solution of the active component X, and the pretreated carrier Y is added to the soluble salt solution of the active component X at a mass ratio of active component X: carrier Y = 0..05:1 for equal volume impregnation, standing for 6-24h, then drying at 60-200°C, and then calcining at 400-800°C for 2-8h to obtain the metal-supported molecular sieve catalyst X / Y.

[0010] Preferably, the deposition precipitation method comprises: dividing the soluble salt solution of the active component X into two parts, A and B, adding the carrier Y to A and the precipitant urea to B, then slowly adding B to A at 40-90°C, maintaining at 40-90°C for 6-24h, drying at 100-200°C for 2-24h, and then calcining at 400-800°C for 2-12h to obtain the metal-supported molecular sieve catalyst X / Y.

[0011] Preferably, the mass ratio of the active component X to the carrier Y in part A is 0.025:1, and the molar ratio of the active component X to urea in part B is 1:6.

[0012] Preferably, the prepared metal-supported molecular sieve catalyst X / Y needs to be reduced before use, and the reduction treatment method includes: in a tubular furnace, a hydrogen pressure of 0.1-2.0 MPa, a hydrogen space velocity of 100-5000 h -1 , reduction temperature 200-600℃, reduction time 1-12h.

[0013] Preferably, the step 1 is carried out in a high-pressure reactor, the reaction temperature is 140-200° C., and the reaction time is 1-12 h.

[0014] Preferably, the reaction temperature is 160-180° C., and the reaction time is 1-6 h.

[0015] Preferably, the step 2 is carried out in a high-pressure reactor, with a hydrogen pressure of 1-5 MPa, a reaction temperature of 120-180° C., and a reaction time of 1-12 h.

[0016] Preferably, the hydrogen pressure is 1-3 MPa, the reaction temperature is 150-180° C., and the reaction time is 1-6 h.

[0017] The present invention has at least the following beneficial effects: using biomass phenol and bio-based cyclic alcohols (cyclopentanol and cyclohexanol) as raw materials, the present invention prepares metal-supported molecular sieve catalysts X / Y to catalyze the alkylation reaction of the biomass phenol and bio-based cyclic alcohols, followed by a further hydrodeoxygenation reaction, thereby achieving a two-step, one-pot production of polycycloalkane high-density aviation fuel. This production process eliminates the need for intermediate separation, thereby reducing production costs and improving production efficiency, providing a preferred route for synthesizing high-density aviation fuel.

[0018] This invention prepares high-density aviation fuel composed of methyl-substituted polycycloalkanes with carbon numbers of 12, 13, 17, and 19 through a one-pot process. The resulting high-density fuel has a density exceeding 0.90 g / mL and exhibits excellent fuel performance. This method eliminates the need for intermediate purification and separation, saving production costs and improving production efficiency. This invention provides a new route for the synthesis of biomass-based high-density aviation fuel.

[0019] Other advantages, objectives and features of the present invention will be reflected in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The present invention provides a synthetic route for the one-pot synthesis of polycycloalkane high-density aviation fuel. DETAILED DESCRIPTION

[0021] The present invention is described in further detail below so that those skilled in the art can implement the invention with reference to the description.

[0022] It should be understood that terms such as “having”, “including” and “comprising” used herein do not preclude the existence or addition of one or more other elements or combinations thereof.

[0023] Example 1

[0024] This embodiment provides a method for preparing a ZSM-5 carrier-supported platinum (Pt) molecular sieve catalyst, comprising:

[0025] The carrier ZSM-5 needs to be pretreated at 200°C for 24 hours before impregnation; a 10% mass fraction of chloroplatinic acid solution is prepared, and the mass ratio of platinum to carrier ZSM-5 is 0.05:1. ZSM-5 is added to the chloroplatinic acid solution in equal volumes for impregnation, left to stand for 24 hours, dried at 100°C, and then calcined at 500°C for 2 hours, and reduced with hydrogen at 500°C for 2 hours. The hydrogen pressure is 0.1MPa and the hydrogen space velocity is 500h-1 After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain a ZSM-5 carrier-supported platinum (Pt) molecular sieve catalyst.

[0026] Example 2

[0027] This embodiment provides a method for preparing a ZSM-5 carrier-supported palladium (Pd) molecular sieve catalyst, comprising:

[0028] The carrier ZSM-5 needs to be pretreated at 200°C for 24 hours before impregnation; a palladium chloride solution with a mass fraction of 10% is prepared, and the carrier ZSM-5 is added to an equal volume of palladium chloride solution according to a mass ratio of palladium to carrier ZSM-5 of 0.05:1 for impregnation, and then allowed to stand for 24 hours, dried at 100°C, and then calcined at 500°C for 2 hours, and reduced with hydrogen at 500°C for 2 hours, with a hydrogen pressure of 0.1 MPa and a hydrogen space velocity of 500h -1 After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain a ZSM-5 carrier-supported palladium (Pd) molecular sieve catalyst.

[0029] Example 3

[0030] This embodiment provides a method for preparing a ZSM-5 carrier-supported ruthenium (Ru) molecular sieve catalyst, comprising:

[0031] The carrier ZSM-5 needs to be pretreated at 200°C for 24 hours before impregnation; a 10% mass fraction of ruthenium chloride solution is prepared, and the carrier ZSM-5 is added to an equal volume of the ruthenium chloride solution according to the mass ratio of ruthenium to carrier ZSM-5 of 0.05:1 for impregnation, and then allowed to stand for 24 hours, dried at 100°C, and then calcined at 500°C for 2 hours, and reduced with hydrogen at 500°C for 2 hours, with a hydrogen pressure of 0.1MPa and a hydrogen space velocity of 500h- 1 After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain a ZSM-5 carrier-loaded ruthenium (Ru) molecular sieve catalyst.

[0032] Example 4

[0033] This embodiment provides a method for preparing a ZSM-5 carrier-supported nickel (Ni) molecular sieve catalyst, comprising:

[0034] The carrier ZSM-5 needs to be pretreated at 200°C for 24 hours before impregnation; a nickel nitrate solution with a mass fraction of 10% is prepared, and the carrier ZSM-5 is added to the nickel nitrate solution in an equal volume for impregnation according to the mass ratio of nickel to carrier ZSM-5 of 0.05:1. The carrier ZSM-5 is allowed to stand for 24 hours, dried at 100°C, and then calcined at 500°C for 2 hours. The carrier is reduced with hydrogen at 500°C for 2 hours, with a hydrogen pressure of 0.1MPa and a hydrogen space velocity of 500h- 1After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain a ZSM-5 carrier-loaded nickel (Ni) molecular sieve catalyst.

[0035] Example 5

[0036] This embodiment provides a method for preparing a ZSM-5 carrier-supported iron (Fe) molecular sieve catalyst, comprising:

[0037] The carrier ZSM-5 needs to be pretreated at 500°C for 24 hours before impregnation; a 10% mass fraction of ferric nitrate solution is prepared, and the ZSM-5 is added to the ferric nitrate solution in an equal volume for impregnation according to the mass ratio of iron to carrier ZSM-5 of 0.05:1. The ZSM-5 is allowed to stand for 24 hours, dried at 100°C, and then calcined at 500°C for 2 hours. The hydrogen reduction is carried out at 500°C for 2 hours, the hydrogen pressure is 0.1MPa, and the hydrogen space velocity is 500h- 1 After the temperature drops to room temperature, O2:N2=1:100 is introduced for passivation to obtain the ZSM-5 carrier-supported iron (Fe) molecular sieve catalyst.

[0038] Example 6

[0039] This embodiment provides a method for preparing a palladium (Pd) molecular sieve catalyst supported on an MCM-41 carrier, comprising:

[0040] The carrier MCM-41 needs to be pretreated at 200°C for 24 hours before impregnation; a palladium chloride solution with a mass fraction of 10% is prepared, and the carrier MCM-41 is added to an equal volume of palladium chloride solution for impregnation according to the mass ratio of palladium to carrier MCM-41 of 0.05:1. The carrier MCM-41 is allowed to stand for 2 hours, dried at 100°C, and then calcined at 500°C for 2 hours. The carrier is reduced with hydrogen at 500°C for 2 hours, with a hydrogen pressure of 0.1 MPa and a hydrogen space velocity of 500h- 1 After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain the MCM-41 carrier-supported palladium (Pd) molecular sieve catalyst.

[0041] Example 7

[0042] This embodiment provides a method for preparing a SBA-15 carrier-supported palladium (Pd) molecular sieve catalyst, comprising:

[0043] The carrier SBA-15 needs to be pretreated at 200°C for 24 hours before impregnation; a palladium chloride solution with a mass fraction of 10% is prepared, and the carrier SBA-15 is added to an equal volume of palladium chloride solution according to a mass ratio of palladium to carrier SBA-15 of 0.05:1 for impregnation, and then allowed to stand for 2 hours, dried at 100°C, and then calcined at 500°C for 2 hours, and reduced with hydrogen at 500°C for 2 hours, with a hydrogen pressure of 0.1 MPa and a hydrogen space velocity of 500h- 1After the temperature drops to room temperature, O2:N2=1:100 is introduced for passivation to obtain the SBA-15 carrier-supported palladium (Pd) molecular sieve catalyst.

[0044] Example 8

[0045] This embodiment provides a method for preparing a Hβ carrier-supported palladium (Pd) molecular sieve catalyst, comprising:

[0046] The carrier Hβ needs to be pretreated at 200°C for 24 hours before impregnation; a palladium chloride solution with a mass fraction of 10% is prepared, and the carrier Hβ is added to an equal volume of palladium chloride solution for impregnation according to a mass ratio of palladium to carrier Hβ of 0.05:1. The carrier Hβ is allowed to stand for 2 hours, dried at 100°C, and then calcined at 500°C for 2 hours. The carrier is reduced with hydrogen at 500°C for 2 hours, the hydrogen pressure is 0.1MPa, and the hydrogen space velocity is 500h-1. After the temperature drops to room temperature, a volume of O2:N2 = 1:100 is introduced for passivation, and different Hβ carrier-loaded palladium (Pd) molecular sieve catalysts can be obtained.

[0047] Example 9

[0048] This embodiment provides a method for preparing a HY-supported palladium (Pd) molecular sieve catalyst, comprising:

[0049] The carrier HY needs to be pretreated at 200 ° C for 24 hours before impregnation; prepare a palladium chloride solution with a mass fraction of 10%, add the carrier HY into the palladium chloride solution according to the mass ratio of palladium to carrier HY of 0.05:1, and impregnate it. Let it stand for 2 hours, dry it at 100 ° C, and then calcine it at 500 ° C for 2 hours, and reduce it with hydrogen at 500 ° C for 2 hours. The hydrogen pressure is 0.1 MPa and the hydrogen space velocity is 500h -1 After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain the HY supported palladium (Pd) molecular sieve catalyst.

[0050] Example 10

[0051] This embodiment provides a method for preparing a palladium (Pd) molecular sieve catalyst X / Y supported on an MCM-22 carrier, comprising:

[0052] The carrier MCM-22 needs to be pretreated at 200°C for 24 hours before impregnation; a palladium chloride solution with a mass fraction of 10% is prepared, and the carrier MCM-22 is added to an equal volume of palladium chloride solution according to a mass ratio of palladium to carrier MCM-22 of 0.05:1, and the carrier MCM-22 is impregnated, left to stand for 2 hours, dried at 100°C, and then calcined at 500°C for 2 hours, and reduced with hydrogen at 500°C for 2 hours, with a hydrogen pressure of 0.1 MPa and a hydrogen space velocity of 500h -1After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain the MCM-22 carrier-supported palladium (Pd) molecular sieve catalyst.

[0053] Example 11

[0054] This embodiment provides a method for preparing a nickel (Ni) molecular sieve catalyst supported on an Hβ carrier, comprising:

[0055] Prepare 100 mL of 0.1 M nickel nitrate solution and divide it into two parts, A and B, with equal volumes. Add 7.3 mg of Hβ carrier and 10 mL of concentrated nitric acid to A, and add 100 mL of 0.3 M urea to B. Add B dropwise to A under the condition of heating at 80 ° C in a water bath. Heat to 80 ° C and stir for 10 h. Filter and wash. Dry at 80 ° C overnight. Then calcine at 500 ° C for 2 h. Reduce with hydrogen at 500 ° C for 2 h. The hydrogen pressure is 0.1 MPa and the hydrogen space velocity is 500 h. -1 After the temperature drops to room temperature, O2:N2 is introduced in a volume ratio of 1:100 for passivation to obtain the Hβ carrier-loaded nickel (Ni) molecular sieve catalyst.

[0056] The carriers, noble metals and loading amounts of Examples 1 to 11 are shown in the following table:

[0057] Table 1 Metal-supported molecular sieve catalyst X / Y

[0058]

[0059]

[0060] Example 12

[0061] like Figure 1 As shown, this embodiment provides a method for preparing an intermediate compound by alkylation reaction, comprising:

[0062] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of the Hβ carrier-supported palladium (Pd) molecular sieve catalyst prepared in Example 8 were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction was completed, samples were taken for GC detection.

[0063] Example 13

[0064] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0065] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of the MCM-41 carrier-supported palladium (Pd) molecular sieve catalyst prepared in Example 6 were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction was completed, samples were taken for GC detection.

[0066] Example 14

[0067] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0068] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of the SBA-15 carrier-supported palladium (Pd) molecular sieve catalyst prepared in Example 7 were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction was completed, samples were taken for GC detection.

[0069] Example 15

[0070] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0071] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of the ZSM-5 carrier-supported palladium (Pd) molecular sieve catalyst prepared in Example 2 were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction was completed, samples were taken for GC detection.

[0072] Example 16

[0073] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0074] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of the HY carrier-supported palladium (Pd) molecular sieve catalyst prepared in Example 9 were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction, samples were taken for GC detection.

[0075] Example 17

[0076] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0077] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of the MCM-22 carrier-supported palladium (Pd) molecular sieve catalyst prepared in Example 10 were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction was completed, samples were taken for GC detection.

[0078] Example 18

[0079] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0080] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of the Hβ carrier-supported nickel (Ni) molecular sieve catalyst prepared in Example 11 were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction was completed, samples were taken for GC detection.

[0081] Example 19

[0082] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0083] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of Hβ-supported ruthenium (Ru) molecular sieve catalyst were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction, samples were taken for GC detection.

[0084] Example 20

[0085] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0086] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of Hβ-supported platinum (Pt) molecular sieve catalyst were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction, samples were taken for GC detection.

[0087] Example 21

[0088] This embodiment provides a method for preparing an intermediate compound by an alkylation reaction, comprising:

[0089] In a 100 mL high-pressure reactor, p-cresol (10 mmol), cyclopentanol (30 mmol), and 1 g of Hβ-supported iron (Fe) molecular sieve catalyst were added, and the mixture was heated at 160° C. and stirred for 6 h. After the reaction, samples were taken for GC detection.

[0090] The GC detection results of the alkylation reactions of Examples 12 to 21 are shown in the following table:

[0091] Table 2 Alkylation reaction results

[0092]

[0093]

[0094] Among the alkylated products, the structural formula of intermediate A is The structural formula of intermediate B is

[0095] It can be seen from Table 2 that Hβ molecular sieve has the best catalytic effect on alkylation as a solid acid catalyst. The metal loading on Hβ molecular sieve has little effect on the conversion rate of the reactants, but has a certain effect on the selectivity of A and B.

[0096] Example 22

[0097] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0098] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 3 MPa and the temperature was 150° C. The reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0099] Example 23

[0100] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0101] Hydrogen was introduced into the high-pressure reactor of Example 21, the pressure was maintained at 3 MPa, the temperature was 150° C., and the reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0102] Example 24

[0103] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0104] Hydrogen was introduced into the high-pressure reactor of Example 12, and the pressure was maintained at 3 MPa and the temperature was 150° C. The reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0105] Example 25

[0106] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0107] Hydrogen was introduced into the high-pressure reactor of Example 19, the pressure was maintained at 3 MPa, the temperature was 150° C., and the reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0108] Example 26

[0109] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0110] Hydrogen was introduced into the high-pressure reactor of Example 20, the pressure was maintained at 3 MPa, the temperature was 150° C., and the reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0111] Example 27

[0112] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0113] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 3 MPa and the temperature was 160° C. The reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0114] Example 28

[0115] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0116] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 3 MPa and the temperature was 170° C. The reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0117] Example 29

[0118] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0119] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 3 MPa and the temperature was 180° C. The reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0120] Example 30

[0121] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0122] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 1 MPa and the temperature was 180° C. The reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0123] Example 31

[0124] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0125] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 2 MPa and the temperature was 180° C. The reaction was carried out for 6 h. After the reaction was completed, samples were taken for GC detection.

[0126] Example 32

[0127] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0128] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 3 MPa and the temperature was 180° C. The reaction was carried out for 3 h. After the reaction was completed, samples were taken for GC detection.

[0129] Example 33

[0130] This embodiment provides a method for preparing polycycloalkane high-density aviation fuel by hydrodeoxygenating an intermediate compound over a molecular sieve catalyst X / Y in a hydrogen atmosphere, comprising:

[0131] Hydrogen was introduced into the high-pressure reactor of Example 18, and the pressure was maintained at 3 MPa and the temperature was 180° C. The reaction was carried out for 1 hour. After the reaction was completed, samples were taken for GC detection.

[0132] The GC test results of the hydrodeoxygenation reactions of Examples 22 to 33 are shown in the following table:

[0133] Table 3 Hydrodeoxygenation reaction results

[0134]

[0135] In the final product, the structural formula of C12 product is The structural formula of the C17 product is

[0136] It can be seen from Table 3 that under the same reaction conditions, the Ni, Pd, Ru, and Pt loaded Hβ molecular sieve catalysts have similar efficiencies in catalyzing the hydrodeoxygenation of alkylation products. However, considering the cost of the catalyst, the Ni / Hβ catalyst is preferably selected as the catalyst for the reaction.

[0137] The properties of the C12, C17, C13, and C19 high-density aviation fuels prepared by the present invention are as follows:

[0138] Table 4 Properties of polycycloalkane high-density aviation fuel

[0139]

[0140] The above examples illustrate the catalyst preparation process and the results of a one-pot catalytic production of polycycloalkane high-density aviation fuel. Under the above reaction conditions, mixed fuels of C12, C17, and C13, C19 were obtained in high yields. These fuels have a density exceeding 0.90 g / mL and can be used directly as fuel or as an additive. This invention reduces production costs and improves production efficiency, providing a new route for the synthesis of biomass-based high-density aviation fuel.

[0141] The number of devices and processing scales described herein are intended to simplify the description of the present invention. Applications, modifications, and variations of the present invention will be readily apparent to those skilled in the art.

[0142] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and implementation methods. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and examples shown and described herein.

Claims

1. A one-pot method for synthesizing polycycloalkane high-density aviation fuel, characterized in that: The following steps are involved: Step 1: In a high-pressure reactor, under solvent-free conditions, metal-supported molecular sieve catalyst X / Y catalyzes the alkylation reaction of p-cresol and cyclopentanol to prepare an intermediate compound at a reaction temperature of 140-200°C and a reaction time of 1-12 h. Step 2: In a high-pressure reactor, under a hydrogen atmosphere, the intermediate compound is subjected to a hydrodeoxygenation reaction over a metal-supported molecular sieve catalyst X / Y to prepare a polycycloalkane high-density aviation fuel. The hydrogen pressure is 1-5 MPa, the reaction temperature is 120-180°C, and the reaction time is 1-12 h. The metal-supported molecular sieve catalyst X / Y comprises an active component X and a carrier Y, wherein the active component X is one or a mixture of two or more of Fe, Ni, Pd, Pt, and Ru; the carrier Y is one or a mixture of two or more of ZSM-5, MCM-41, SBA-15, Hβ, HY, and MCM-22; the metal-supported molecular sieve catalyst X / Y is prepared by a deposition precipitation method; The deposition precipitation method comprises: dividing a soluble salt solution of the active component X into two parts, A and B, of equal mass, adding a carrier Y to A and a precipitant, urea, to B, then slowly adding B to A at 40-90°C, maintaining the temperature at 40-90°C for 6-24 hours, drying at 100-200°C for 2-24 hours, and then calcining at 400-800°C for 2-12 hours to obtain the metal-supported molecular sieve catalyst X / Y; The mass ratio of the active component X to the carrier Y in A is 0.025:1, and the molar ratio of the active component X to urea in B is 1:

6.

2. The one-pot method for synthesizing polycycloalkane high-density aviation fuel according to claim 1, characterized in that: The prepared metal-supported molecular sieve catalyst X / Y needs to be reduced before use. The reduction treatment method includes: in a tubular furnace, a hydrogen pressure of 0.1-2.0 MPa, a hydrogen space velocity of 100-5000 h -1 , reduction temperature 200-600℃, reduction time 1-12h.

3. The one-pot method for synthesizing polycycloalkane high-density aviation fuel according to claim 1, characterized in that: In the step 1, the reaction temperature is 160-180° C., and the reaction time is 1-6 h.

4. The one-pot method for synthesizing polycycloalkane high-density aviation fuel according to claim 1, characterized in that: In the step 2, the hydrogen pressure is 1-3 MPa, the reaction temperature is 150-180° C., and the reaction time is 1-6 h.

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