Method for preparing JP-10 aviation fuel

Abstract

The invention provides a method for preparing JP-10 aviation fuel, which comprises the following steps: A) carrying out rearrangement reaction on furfural in the presence of hydrogen and a first catalyst to prepare cyclopentenone; (B) carrying out self dimerization reaction on cyclopentenone under the condition of ultraviolet light to obtain a C10 four-membered ring oxygen-containing compound; and C) performing hydrodeoxygenation and rearrangement reaction on the C10 four-membered ring oxygen-containing compound under the action of hydrogen and a second catalyst to obtain the JP-10 aviation fuel, the second catalyst comprises a molecular sieve supported catalyst and / or an activated carbon supported catalyst. According to the method, a five-membered carbon ring molecule cyclopentenone is prepared through furfural molecule reconstruction, a four-membered tension carbon ring is constructed through green and efficient photocatalytic [2 + 2] cycloaddition, and finally a cycloalkane product is efficiently prepared through a skeleton rearrangement hydrodeoxygenation reaction through a metal-loaded molecular sieve catalyst. Wherein the maximum selectivity of the hanging tetrahydrodicyclopentadiene can reach 93%.

Description

Technical Field

[0001] This invention belongs to the field of organic fuel technology, and in particular relates to a method for preparing JP-10 aviation fuel. Background Technology

[0002] The dwindling fossil resources and the massive greenhouse gas emissions from fossil fuel combustion are increasingly prominent environmental problems. Coupled with the continuously increasing societal demand for energy, the development of new energy sources to replace fossil resources is imperative. The application of biomass as a renewable organic carbon source in the production of carbon materials, fuels, and chemicals has become a hot research topic.

[0003] JP-10 aviation fuel is a commonly used high-density aviation fuel internationally. According to the US military standard MIL-P-87107C-1989, its density is 0.935 g / cm³. 3 With a freezing point of -78℃ and a calorific value of 42.1 MJ / kg, JP-10 possesses a higher energy density than conventional hydrocarbon fuels, making it a high-performance aviation fuel. It is widely used in supersonic fighter jets, cruise missiles, rockets, and other aircraft. JP-10 is a single-component fuel composed of bridging tetrahydrodicyclopentadiene with a purity of 98.5%. The current synthesis route for JP-10 involves using bridging dicyclopentadiene as a raw material, hydrogenating it to bridging tetrahydrodicyclopentadiene, and then isomerizing it under the catalysis of catalysts such as AlCl3 and H2SO4 to form bridging tetrahydrodicyclopentadiene. This method produces numerous byproducts at each step, requiring complex separation processes. The acid-catalyzed isomerization step causes severe environmental pollution and results in low yields. Other methods exist for synthesizing JP-10 aviation fuel, but these all rely on cyclopentadiene or dicyclopentadiene derived from fossil fuels, making them highly dependent on non-renewable fossil energy sources. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing JP-10 aviation fuel. The method of this invention uses simple and readily available catalysts and raw materials, and the reaction has high yield and selectivity.

[0005] This invention provides a method for preparing JP-10 aviation fuel, comprising the following steps:

[0006] A) Cyclopentenone was prepared by rearrangement reaction of furfural under hydrogen and a first catalyst.

[0007] B) The cyclopentenone was subjected to its own dimerization reaction under ultraviolet light to obtain a C10 four-membered ring oxygen-containing compound.

[0008] C) The C10 four-membered ring oxygen-containing compound is subjected to hydrogenation, deoxygenation and rearrangement reaction under the action of hydrogen and a second catalyst to obtain JP-10 aviation fuel;

[0009] The second catalyst includes a molecular sieve-supported catalyst and / or an activated carbon-supported catalyst;

[0010] The molecular sieve-supported catalyst is a molecular sieve-supported metal catalyst. The molecular sieve in the molecular sieve-supported catalyst includes one or more of the following: HY molecular sieve, LaY molecular sieve, CeY molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve; the supported metal includes one or more of Pd, Rh, Pt, and Ru.

[0011] The activated carbon supported catalyst includes an activated carbon supported metal catalyst and an auxiliary agent; the activated carbon supported metal catalyst includes one or more of Pd / C catalyst, Rh / C catalyst, Pt / C catalyst and Ru / C catalyst; the auxiliary agent includes molecular sieve and / or heteropoly acid.

[0012] Preferably, the first catalyst is a co-catalyst of a pentamethylcyclopentadienyl transition metal complex and a Lewis acid.

[0013] The transition metal in pentamethylcyclopentadienyl transition metal complexes includes one or more of iridium, ruthenium, and rhodium;

[0014] The ratio of the pentamethylcyclopentadienyl transition metal complex to the Lewis acid is (0.005~0.2) mmol: 1 mg;

[0015] The rearrangement reaction is carried out at a temperature of 0~300℃ for 0.5~24 hours, and the hydrogen pressure is 0.1~10MPa.

[0016] Preferably, in step B), the temperature of the dimerization reaction is 0~80℃ and the time of the dimerization reaction is 0.1~24 hours.

[0017] Preferably, in the molecular sieve supported metal catalyst, the molar ratio of SiO2 to Al2O3 is 10~200;

[0018] The mass of the metal element in the molecular sieve-supported metal catalyst is 0.01~50 wt% of the molecular sieve mass.

[0019] 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.

[0020] Preferably, the molar ratio of SiO2 to Al2O3 in the molecular sieve of the activated carbon supported catalyst is 10 to 200.

[0021] The metal in the activated carbon-supported metal catalyst is 0.5-20 wt% of the activated carbon mass.

[0022] The molar ratio of the metal in the activated carbon-supported metal catalyst to the C10 four-membered ring oxygen-containing compound is (0.0001~0.1):1.

[0023] Preferably, the molecular sieve in the additive includes one or more of the following: HY molecular sieve, LaY molecular sieve, CeY molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve.

[0024] The heteropoly acid includes one or more of trifluoromethanesulfonate, silicotungstic acid, phosphotungstic acid, or phosphomolybdic acid.

[0025] The mass ratio of the activated carbon-supported metal catalyst to the additive is (0.01~10):1.

[0026] Preferably, the temperature of the hydrogenation deoxygenation and rearrangement reaction in step C) is 100~350℃, the reaction time is 0.5~24 hours, and the hydrogen pressure is 0.1~10MPa.

[0027] Preferably, the rearrangement reaction in step A) is carried out in a first solvent, which includes one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide.

[0028] The dimerization reaction in step B) is carried out in a second solvent, which includes one or more of water, acetonitrile, ethyl acetate, benzene, toluene, cyclohexane, n-hexane, dichloromethane, and trichloromethane.

[0029] The hydrogenation-deoxygenation and rearrangement reactions in step C) are carried out in a third solvent, which includes one or more of cyclohexane, n-hexane, cyclopentane, and n-pentane.

[0030] Preferably, the concentration of the C10 four-membered ring oxygen-containing compound in the third solvent is 0.05~1 mol / L.

[0031] This invention provides a method for preparing JP-10 aviation fuel, comprising the following steps: A) preparing cyclopentenone by rearrangement reaction of furfural under hydrogen and a first catalyst; B) subjecting the cyclopentenone to self-dimerization under ultraviolet light to obtain a C10 four-membered ring oxygen-containing compound; C) subjecting the C10 four-membered ring oxygen-containing compound to hydrogenation, deoxygenation, and rearrangement reaction 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, and the molecular sieve in the molecular sieve supported catalyst includes HY molecular sieve, LaY molecular sieve, Ce The catalyst comprises one or more of the following: Y molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve; the supported metal comprises one or more of Pd, Rh, Pt, and Ru; the activated carbon supported catalyst comprises an activated carbon supported metal catalyst and an auxiliary agent; the activated carbon supported metal catalyst comprises one or more of Pd / C catalyst, Rh / C catalyst, Pt / C catalyst, and Ru / C catalyst; the auxiliary agent comprises molecular sieve and / or heteropolyacid.

[0032] This invention achieves highly selective preparation of high-purity straddle-shaped tetrahydrodicyclopentadiene from furfural through a three-step reaction, which, after purification, can be used as JP-10 aviation fuel. The novel reaction pathway involves the reconstruction of furfural molecules to prepare the five-membered carbon ring molecule cyclopentenone, followed by the construction of a four-membered strained carbon ring via a green and efficient photocatalytic [2+2] cycloaddition, and finally, the efficient preparation of cycloalkane products through a metal-supported molecular sieve catalyst for skeletal rearrangement and hydrodeoxygenation. The selectivity for straddle-shaped tetrahydrodicyclopentadiene can reach up to 93%, and the catalyst is simple to synthesize, suitable for large-scale preparation. After simple subsequent purification, it can be used as JP-10 aviation fuel or directly as a special aviation fuel. This route is green and environmentally friendly, and is an efficient method for synthesizing JP-10 aviation fuel from the renewable biomass platform compound furfural, which is beneficial for promoting the high-value utilization of biomass resources. Attached Figure Description

[0033] 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, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0034] Figure 1The furfural rearrangement product cyclopentenone in Example 1 of this invention 1 H-NMR spectrum;

[0035] Figure 2 The furfural rearrangement product cyclopentenone in Example 1 of this invention 13 C-NMR spectrum;

[0036] Figure 3 The C10 four-membered ring oxygen-containing compound, which is the self-dimerization product of cyclopentenone in Example 1 of this invention. 1 H-NMR spectrum;

[0037] Figure 4 The C10 four-membered ring oxygen-containing compound, which is the self-dimerization product of cyclopentenone in Example 1 of this invention. 13 C-NMR spectrum;

[0038] Figure 5 The product of hydrogenation and deoxygenation of the C10 four-membered ring oxygen-containing compound in Example 1 of this invention. 1 H-NMR spectrum;

[0039] Figure 6 The product of hydrogenation and deoxygenation of the C10 four-membered ring oxygen-containing compound in Example 1 of this invention. 13 C-NMR spectrum;

[0040] Figure 7 This is a gas chromatogram of the hydrogenation deoxygenation product of the C10 four-membered ring oxygen-containing compound in Example 1 of the present invention;

[0041] Figure 8 This is the mass spectrum of the hanging tetrahydrodicyclopentadiene in Example 1 of the present invention;

[0042] Figure 9 This is the mass spectrum of the bridged tetrahydrodicyclopentadiene in Example 1 of the present invention. Detailed Implementation

[0043] This invention provides a method for preparing JP-10 aviation fuel, comprising the following steps:

[0044] A) Cyclopentenone was prepared by rearrangement reaction of furfural under hydrogen and a first catalyst.

[0045] B) The cyclopentenone was subjected to its own dimerization reaction under ultraviolet light to obtain a C10 four-membered ring oxygen-containing compound.

[0046] C) The C10 four-membered ring oxygen-containing compound is subjected to hydrogenation, deoxygenation and rearrangement reaction under the action of hydrogen and a second catalyst to obtain JP-10 aviation fuel;

[0047] The second catalyst includes a molecular sieve-supported catalyst and / or an activated carbon-supported catalyst;

[0048] The molecular sieve-supported catalyst is a molecular sieve-supported metal catalyst. The molecular sieve in the molecular sieve-supported catalyst includes one or more of the following: HY molecular sieve, LaY molecular sieve, CeY molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve; the supported metal includes one or more of Pd, Rh, Pt, and Ru.

[0049] The activated carbon supported catalyst includes an activated carbon supported metal catalyst and an auxiliary agent; the activated carbon supported metal catalyst includes one or more of Pd / C catalyst, Rh / C catalyst, Pt / C catalyst and Ru / C catalyst; the auxiliary agent includes molecular sieve and / or heteropoly acid.

[0050] This invention involves three reactions to prepare JP-10 aviation fuel using furfuryl alcohol as a raw material:

[0051]

[0052] Reaction 1 involves the rearrangement reaction of furfural solution under the first catalyst and hydrogen conditions to prepare cyclopentenone (see Applied Catalysis A, 2017, 543, 266-273).

[0053] Reaction 2 involves the self-dimerization of cyclopentenone under ultraviolet light to generate a C10 four-membered ring oxygen-containing compound;

[0054] Reaction 3 involves the hydrogenation and deoxygenation of the C10 four-membered ring oxygen-containing compound generated in the previous step, involving a novel method for constructing a tetrahydrodicyclopentadiene skeleton. During this process, rearrangement occurs to generate a product primarily composed of hanging tetrahydrodicyclopentadiene. The obtained product, after purification, can be used as JP-10 aviation fuel, or directly as a special fuel with JP-10 as its main component.

[0055] In this invention, the first catalyst is a co-catalyst of a pentamethylcyclopentadienyl transition metal complex and a Lewis acid, wherein the transition metal in the pentamethylcyclopentadienyl transition metal complex includes one or more of iridium, ruthenium, and rhodium; specifically, in some embodiments of this invention, the pentamethylcyclopentadienyl transition metal complex includes the following 15 structures;

[0056]

[0057] Specifically, in some embodiments of the present invention, the pentamethylcyclopentadienyl transition metal complex is preferably a pentamethylcyclopentadienyl iridium(III) complex (hereinafter referred to as Cp*Ir(III) complex), wherein the Cp*Ir(III) complex is preferably [Cp*Ir(4,4'-(OH)2-bpy)(H2O)]SO4 (i.e., the structure in Formula 1 where R is -OH), and the Lewis acid preferably includes one or more of γ-Al2O3-2, γ-Al2O3-1, Ta2O5, TiO2, α-Al2O3, WO3, ZrO2 and Nb2O5. Multiple; the molar ratio of the pentamethylcyclopentadienyl transition metal complex to furfural is preferably (0.01~0.5):1, more preferably (0.1~0.4):1, such as 0.01:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, preferably a range of values ​​with any of the above as the upper or lower limit; the molar ratio of the pentamethylcyclopentadienyl transition metal complex to Lewis acid is preferably (0.002~0.1) mmol:1 mg, more preferably (0.01~0.08) mmol:1 mg, such as 0.002... mmol: 1 mg, 0.005 mmol: 1 mg, 0.01 mmol: 1 mg, 0.02 mmol: 1 mg, 0.03 mmol: 1 mg, 0.04 mmol: 1 mg, 0.05 mmol: 1 mg, 0.06 mmol: 1 mg, 0.07 mmol: 1 mg, 0.08 mmol: 1 mg, 0.09 mmol: 1 mg, 0.1 mmol: 1 mg, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0058] In this invention, the furfural is preferably subjected to the rearrangement reaction in a first solution, which preferably includes one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide. The concentration of furfural in the furfural solution is preferably 0.01~0.1 mol / L, more preferably 0.05~0.08 mol / L, such as 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0059] In this invention, the temperature of the rearrangement reaction is preferably 0~300℃, more preferably 50~250℃, such as 0℃, 50℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 250℃, 300℃, preferably within the range of any of the above values ​​as the upper or lower limit; the time of the rearrangement reaction is preferably 0.5~24 hours, more preferably 6~12 hours; the rearrangement reaction is preferably carried out in a reaction vessel or a fixed-bed reactor; the pressure of hydrogen in the rearrangement reaction is preferably 0.1~10MPa, more preferably 1~8MPa, such as 0.1 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, preferably within the range of any of the above values ​​as the upper or lower limit.

[0060] After obtaining cyclopentenone, the present invention mixes the cyclopentenone with a second solvent and carries out its own dimerization reaction under ultraviolet light to obtain a C10 four-membered ring oxygen-containing compound. The C10 four-membered ring oxygen-containing compound product is a mixture of various isomers (involving head-to-head and head-to-tail isomers, as well as cis-trans isomers of fused rings), and the different isomers have the same activity and product properties after hydrogenation and deoxygenation.

[0061] In this invention, the second solvent preferably includes one or more of water, acetonitrile, ethyl acetate, benzene, toluene, cyclohexane, n-hexane, dichloromethane, and chloroform. In the dimerization reaction system, the concentration of cyclopentenone is preferably 0.1~1 mol / L, more preferably 0.2~0.8 mol / L, such as 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, preferably within the range of any of the above values ​​as the upper or lower limit.

[0062] In this invention, the temperature of the dimerization reaction is preferably 0~80℃, more preferably 10~70℃, such as 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, preferably within a range where any of the above values ​​is the upper or lower limit. The time of the dimerization reaction is preferably 0.1~24 hours, more preferably 8~12 hours. The wavelength of the ultraviolet light is preferably 180~500nm, more preferably 185~254nm. The irradiance of the ultraviolet light is preferably 3~10 W / cm². 2 More preferably 5~8 W / cm 2 .

[0063] After obtaining the C10 four-membered ring oxygen-containing compound, the present invention mixes the C10 four-membered ring oxygen-containing compound, a second catalyst, and a third solvent, and carries out a one-step hydrodeoxygenation and rearrangement reaction under hydrogen conditions to obtain JP-10 aviation fuel. It can be prepared using a reaction vessel or a fixed-bed reactor.

[0064] In this invention, the second catalyst is a molecular sieve supported catalyst and / or an activated carbon supported catalyst.

[0065] In this invention, the molecular sieve-supported catalyst is a molecular sieve-supported metal catalyst. The molecular sieve in the molecular sieve-supported catalyst includes one or more of the following: HY molecular sieve, LaY molecular sieve, CeY molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve. The molar ratio of SiO2 to Al2O3 in the molecular sieve is preferably 10-200, more preferably 50-150, and even more preferably the supported metal includes one or more of Pd, Rh, Pt, and Ru. In this invention, the metal in the molecular sieve-supported metal catalyst exists in the form of a metal oxide, wherein the mass of the metal element is preferably 0.01-50 wt% of the molecular sieve mass, more preferably 1-30 wt%, such as 0.01 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%. wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0066] In this invention, the molar ratio of the metal element in the molecular sieve-supported metal catalyst to the C10 four-membered ring oxygen-containing compound is preferably (0.0001~0.1):1, more preferably (0.001~0.08):1, such as 0.0001:1, 0.001:1, 0.005:1, 0.01:1, 0.012:1, 0.015:1, 0.018:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0067] In this invention, the molecular sieve-supported metal catalyst can be prepared using conventional synthesis methods in the art, such as impregnation. In some embodiments of this invention, the specific steps include:

[0068] The metal compound and molecular sieve were mixed and stirred in a solvent, the turbid liquid was dried, the resulting solid was washed with water and dried, and then calcined in air to obtain a molecular sieve-supported metal catalyst.

[0069] In this invention, the metal compound is preferably one or more of Pd compounds, Rh compounds, Pt compounds, and Ru compounds; the type of molecular sieve is the same as that described above, and will not be repeated here. The metal compound and molecular sieve are mixed in the proportions described above, and will not be repeated here.

[0070] In this invention, the mixing temperature is preferably 15~25℃, more preferably 20~25℃, and the mixing time is preferably 1~10 hours, more preferably 4~8 hours; the solvent used is preferably water.

[0071] In this invention, the drying temperature of the suspension is preferably 100~150℃, more preferably 120~130℃, and the drying time of the suspension is preferably 8~24 hours, more preferably 12~18 hours; the drying temperature after washing is preferably 100~150℃, more preferably 120~130℃.

[0072] In this invention, the calcination temperature is preferably 300~500℃, more preferably 400~450℃, and the calcination holding time is preferably 3~6 hours, more preferably 4~5 hours; the calcination heating rate is preferably 1~10℃ / min, more preferably 3~8℃ / min, and most preferably 5~6℃ / min; the cooling rate after the holding time is preferably 1~10℃ / min, more preferably 3~8℃ / min, and most preferably 5~6℃ / min.

[0073] In this invention, the activated carbon-supported catalyst comprises an activated carbon-supported metal catalyst and an additive; the activated carbon-supported metal catalyst comprises one or more of Pd / C catalyst, Rh / C catalyst, Pt / C catalyst, and Ru / C catalyst; the mass of the metal in the activated carbon-supported metal catalyst is preferably 0.5-20 wt% of the activated carbon mass, more preferably 5-10 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0074] In this invention, the additive preferably comprises molecular sieves and / or heteropoly acids, wherein the molecular sieves include one or more of HY molecular sieves, LaY molecular sieves, CeY molecular sieves, NaY molecular sieves, ReY molecular sieves, NH4Y molecular sieves, USY molecular sieves, mesoporous Y molecular sieves, ZSM-5 molecular sieves, ZSM-35 molecular sieves, MCM-22 molecular sieves, β molecular sieves, SAPO molecular sieves, MCM-49 molecular sieves, ERB-1 molecular sieves, and ITQ-1 molecular sieves; and the heteropoly acids include one or more of trifluoromethanesulfonate, silicotungstic acid, phosphotungstic acid, or phosphomolybdic acid.

[0075] In this invention, the mass ratio of the activated carbon-supported metal catalyst to the auxiliary agent is preferably (0.01~100):1, more preferably (1~80):1, such as 0.01:1, 0.5:1, 1:1, 5:1, 10:1, 15:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0076] In this invention, the molar ratio of the metal in the activated carbon-supported catalyst to the C10 four-membered ring oxygen-containing compound is preferably (0.0001~0.1):1, more preferably (0.001~0.08):1, such as 0.0001:1, 0.001:1, 0.005:1, 0.01:1, 0.012:1, 0.015:1, 0.018:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, and preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0077] In this invention, the third solvent preferably includes one or more of cyclohexane, n-hexane, cyclopentane, and n-pentane; the concentration of the C10 four-membered ring oxygen-containing compound in the third solvent is preferably 0.01~1 mol / L, more preferably 0.05~0.8 mol / L, such as 0.01 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, preferably a range of values ​​with any of the above values ​​as the upper or lower limit.

[0078] In this invention, the temperature of the hydrodeoxygenation and rearrangement reaction is preferably 100~350℃, more preferably 150~300℃, such as 100℃, 150℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 350℃, preferably within the range of any of the above values ​​as the upper or lower limit; the time of the hydrodeoxygenation and rearrangement reaction is preferably 3~12 hours, more preferably 6~10 hours; during the hydrodeoxygenation and rearrangement reaction, the pressure of hydrogen is preferably 0.1~10 MPa, more preferably 1~8 MPa, such as 0.1 MPa, 1 MPa, 2 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, preferably within the range of any of the above values ​​as the upper or lower limit.

[0079] This invention provides a method for preparing JP-10 aviation fuel, comprising the following steps: A) preparing cyclopentenone by rearrangement reaction of furfural under hydrogen and a first catalyst; B) subjecting the cyclopentenone to self-dimerization under ultraviolet light to obtain a C10 four-membered ring oxygen-containing compound; C) subjecting the C10 four-membered ring oxygen-containing compound to hydrogenation, deoxygenation, and rearrangement reaction 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, and the molecular sieve in the molecular sieve supported catalyst includes HY molecular sieve, LaY molecular sieve, Ce The catalyst comprises one or more of the following: Y molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve; the supported metal comprises one or more of Pd, Rh, Pt, and Ru; the activated carbon supported catalyst comprises an activated carbon supported metal catalyst and an auxiliary agent; the activated carbon supported metal catalyst comprises one or more of Pd / C catalyst, Rh / C catalyst, Pt / C catalyst, and Ru / C catalyst; the auxiliary agent comprises molecular sieve and / or heteropolyacid.

[0080] This invention achieves highly selective preparation of high-purity straddle-shaped tetrahydrodicyclopentadiene from furfural through a three-step reaction, which, after purification, can be used as JP-10 aviation fuel. The novel reaction pathway involves the reconstruction of furfural molecules to prepare the five-membered carbon ring molecule cyclopentenone, followed by the construction of a four-membered strained carbon ring via a green and efficient photocatalytic [2+2] cycloaddition, and finally, the efficient preparation of cycloalkane products through a metal-supported molecular sieve catalyst for skeletal rearrangement and hydrodeoxygenation. The selectivity for straddle-shaped tetrahydrodicyclopentadiene can reach up to 93%, and the catalyst is simple to synthesize, suitable for large-scale preparation. After simple subsequent purification, it can be used as JP-10 aviation fuel or directly as a special aviation fuel. This route is green and environmentally friendly, and is an efficient method for synthesizing JP-10 aviation fuel from the renewable biomass platform compound furfural, which is beneficial for promoting the high-value utilization of biomass resources.

[0081] To further illustrate the present invention, the following describes in detail a method for preparing JP-10 aviation fuel provided by the present invention with reference to embodiments, but it should not be construed as limiting the scope of protection of the present invention.

[0082] Example 1: Preparation of cyclopentenone from furfural

[0083]

[0084] 6 mL of water was added to a 35 mL steel reactor, followed by 0.4 mmol of furfural, 0.4 μmol of Cp*Ir(4,4'-(OH)2-bpy)(H2O)]SO4, and 20 mg of γ-Al2O3-1. After assembling the reactor, it was purged three times with high-pressure nitrogen and three times with high-pressure hydrogen, and finally purged with 3 MPa of hydrogen. The temperature was increased from room temperature to 130 °C at a rate of 5 °C / min, and the reaction was stirred for 2 h before cooling to room temperature. The conversion rate of the starting material was 100%, and the yield of cyclopentenone was 60%. Pure cyclopentenone was obtained by column chromatography with a petroleum ether:ethyl acetate ratio of 6:1 as the eluent.

[0085] Following the operating steps of Example 1, cyclopentenone was prepared using the remaining 14 catalysts listed below, and the feed conversion and product yield of different catalysts are listed in Table 1.

[0086]

[0087] Table 1. Feed conversion and product yield for the preparation of cyclopentenone using different catalysts

[0088]

[0089] Example 2: Cyclopentenone undergoes self-dimerization under ultraviolet light to generate a C10 four-membered ring oxygen-containing compound.

[0090]

[0091] 10 mL of acetonitrile was added to a quartz glass tube, followed by 4 mmol of cyclopentenone. The mixture was bubbled with nitrogen for 0.5 h under stirring, then sealed with a condenser. The cooling water was turned on to maintain the copolymerization temperature at 20 °C, and the mixture was irradiated with a 185-254 nm UV lamp for 8 h. The reaction solution was separated by column chromatography to obtain a C10 four-membered ring oxygen-containing cyclopentenone dimer, with a petroleum ether:ethyl acetate ratio of 3:1 as the eluent. The product was a mixture of various isomers (involving head-to-head and head-to-tail isomers, as well as cis-trans isomers of the four-membered ring). The different isomers exhibited similar reactivity and product properties upon hydrogenation deoxygenation.

[0092] Following the operating steps of Example 2, the conversion rates of raw materials and the yields of products under different reaction conditions are listed in Table 2.

[0093] Table 2. Conversion rate of cyclopentenone and yield of C10 four-membered ring oxygen-containing compound under different reaction conditions.

[0094]

[0095] Example 3: Preparation of JP-10 by hydrogenation and deoxygenation of C10 four-membered ring oxygen-containing compound

[0096]

[0097] 5 mL of cyclohexane was added to a 35 mL steel reactor, followed by 0.5 mmol of a C10 four-membered ring oxygen-containing compound and 35 mg of 2 wt% Pd-supported MCM-22 molecular sieve catalyst. After assembling the reactor, it was purged three times with high-pressure nitrogen and three times with high-pressure hydrogen, and finally purged with 5 MPa of hydrogen. The temperature was increased from room temperature to 220 °C at a rate of 5 °C / min, and the reaction was stirred for 8 h before cooling to room temperature. The feed conversion rate was 100%, the yield of bridged tetrahydrodicyclopentadiene was 93%, and the reaction product also contained small amounts of bridged tetrahydrodicyclopentadiene and decahydronaphthalene.

[0098] The preparation method of 2 wt% Pd-supported MCM-22 molecular sieve catalyst by impregnation is as follows: 43 mg of Pd(NO3)2 and 1 g of MCM-22 molecular sieve are mixed and stirred in water at room temperature for 3 h. The suspension is dried in air at 120 °C. The resulting solid is washed three times with water using a centrifuge and dried in air at 120 °C. Finally, the temperature is raised from room temperature to 400 °C in air at a rate of 5 °C / min in a tube furnace, held for 4 h, and then cooled to room temperature to obtain 2 wt% Pd-supported MCM-22 molecular sieve catalyst.

[0099] Following the operating steps of Example 3, the conversion rates of the raw materials (C10 four-membered ring oxygen-containing compounds) and the yields of the products (hanging tetrahydrodicyclopentadiene) under different reaction conditions are listed in Table 3.

[0100] Table 3. Conversion rate of raw material (C10 four-membered ring oxygen-containing compound) and yield of product (hanging tetrahydrodicyclopentadiene) under different conditions.

[0101]

[0102] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing JP-10 aviation fuel, comprising the following steps: A) Cyclopentenone was prepared by rearrangement reaction of furfural under hydrogen and a first catalyst. B) The cyclopentenone was subjected to its own dimerization reaction under ultraviolet light to obtain a C10 four-membered ring oxygen-containing compound. C) The C10 four-membered ring oxygen-containing compound is subjected to hydrogenation, deoxygenation and rearrangement reaction under the action of hydrogen and a second catalyst to obtain JP-10 aviation fuel; The second catalyst includes a molecular sieve-supported catalyst and / or an activated carbon-supported catalyst; The molecular sieve-supported catalyst is a molecular sieve-supported metal catalyst. The molecular sieve in the molecular sieve-supported catalyst includes one or more of the following: HY molecular sieve, LaY molecular sieve, CeY molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve; the supported metal includes one or more of Pd, Rh, Pt, and Ru. The activated carbon supported catalyst includes an activated carbon supported metal catalyst and an auxiliary agent; the activated carbon supported metal catalyst includes one or more of Pd / C catalyst, Rh / C catalyst, Pt / C catalyst and Ru / C catalyst; the auxiliary agent includes molecular sieve and / or heteropoly acid.

2. The method for preparing JP-10 aviation fuel according to claim 1, characterized in that, The first catalyst is a co-catalyst of a pentamethylcyclopentadienyl transition metal complex and a Lewis acid. The transition metal in pentamethylcyclopentadienyl transition metal complexes includes one or more of iridium, ruthenium, and rhodium; The ratio of the pentamethylcyclopentadienyl transition metal complex to the Lewis acid is (0.005~0.2) mmol: 1 mg; The rearrangement reaction is carried out at a temperature of 0~300℃ for 0.5~24 hours, and the hydrogen pressure is 0.1~10MPa.

3. The method for preparing JP-10 aviation fuel according to claim 1, characterized in that, In step B), the temperature of the dimerization reaction is 0~80℃, and the time of the dimerization reaction is 0.1~24 hours.

4. The method for preparing JP-10 aviation fuel according to claim 1, characterized in that, In the molecular sieve supported metal catalyst, the molar ratio of SiO2 to Al2O3 is 10~200. The mass of the metal element in the molecular sieve-supported metal catalyst is 0.01~50 wt% of the molecular sieve mass.

5. The method for preparing JP-10 aviation fuel 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 (0.0001~0.1):

1.

6. The method for preparing JP-10 aviation fuel according to claim 1, characterized in that, In the molecular sieve of the activated carbon supported catalyst, the molar ratio of SiO2 to Al2O3 is 10~200; The metal in the activated carbon-supported metal catalyst is 0.5-20 wt% of the activated carbon mass. The molar ratio of the metal in the activated carbon-supported metal catalyst to the C10 four-membered ring oxygen-containing compound is (0.0001~0.1):

1.

7. The method for preparing JP-10 aviation fuel according to claim 1, characterized in that, The molecular sieves in the additives include one or more of the following: HY molecular sieve, LaY molecular sieve, CeY molecular sieve, NaY molecular sieve, ReY molecular sieve, NH4Y molecular sieve, USY molecular sieve, mesoporous Y molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, β molecular sieve, SAPO molecular sieve, MCM-49 molecular sieve, ERB-1 molecular sieve, and ITQ-1 molecular sieve. The heteropoly acid includes one or more of trifluoromethanesulfonate, silicotungstic acid, phosphotungstic acid, or phosphomolybdic acid. The mass ratio of the activated carbon-supported metal catalyst to the additive is (0.01~10):

1.

8. The method for preparing JP-10 aviation fuel according to claim 1, characterized in that, The temperature of the hydrogenation, deoxygenation and rearrangement reaction in step C) is 100~350℃, the reaction time is 0.5~24 hours, and the hydrogen pressure is 0.1~10MPa.

9. The method for preparing JP-10 aviation fuel according to claim 1, characterized in that, In step A), the rearrangement reaction is carried out in a first solvent, which includes one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, and N,N-dimethylformamide. The dimerization reaction in step B) is carried out in a second solvent, which includes one or more of water, acetonitrile, ethyl acetate, benzene, toluene, cyclohexane, n-hexane, dichloromethane, and trichloromethane. The hydrogenation-deoxygenation and rearrangement reactions in step C) are carried out in a third solvent, which includes one or more of cyclohexane, n-hexane, cyclopentane, and n-pentane.

10. The method for preparing JP-10 aviation fuel according to claim 9, characterized in that, The concentration of the C10 four-membered ring oxygen-containing compound in the third solvent is 0.05~1 mol / L.

Images