Process for the preparation of high-tension tetranuclear cycloalkane fuels from cyclic ketones or cyclic alcohols in one pot and use of the fuels

Abstract

The application discloses a method for preparing high-tension four-membered ring alkane fuel by one-pot method of cyclic ketone or cyclic alcohol and application of the fuel, wherein the fuel synthesis process is as follows: wherein n=1 or 2, 3, R1, R2, R3, R4, R5 and R6=H or-CH3 or-CH2CH3; the four-membered ring fuel matrix is prepared by one-pot method of oxidation / [2+2] cycloaddition of biomass-derived cyclic ketone or cyclic alcohol in the presence of an oxidant and a light source, the reaction temperature of the process is 0-80 DEG C, the reaction time is 12-36h, and the fuel matrix is obtained by reaction, and the yield is about 95%. The raw material of the application has low price, the reaction condition is mild, the synthesis cost is low, and the post-treatment is simple; the four-membered ring alkane fuel has excellent performances of high density, high calorific value and low freezing point.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of liquid fuel propellants, and particularly relates to a method for preparing high-tension four-membered ring alkane fuel from cyclic ketones or cyclic alcohols by one-pot method and application of the fuel. BACKGROUND

[0002] High-density hydrocarbon fuel refers to fuel with a density greater than 0.8 g / cm 3 Artificially synthesized alkane fuel, which provides important power support for aerospace vehicles and provides more possibilities for exploring unknown space, has a density greater than 0.8 g / cm

[0003] Traditional aerospace fuels are mostly prepared from petroleum-based derivatives, such as widely used JP-10 fuel and RJ-4 fuel. With the shortage of fossil resources and the deterioration of environmental problems, biomass, as the only renewable organic carbon source in nature, can effectively solve the energy crisis and realize the sustainable development of energy. At present, the main biomass raw materials for synthesizing high-density hydrocarbon fuel are cellulose, hemicellulose, terpene compounds, lignin and its derivatives, and other biomass platform compounds. Although it has been reported that biomass-derived enones can be used as raw materials to synthesize four-membered ring fuel, the synthesis route of this method is long, the overall yield is low, and the price of the raw material is high, resulting in high cost of the target fuel synthesis. Therefore, it is a great challenge to use biomass platform compounds with large output and low price to prepare high-density four-membered ring fuel. SUMMARY

[0004] To solve the technical problems in the background art, the first aspect of the present application provides a method for preparing high-tension four-membered ring alkane fuel from cyclic ketones or cyclic alcohols by one-pot method, which comprises the following steps:

[0005] S1: one-pot oxidation / [2+2] cycloaddition reaction of biomass-derived cyclic ketones or cyclic alcohols in the presence of an oxidizing agent and a light source to obtain a four-membered ring fuel parent molecule:

[0006]

[0007] S2: hydrogenation and deoxygenation of the four-membered ring fuel parent molecule obtained in step S1 to obtain a four-membered ring fuel molecule:

[0008] .

[0009] Further, in the method, n=1 or 2, 3; R1, R2, R3, R4, R5, R6=H or -CH3 or -CH2CH3.

[0010] Further, when n=1, the density of the tetranuclear ring fuel molecule is 0.87-0.93 g / cm 3 , the freezing point is not higher than -55℃, and the mass heat value is not lower than 42.2 MJ / kg.

[0011] Further, in step S1, the oxidant is one or several of potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, hydrogen peroxide, silver oxide, diphenylhydrazyl, 2-iodoxybenzoic acid, 2-iodoxybenzoic acid·4-methoxypyridine-N-oxide, 2-iodoxybenzoic acid·N-methylmorpholine-N-oxide, 2-iodoxybenzoic acid·trimethylamine oxide, 2-iodoxyacetylbenzoic acid, 2-iodoxybenzoic acid·tetrahydrofuran, and 2-iodoxybenzoic acid·dimethyl sulfoxide; and the addition amount of the oxidant is 5wt%-80wt% of the reactants.

[0012] Further, in step S1, the conditions of the oxidation / [2+2] cycloaddition reaction are: the light source is a 200-500w high-pressure mercury lamp or a xenon lamp, the reaction temperature is 0-80℃, and the reaction time is 12-36h.

[0013] Further, in step S1, the cyclic ketone is one or more of cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,3-dimethylcyclopentanone, 2,4-dimethylcyclopentanone, 2,5-dimethylcyclopentanone, 2-ethylcyclopentanone, 3-ethylcyclopentanone, 2,3-diethylcyclopentanone, 2,4-diethylcyclopentanone, 2,5-diethylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,2-dimethylcyclohexanone, 2,3-dimethylcyclohexanone, 2,4-dimethylcyclohexanone, 2,5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, 3,4-dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 3,6-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 2,2,3-trimethylcyclohexanone, 2,2,4-trimethylcyclohexanone, 2,2,5-trimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, 2,3,3-trimethylcyclohexanone, 2,3,4-trimethylcyclohexanone, 2,3,5-trimethylcyclohexanone, 2,3,6-trimethylcyclohexanone, 2,4,4-trimethylcyclohexanone, 2,4,5-trimethylcyclohexanone, 2,4,6-trimethylcyclohexanone, 3,3,4-trimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,3,6-trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 3,4,5-trimethylcyclohexanone, ethylcyclohexanone, 3-ethylcyclohexanone, 4-ethylcyclohexanone, 2,3-diethylcyclohexanone, 2,4-diethylcyclohexanone, 3,4-diethylcyclohexanone.

[0014] Further, in step S1, the cyclic alcohol is one or more of cyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 2,2-dimethylcyclopentanol, 2,3-dimethylcyclopentanol, 2,4-dimethylcyclopentanol, 2,5-dimethylcyclopentanol, 2-ethylcyclopentanol, 3-ethylcyclopentanol, 2,3-diethylcyclopentanol, 2,4-diethylcyclopentanol, 2,5-diethylcyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 2,2-dimethylcyclohexanol, 2,3-dimethylcyclohexanol, 2,4-dimethylcyclohexanol, 2,5-dimethylcyclohexanol, 2,6-dimethylcyclohexanol, 3,3-dimethylcyclohexanol, 3,4-dimethylcyclohexanol, 3,5-dimethylcyclohexanol, 3,6-dimethylcyclohexanol, 4,4-dimethylcyclohexanol, 2,2,3-trimethylcyclohexanol, 2,2,4-trimethylcyclohexanol, 2,2,5-trimethylcyclohexanol, 2,2,6-trimethylcyclohexanol, 2,3,3-trimethylcyclohexanol, 2,3,4-trimethylcyclohexanol, 2,3,5-trimethylcyclohexanol, 2,3,6-trimethylcyclohexanol, 2,4,4-trimethylcyclohexanol, 2,4,5-trimethylcyclohexanol, 2,4,6-trimethylcyclohexanol, 3,3,4-trimethylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3,3,6-trimethylcyclohexanol, 3,4,4-trimethylcyclohexanol, 3,4,5-trimethylcyclohexanol, ethylcyclohexanol, 3-ethylcyclohexanol, 4-ethylcyclohexanol, 2,3-diethylcyclohexanol, 2,4-diethylcyclohexanol, 3,4-diethylcyclohexanol.

[0015] Further, in step S2, the conditions for the hydrodeoxygenation of the fuel precursor molecule are: in the presence of a catalyst, a reaction temperature of 150-220℃, a hydrogen pressure of 4-8 MPa, and a reaction time of 24-48 h.

[0016] Further, the catalyst is a supported catalyst formed by loading a metal on a carrier; wherein the metal is one or more of copper, nickel, gold, platinum and palladium; and the carrier is one or more of Al2O3, SiO2, Al-MCM-41, HZSM-5, Hβ and HY.

[0017] The second aspect of the present application provides the use of the high-tension four-membered ring alkane fuel prepared by the method described in the above technical solution in aircraft liquid fuel propellants.

[0018] Compared with the prior art, the present application has the following beneficial technical effects:

[0019] (1) All raw materials in the present application are derived from biomass-derived platform compounds, which have the characteristics of being renewable, low-cost and high-yield.

[0020] (2) The high-tension four-membered ring fuel in the application has simple preparation process, mild reaction conditions, high target yield, good universality for various types of substituted cycloalcohols and substituted cycloketones derived from biomass, and high industrial application value. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0022] Although it is reported that biomass-derived enone can be used as a raw material to synthesize four-membered ring fuel, the synthesis route of this method is long, the comprehensive yield is low, and the raw material price is high, resulting in high cost of target fuel synthesis. Based on this, the application proposes a new process for preparing high-tension four-membered ring alkane fuel from cycloketone or cycloalcohol by one-pot method, develops a one-pot oxidation / [2+2] cycloaddition preparation process, and the synthesized fuel molecules have excellent properties of high density, high heat value and low freezing point. Specifically, the method comprises the following steps:

[0023] S1: one-pot oxidation / [2+2] cycloaddition reaction of biomass-derived cycloketone or cycloalcohol in the presence of an oxidizing agent and a light source to obtain a four-membered ring fuel precursor molecule:

[0024]

[0025] In some embodiments, in step S1, the oxidizing agent is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, hydrogen peroxide, silver oxide, benzil, 2-iodoxybenzoic acid, 2-iodoxybenzoic acid·4-methoxypyridine-N-oxide, 2-iodoxybenzoic acid·N-methylmorpholine-N-oxide, 2-iodoxybenzoic acid·trimethylamine oxide, 2-iodoxyacetylbenzoic acid, 2-iodoxybenzoic acid·tetrahydrofuran, and 2-iodoxybenzoic acid·dimethyl sulfoxide.

[0026] In some embodiments, the amount of the above-mentioned oxidizing agent added is 5wt%-80wt% of the reactants; for example, it can be 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, and the like.

[0027] In some embodiments, the conditions of the above oxidation / photochemical [2+2] cycloaddition reaction are: the light source is a 200-500w high-pressure mercury lamp or a xenon lamp, which can be, for example, 200w, 300w, 350w, 400w, 500w, etc.; the reaction temperature is 0-80℃, which can be, for example, 0℃, 10℃, 15℃, 20℃, 25℃, 30℃, 50℃, 60℃, 70℃, 80℃, etc.; the reaction time is 12-36h, which can be, for example, 12h, 18h, 24h, 34h, 36h, etc.

[0028] In some embodiments, in step S1, the cyclic ketone is one or more of cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,3-dimethylcyclopentanone, 2,4-dimethylcyclopentanone, 2,5-dimethylcyclopentanone, 2-ethylcyclopentanone, 3-ethylcyclopentanone, 2,3-diethylcyclopentanone, 2,4-diethylcyclopentanone, 2,5-diethylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,2-dimethylcyclohexanone, 2,3-dimethylcyclohexanone, 2,4-dimethylcyclohexanone, 2,5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, 3,4-dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 3,6-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 2,2,3-trimethylcyclohexanone, 2,2,4-trimethylcyclohexanone, 2,2,5-trimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, 2,3,3-trimethylcyclohexanone, 2,3,4-trimethylcyclohexanone, 2,3,5-trimethylcyclohexanone, 2,3,6-trimethylcyclohexanone, 2,4,4-trimethylcyclohexanone, 2,4,5-trimethylcyclohexanone, 2,4,6-trimethylcyclohexanone, 3,3,4-trimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,3,6-trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 3,4,5-trimethylcyclohexanone, ethylcyclohexanone, 3-ethylcyclohexanone, 4-ethylcyclohexanone, 2,3-diethylcyclohexanone, 2,4-cyclohexanone, 3,4-diethylcyclohexanone.

[0029] In some embodiments, in step S1, the cyclic alcohol is one or more of cyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 2,2-dimethylcyclopentanol, 2,3-dimethylcyclopentanol, 2,4-dimethylcyclopentanol, 2,5-dimethylcyclopentanol, 2-ethylcyclopentanol, 3-ethylcyclopentanol, 2,3-diethylcyclopentanol, 2,4-diethylcyclopentanol, 2,5-diethylcyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 2,2-dimethylcyclohexanol, 2,3-dimethylcyclohexanol, 2,4-dimethylcyclohexanol, 2,5-dimethylcyclohexanol, 2,6-dimethylcyclohexanol, 3,3-dimethylcyclohexanol, 3,4-dimethylcyclohexanol, 3,5-dimethylcyclohexanol, 3,6-dimethylcyclohexanol, 4,4-dimethylcyclohexanol, 2,2,3-trimethylcyclohexanol, 2,2,4-trimethylcyclohexanol, 2,2,5-trimethylcyclohexanol, 2,2,6-trimethylcyclohexanol, 2,3,3-trimethylcyclohexanol, 2,3,4-trimethylcyclohexanol, 2,3,5-trimethylcyclohexanol, 2,3,6-trimethylcyclohexanol, 2,4,4-trimethylcyclohexanol, 2,4,5-trimethylcyclohexanol, 2,4,6-trimethylcyclohexanol, 3,3,4-trimethylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3,3,6-trimethylcyclohexanol, 3,4,4-trimethylcyclohexanol, 3,4,5-trimethylcyclohexanol, ethylcyclohexanol, 3-ethylcyclohexanol, 4-ethylcyclohexanol, 2,3-diethylcyclohexanol, 2,4-diethylcyclohexanol, 3,4-diethylcyclohexanol.

[0030] S2: hydrogenating and deoxidizing the four-membered ring fuel mother molecule obtained in step S1 to obtain a four-membered ring fuel molecule:

[0031] .

[0032] In some embodiments, in step S2, the hydrogenation and deoxidization conditions of the fuel mother molecule are as follows: the reaction temperature is 150-220℃, for example, it can be 150℃, 160℃, 180℃, 200℃, 220℃, etc.; the hydrogen pressure is 4-8 MPa, for example, it can be 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, etc.; the reaction time is 24-48 h, for example, it can be 24 h, 30 h, 36 h, 42 h, 48 h, etc.

[0033] In some embodiments, the catalyst in the above hydrogenation and deoxidization process is a supported catalyst formed by loading a metal on a carrier; wherein the metal is one or more of copper, nickel, gold, platinum and palladium; and the carrier is one or more of Al2O3, SiO2, Al-MCM-41, HZSM-5, Hβ and HY.

[0034] In the preparation method, n = 1 or 2, 3; R1, R2, R3, R4, R5, R6 = H or -CH3 or -CH2CH3; when n = 1, the density of the four-membered ring fuel molecule is 0.87-0.93 g / cm 3 , the freezing point is not higher than -55℃, and the mass heat value is not lower than 42.2 MJ / kg.

[0035] The following examples in the following table further illustrate the present application.

[0036] Table 1 is an example of a four-membered ring fuel parent molecule synthesis reaction.

[0037] Table 1 is an example of a four-membered ring fuel parent molecule synthesis reaction.

[0038] No. Reactant Raw material mass / g Oxidizing agent Oxidizing agent amount / wt% Reaction temperature / °C Reaction time / h Fuel parent yield / % Example 1 Cyclopentanol 20 2-iodoxybenzoic acid · 4-methoxypyridine-N-oxide 5 25 12 95 Example 2 Cyclohexanone 20 2-iodoxybenzoic acid · 4-methoxypyridine-N-oxide 5 25 24 92 Example 3 Cyclopentanone 20 2-iodoxybenzoic acid · 4-methoxypyridine-N-oxide 5 25 12 96 Example 4 Cyclohexanol 20 Sodium persulfate 10 25 24 81 Example 5 3-methyl-cyclohexanone 20 2-iodoxybenzoic acid 5 20 24 94 Example 6 2-methyl-cyclohexanone 20 2-iodoxybenzoic acid 5 10 24 93 Example 7 2,4-dimethyl-cyclopentanone 20 2-iodoxybenzoic acid · N-methylmorpholine-N-oxide 5 10 24 87 Example 8 2,3,5-trimethyl-cyclohexanone 15 2-iodoxybenzoic acid · N-methylmorpholine-N-oxide 50 25 24 92 Example 9 3-ethyl-cyclopentanone 15 Hydrogen peroxide 80 30 24 76 Example 10 3-ethyl-2-cyclohexanone 15 2-iodoxybenzoic acid · trimethylamine oxide 80 25 24 80 Example 11 3-methyl-cyclohexanol 20 2-iodoxybenzoic acid · trimethylamine oxide 10 60 24 70 Example 12 2-methyl-cyclohexanol 20 2-iodoxybenzoic acid · trimethylamine oxide 10 30 24 65 Example 13 2-methylcyclopentanone 10 2-iodoxyacetylbenzoic acid 30 15 36 96 Example 14 3-methyl-2-cyclopentanone 15 2-iodoxyacetylbenzoic acid 50 80 34 95 Example 15 4,4'-dimethyl-cyclohexanone 15 Bibenzoyl 50 30 24 92 Example 16 3,4,5-trimethyl-cyclohexanone 15 2-iodoxyacetylbenzoic acid 60 0 36 90 Example 17 2,3-dimethylcyclopentanone 15 2-iodoxyacetylbenzoic acid 20 15 36 97 Example 18 3-methyl-cyclohexanol 15 2-iodoxybenzoic acid · trimethylamine oxide 60 15 36 96 Example 19 3,5-dimethyl-2-cyclohexanol 20 Potassium persulfate 30 0 24 84 Example 20 2,3,5-trimethyl-cyclohexanone 20 2-iodoxybenzoic acid · trimethylamine oxide 30 0 24 92 Example 21 3-ethyl-cyclopentanol 20 Ammonium persulfate 30 0 12 82 Example 22 3-ethyl-cyclohexanone 20 2-iodoxybenzoic acid · N-methylmorpholine-N-oxide 50 70 24 93 Example 23 3,3-dimethyl-cyclohexanone 20 2-iodoxybenzoic acid · N-methylmorpholine-N-oxide 50 0 24 99

[0039] Specific reactions are taken as examples 13 and 17 in Table 1, and the specific steps are as follows: 10 g of 2-methylcyclopentanone (or 15 g of 2,3-dimethylcyclopentanone) is added to a 25 mL single-neck jacketed glass reactor, 3 g of oxidant 2-iodoxyacetylbenzoic acid is added, then sealed, and the 15℃ circulating water is turned on, and the high-pressure mercury lamp is irradiated for 36 h. Gas chromatography-mass spectrometry is used to analyze the reaction liquid, and the product is qualitatively determined and the reaction yield is calculated. For the oxidation / cycloaddition reaction of 2-methylcyclopentanone, the yield of the four-membered ring fuel parent molecule is 96%; for the oxidation / cycloaddition reaction of 2,3-dimethylcyclopentanone, the yield of the four-membered ring fuel parent is 97%. The reaction conditions and yield are shown in Table 1.

[0040] Table 2 is an example of a high-tension four-membered ring fuel parent hydrodeoxygenation reaction.

[0041] Table 2 is an example of a high-tension four-membered ring fuel parent hydrodeoxygenation reaction.

[0042]

[0043] The four-membered ring fuel parent molecule hydrodeoxygenation reaction is taken as example 29 in Table 2, and the specific steps are as follows: the fuel parent molecule obtained in example 13 and 5 g of Pd / Hβ catalyst are added to a 100 mL autoclave, sealed, replaced with N2 for 3 times, then 6 MPa of H2 is added, stirred to 160℃, and reacted for 48 h. Gas chromatography-mass spectrometry is used to analyze the reaction liquid, and the product is qualitatively determined and the reaction yield is calculated. The fuel parent is completely converted, and the yield of the target four-membered ring fuel molecule is 92%. The reaction conditions and yield of examples 24-28, 30-39 are shown in Table 2.

[0044] As can be seen from the above, the biomass-derived cyclic ketone or cyclic alcohol can be obtained by one-pot oxidation / cycloaddition and solvent-free hydrodeoxygenation to obtain fuel molecules with high-tension four-membered ring structure in high yield. The high-tension four-membered ring fuel, which is prepared by hydrodeoxygenation of the fuel precursor molecule synthesized in Example 3 by Example 26, has a density of 0.88 g / cm 3 , a freezing point of -60°C, and a mass heat value of 42.3 MJ / kg; the high-tension four-membered ring fuel, which is prepared by hydrodeoxygenation of the fuel precursor molecule synthesized in Example 7 by Example 36, has a density of 0.90 g / cm 3 , a freezing point of -50°C, and a mass heat value of 42.5 MJ / kg. Comparing the two fuel molecules, it is found that the density and low-temperature properties of the fuel molecule with symmetric substitution of methyl groups on the ring are reduced to a certain extent, which is of certain guiding significance for the design and preparation of fuel molecules in the future.

[0045] (1) Schematic diagram of the four-membered ring fuel prepared by hydrodeoxygenation of the fuel precursor molecule synthesized in Example 3 by Example 26:

[0046]

[0047] (2) Schematic diagram of the four-membered ring fuel prepared by hydrodeoxygenation of the fuel precursor molecule synthesized in Example 7 by Example 36:

[0048]

[0049] It should be noted that in this document, terms such as the term "comprise", "comprise" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such a process, method, article or device.

[0050] Although embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations can be made thereto without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing high-strain four-membered cycloalkane fuels from cyclic ketones or cyclic alcohols in a one-pot process, characterized in that, The method includes the following steps: S1: In the presence of an oxidant and a light source, biomass-derived cyclic ketones or cyclic alcohols are subjected to a one-pot oxidation / photochemical [2+2] cycloaddition reaction to obtain a four-membered ring fuel parent molecule: ； Where n = 1 or 2, 3; R1, R2, R3, R4, R5, R6 = H or -CH3 or -CH2CH3; The oxidant is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, hydrogen peroxide, silver oxide, bibenzoyl, 2-iodobenzoic acid, 2-iodobenzoic acid·4-methoxypyridine-N-oxide, 2-iodobenzoic acid·N-methylmorpholine-N-oxide, 2-iodobenzoic acid·trimethylamine oxide, 2-iodoacetylbenzoic acid, 2-iodobenzoic acid·tetrahydrofuran, and 2-iodobenzoic acid·dimethyl sulfoxide; the amount of the oxidant added is 5wt%-80wt% of the reactants. S2: Hydrogenation and deoxygenation of the four-membered ring fuel parent molecule obtained in step S1 yields a four-membered ring fuel molecule: 。 2. The method for preparing high-strength four-membered cycloalkane fuel from cyclic ketones or cyclic alcohols in a one-pot process as described in claim 1, characterized in that, When n=1, the density of the four-membered ring fuel molecule is 0.87–0.93 g / cm³. 3 The freezing point is not higher than -55℃ and the calorific value is not lower than 42.2MJ / kg.

3. The method for preparing high-strain four-membered cycloalkane fuel from cyclic ketones or cyclic alcohols in a one-pot process as described in claim 1, characterized in that, In step S1, the conditions for the oxidation / [2+2] cycloaddition reaction are: the light source is a 200-500W high-pressure mercury lamp or xenon lamp, the reaction temperature is 0~80℃, and the reaction time is 12-36h.

4. The method for preparing high-strength four-membered cycloalkane fuel from cyclic ketones or cyclic alcohols in a one-pot process as described in claim 1, characterized in that, In step S1, the cyclic ketone is cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,3-dimethylcyclopentanone, 2,4-dimethylcyclopentanone, 2,5-dimethylcyclopentanone, 2-ethylcyclopentanone, 3-ethylcyclopentanone, 2,3-diethylcyclopentanone, 2,4-diethylcyclopentanone, 2,5-diethylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,2-dimethylcyclohexanone, 2,3-dimethylcyclohexanone, 2,4-dimethylcyclohexanone, 2,5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, 3,4-dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 3,6-dimethylcyclohexanone, 4,4 ...4-dimethylcyclohexanone, 2,4-dimethylcyclohexanone, 2,4-dimethylcyclohexanone, 2,4-dimethylcyclohexanone, 2,4-dimethylcyclohexan One or more of the following: 2,2,3-trimethylcyclohexanone, 2,2,4-trimethylcyclohexanone, 2,2,5-trimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, 2,3,3-trimethylcyclohexanone, 2,3,4-trimethylcyclohexanone, 2,3,5-trimethylcyclohexanone, 2,3,6-trimethylcyclohexanone, 2,4,4-trimethylcyclohexanone, 2,4,5-trimethylcyclohexanone, 2,4,6-trimethylcyclohexanone, 3,3,4-trimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,3,6-trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 3,4,5-trimethylcyclohexanone, 3-ethylcyclohexanone, 4-ethylcyclohexanone, 2,3-diethylcyclohexanone, and 3,4-diethylcyclohexanone.

5. The method for preparing high-strength four-membered cycloalkane fuel from cyclic ketones or cyclic alcohols in a one-pot process as described in claim 1, characterized in that, In step S1, the cycloalcohol is cyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 2,2-dimethylcyclopentanol, 2,3-dimethylcyclopentanol, 2,4-dimethylcyclopentanol, 2,5-dimethylcyclopentanol, 2-ethylcyclopentanol, 3-ethylcyclopentanol, 2,3-diethylcyclopentanol, 2,4-diethylcyclopentanol, 2,5-diethylcyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 2,2-dimethylcyclohexanol, 2,3-dimethylcyclohexanol, 2,4-dimethylcyclohexanol, 2,5-dimethylcyclohexanol, 2,6-dimethylcyclohexanol, 3,3-dimethylcyclohexanol, 3,4-dimethylcyclohexanol, 3,5-dimethylcyclohexanol, 3,6-dimethylcyclohexanol, 4,4 ...4-dimethylcyclohexanol, 2,3-dimethylcyclohexanol, 2,4-dimethylcyclohexanol, 2,4-dimethylcyclohexanol, 2,4-dimethylcyclohexan One or more of the following: 2,2,3-trimethylcyclohexanol, 2,2,4-trimethylcyclohexanol, 2,2,5-trimethylcyclohexanol, 2,2,6-trimethylcyclohexanol, 2,3,3-trimethylcyclohexanol, 2,3,4-trimethylcyclohexanol, 2,3,5-trimethylcyclohexanol, 2,3,6-trimethylcyclohexanol, 2,4,4-trimethylcyclohexanol, 2,4,5-trimethylcyclohexanol, 2,4,6-trimethylcyclohexanol, 3,3,4-trimethylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3,3,6-trimethylcyclohexanol, 3,4,4-trimethylcyclohexanol, 3,4,5-trimethylcyclohexanol, 3-ethylcyclohexanol, 4-ethylcyclohexanol, 2,3-diethylcyclohexanol, and 3,4-diethylcyclohexanol.

6. The method for preparing high-strength four-membered cycloalkane fuel from cyclic ketones or cyclic alcohols in a one-pot process as described in claim 1, characterized in that, In step S2, the conditions for hydrogenation and deoxygenation of the fuel matrix molecule are as follows: in the presence of a catalyst, the reaction temperature is 150℃~220℃, the hydrogen pressure is 4~8MPa, and the reaction time is 24h~48h.

7. The method for preparing high-strength four-membered cycloalkane fuel from cyclic ketones or cyclic alcohols in a one-pot process as described in claim 6, characterized in that... The catalyst is a supported catalyst formed by loading a metal onto a support; wherein the metal is one or more of copper, nickel, gold, platinum and palladium; and the support is one or more of Al2O3, SiO2, Al-MCM-41, HZSM-5, Hβ and HY.

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