Synthesis method for efficiently preparing JP-10 fuel from cyclopentanone and application

Abstract

The invention discloses a synthesis method for efficiently preparing JP-10 fuel from cyclopentanone and application, belongs to the technical field of fuel, and aims to solve the technical problems of high production cost and long preparation process period of the JP-10 fuel in the prior art. The synthesis method for efficiently preparing the JP-10 fuel from cyclopentanone comprises the following steps: carrying out catalytic oxidation / Diels-Alder reaction on cyclopentanone in the presence of a catalyst under specific reaction conditions to obtain tricyclic fuel parent molecules; under the condition of a catalyst system, the tricyclic fuel parent molecules are subjected to hydrodeoxygenation and isomerization reaction, and the JP-10 fuel is obtained; the synthesis method for efficiently preparing the JP-10 fuel from cyclopentanone, provided by the invention, not only is simple in preparation steps and shortened in preparation process period, but also has the advantage of low cost; the method has the advantages of high yield and certain economic value.

Description

Technical Field

[0001] The present invention relates to the field of fuel technology, and in particular to a synthesis method for efficiently preparing JP-10 fuel from cyclopentanone and application thereof. Background Art

[0002] Aviation fuel JP-10 is a high-density aviation fuel commonly used internationally. Its physical and chemical properties such as density, volumetric calorific value, and freezing point are superior to most conventional hydrocarbon fuels, and therefore it is widely used in the military and aerospace fields. JP-10, also known as tetrahydrodicyclopentadiene, is an artificial product synthesized from dicyclopentadiene. Currently, JP-10 fuel is mainly synthesized by hydrogenation isomerization of dicyclopentadiene, which is usually extracted from coal tar in a low yield or obtained through naphtha steam cracking. Fossil energy itself is a non-renewable resource. With the increasing global concern about the energy crisis and carbon emissions, the development of renewable biomass resources to replace traditional fossil raw materials is of great significance to achieving the aviation industry's "carbon peak and carbon neutrality" goals. In addition, the high market price of JP-10 fuel further limits its promotion and application in the civil aviation field.

[0003] Currently, it is known that biomass-based furfuryl alcohol is used as the starting material, which is rearranged in water to obtain hydroxycyclopentenone, and then subjected to hydrogenation, dehydration, Diels-Alder reaction, hydrogenation, and isomerization reaction to prepare JP-10 fuel. Furfuryl alcohol is used to replace part of the cyclopentadiene, which reduces the production cost of JP-10. However, the carbon yield is 63.3%, which needs to be further improved. A Chinese patent discloses a method for preparing JP-10 aviation fuel from furfuryl alcohol. This invention uses biomass-based furfuryl alcohol as a raw material to prepare JP-10 aviation fuel. Specifically, a furfuryl alcohol solution is subjected to a rearrangement reaction in the presence of an alkaline catalyst or without a catalyst to produce hydroxycyclopentenone; the hydroxycyclopentenone is reacted with hydrogen in the presence of a hydrogenation catalyst to produce 1,3-cyclopentanediol; the 1,3-cyclopentanediol is dehydrated over an acid catalyst to produce cyclopentadiene or dicyclopentadiene; cyclopentadiene and dicyclopentadiene are isomerized to produce exo-dicyclopentadiene; exo-dicyclopentadiene is hydrogenated to produce exo-tetrahydrodicyclopentadiene, which is then purified by distillation to obtain JP-10 aviation fuel. This invention involves multiple steps in preparing JP-10 fuel, resulting in a long preparation cycle, which limits its application. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides a synthesis method for efficiently preparing JP-10 fuel from cyclopentanone and its application, which solves the technical problems of high production cost and long preparation process cycle of JP-10 fuel. The synthesis method for efficiently preparing JP-10 fuel from cyclopentanone proposed in the present invention is green, low-consumption, cost-controlled and highly efficient. The prepared JP-10 fuel can be used as fuel in the aviation field.

[0005] To achieve the above object, the present invention provides a method for efficiently preparing JP-10 fuel from cyclopentanone, comprising the following steps: Step (1) cyclopentanone is subjected to catalytic oxidation / Diels-Alder reaction under a catalyst and specific reaction conditions to obtain a tricyclic fuel parent molecule; Among them, the synthesis reaction principle of the three-ring fuel parent molecule is: Step (2) Under the conditions of the catalyst system, the three-ring fuel parent molecule undergoes hydrodeoxygenation and isomerization reaction to obtain JP-10 fuel; Among them, the synthesis reaction principle of JP-10 fuel is: Preferably, in step (1), the catalyst is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, selenium oxide, hydrogen peroxide, silver oxide, 2,3-dichloro-5,6-dicyano-p-benzoquinone, dibenzoyl, 2-iodobenzoic acid, 2-iodobenzoic acid·4-methoxypyridine-N-oxide, manganese dioxide, 2-iodobenzoic acid·N-methylmorpholine-N-oxide, 2-iodobenzoic acid·trimethylamine oxide, Dess-Martin periodinane, 2-iodoacetylbenzoic acid, 2-iodobenzoic acid·tetrahydrofuran and 2-iodobenzoic acid·dimethyl sulfoxide; and the amount of the catalyst added is 10% to 80% of the mass of cyclopentanone.

[0006] Preferably, in step (1), the specific reaction conditions are: reaction temperature of 10-80° C., and reaction time of 12-24 h.

[0007] Preferably, in step (2), the catalyst required for the hydrodeoxygenation and isomerization reaction is one or more of copper, nickel, rhodium, platinum, ruthenium, gold or palladium supported on carbon or a carrier molecular sieve Al2O3, SiO2, HZSM-5, Al-MCM-41, Hβ, SBA-15, H-USY, LaY, H-SSY or HY; the amount of the catalyst added accounts for 5% to 40% of the molecular weight of the three-ring fuel matrix.

[0008] Preferably, in step (2), the reaction temperature is 200°C to 280°C, the hydrogen pressure is 6 to 8 MPa, and the reaction time is 24h to 48h.

[0009] A JP-10 fuel is prepared by the synthesis method for efficiently preparing the JP-10 fuel from cyclopentanone.

[0010] Compared with the prior art, the present invention has the following beneficial effects: 1. The cyclopentanone used in the present invention can be derived from a biomass-derived platform compound, which is renewable, low-cost, and high-yield. The present invention uses cyclopentanone to efficiently produce JP-10 fuel in two steps, significantly reducing the number of process steps compared to other preparation processes and showing promising application prospects.

[0011] 2. In the synthesis method for efficiently preparing JP-10 fuel from cyclopentanone provided by the present invention, cyclopentanone can undergo catalytic oxidation / Diels-Alder reaction under relatively mild conditions, followed by hydrodeoxygenation and isomerization reaction to produce JP-10 fuel. The reaction process has the characteristics of low energy consumption, simple preparation steps, high yield, and high selectivity for the target product, thus having high industrial application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 Schematic diagram of the preparation process of JP-10 fuel efficiently prepared from cyclopentanone in the present invention; Figure 2 The three-ring fuel parent molecule prepared in Examples 1-8 of the present invention is 1 H-NMR spectrum; Figure 3 The three-ring fuel parent molecule prepared in Examples 1-8 of the present invention is 13 C-NMR spectrum; Figure 4 This is the mass spectrum of the three-ring fuel parent molecule prepared in Examples 1-8 of the present invention. DETAILED DESCRIPTION

[0013] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0014] Example 1. Experimental study on obtaining tricyclic fuel precursor molecules from cyclopentanone via catalytic oxidation / Diels-Alder reaction The catalyst was added to dimethyl sulfoxide and stirred at room temperature for 60 minutes. Cyclopentanone was slowly added to the reaction solution, heated, and stirred for reaction. After the reaction, extraction was performed and the yield was obtained by quantitative analysis using a gas chromatograph. The specific yield is shown in Table 1. Table 1 The test results in Table 1 show that in the presence of a catalyst, cyclopentanone is first oxidized to cyclopentadienone. However, cyclopentadienone cannot remain stable and spontaneously undergoes a two-molecule Diels-Alder reaction, yielding a tricyclic fuel precursor molecule. The yield of tricyclic fuel precursor molecules in Examples 1-1 to 1-10 of the present invention reached up to 94%. A higher yield of tricyclic fuel precursor molecules, as a synthetic fuel precursor for JP-10 fuel, improves the overall yield from the starting material cyclopentanone to the final product, JP-10 fuel.

[0015] 2. Experimental study on the hydrodeoxygenation and isomerization of the three-ring fuel parent molecule to obtain JP-10 fuel The three-ring fuel precursor molecule and the catalyst were added to an autoclave, sealed, replaced with N2 three times, and then filled with H2. The mixture was stirred and heated to allow the reaction to proceed. After the reaction, the reaction liquid was analyzed by gas chromatography-mass spectrometry to characterize the product and calculate the yield. The details are shown in Table 2. Table 2 The test results in Table 2 indicate that the JP-10 fuel produced in Examples 2-5 achieved the optimal yield of 95%. Combining Tables 1 and 2, it can be seen that in the present invention, the optimal cumulative total yield of JP-10 fuel obtained through catalytic oxidation / Diels-Alder reaction, hydrodeoxygenation, and isomerization of cyclopentanone was 89.3%. The preparation process is simple, post-processing is straightforward, and the method is highly efficient, demonstrating enhanced practicality.

[0016] Comparative Example This comparative example provides a method for preparing JP-10 fuel, and the specific steps are as follows: Step (1) cyclopentanone is catalytically oxidized to obtain cyclopentadienone; 2-iodoxybenzoic acid was added to dimethyl sulfoxide and stirred at room temperature. Cyclopentanone was slowly added to the reaction solution and reacted at 80°C for 20 hours. After the reaction was completed, the mixture was poured into ice water, extracted with ether, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then purified by silica gel column chromatography (V (石油醚) :V (乙酸乙酯) = 20:1) to obtain cyclopentadienone, and the yield of cyclopentadienone was quantitatively analyzed; wherein, the specific reaction conditions and cyclopentadienone yield are shown in Table 3; Step (2) cyclopentadienone undergoes a Diels-Alder reaction to obtain a tricyclic fuel precursor molecule; Cyclopentadienone was added to anhydrous toluene, heated to 80°C and kept warm for 10 hours. After the reaction was completed, the mixture was cooled to room temperature and concentrated under reduced pressure to remove the solvent. The residue was purified by silica gel column chromatography (V (石油醚) :V (乙酸乙酯)= 50:1) to obtain the three-ring fuel precursor molecule, and the yield of the three-ring fuel precursor molecule was obtained by quantitative analysis; wherein, the specific reaction conditions and the yield of the three-ring fuel precursor molecule are shown in Table 3; Step (3) the three-ring fuel parent molecule is subjected to a hydrogenation and deoxygenation reaction to obtain bridged tetrahydrodicyclopentadiene; In a 100 mL reactor, the three-ring fuel precursor molecule and the Pd / Al2O3 catalyst were mixed, replaced with hydrogen and filled with 6 MPa pressure, and reacted at 220 ° C for 20 h. After the reaction, it was cooled to room temperature, the catalyst was filtered out, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (V (石油醚) :V (乙酸乙酯) = 100:1) to obtain bridged tetrahydrodicyclopentadiene; wherein the specific reaction conditions and bridged tetrahydrodicyclopentadiene yield are shown in Table 3; Step (4) isomerizing the bridged tetrahydrodicyclopentadiene to obtain JP-10 fuel; In a 100 mL reactor, bridged tetrahydrodicyclopentadiene and HZSM-5 catalyst were mixed and heated to 200°C for 10 hours. After the reaction, the mixture was cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure to obtain JP-10 fuel. The JP-10 fuel yield was quantitatively analyzed. The specific reaction conditions and JP-10 fuel yields are shown in Table 3. Table 3 Calculations from the data in Table 3 show that the cumulative yield of the three-ring fuel parent molecule prepared in the comparative example is 74.4%; the cumulative total yield of the JP-10 fuel obtained from cyclopentanone through four steps of reaction is calculated to be 63.6%.

[0017] Combining Tables 1, 2, and 3, it can be seen that the step yield of preparing the three-ring fuel precursor molecule by catalytic oxidation / Diels-Alder reaction of cyclopentanone in the embodiment of the present invention is as high as 94%, which is better than the comparative example. Compared with the preparation of the three-ring fuel precursor molecule in the comparative example, not only the reaction steps are reduced, the preparation time is shortened, and the problem of the intermediate cyclopentadienone requiring separation and purification is solved. In the present invention, the three-ring fuel precursor molecule achieves efficient hydrodeoxygenation and isomerization reactions under the action of a bifunctional catalyst, further shortening the preparation process and simultaneously obtaining JP-10 fuel with a higher step yield. In the embodiment of the present invention, the optimal cumulative total yield of JP-10 fuel prepared from cyclopentanone is 89.3%, which is higher than the cumulative total yield of 63.6% in the comparative example, and has certain practical significance.

[0018] Although the embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to these embodiments without departing from the principles and spirit of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for efficiently preparing JP-10 fuel from cyclopentanone, characterized in that: The following steps are involved: Step (1) cyclopentanone is subjected to catalytic oxidation / Diels-Alder reaction under a catalyst and specific reaction conditions to obtain a tricyclic fuel parent molecule; In step (2), under the conditions of the catalyst system, the three-ring fuel parent molecule undergoes hydrodeoxygenation and isomerization reaction to obtain JP-10 fuel.

2. The method for efficiently preparing JP-10 fuel from cyclopentanone according to claim 1, characterized in that: In the step (1), the catalyst is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium permanganate, selenium oxide, hydrogen peroxide, silver oxide, 2,3-dichloro-5,6-dicyano-p-benzoquinone, dibenzoyl, 2-iodobenzoic acid, 2-iodobenzoic acid·4-methoxypyridine-N-oxide, manganese dioxide, 2-iodobenzoic acid·N-methylmorpholine-N-oxide, 2-iodobenzoic acid·trimethylamine oxide, Dess-Martin periodinane, 2-iodoacetylbenzoic acid, 2-iodobenzoic acid·tetrahydrofuran and 2-iodobenzoic acid·dimethyl sulfoxide; and the amount of the catalyst added is 10% to 80% of the mass of cyclopentanone.

3. The method for efficiently preparing JP-10 fuel from cyclopentanone according to claim 1, characterized in that: In the step (1), the specific reaction conditions are: reaction temperature is 10-80°C, and reaction time is 12-24h.

4. The method for efficiently preparing JP-10 fuel from cyclopentanone according to claim 1, characterized in that: In the step (2), the catalyst required for the hydrodeoxygenation and isomerization reaction is one or more of copper, nickel, rhodium, platinum, ruthenium, gold or palladium supported on carbon or a carrier molecular sieve Al2O3, SiO2, HZSM-5, Al-MCM-41, Hβ, SBA-15, H-USY, LaY, H-SSY or HY, or a combination thereof; the amount of the catalyst added accounts for 5% to 40% of the molecular weight of the three-ring fuel matrix.

5. The method for efficiently preparing JP-10 fuel from cyclopentanone according to claim 1, characterized in that: In the step (2), the reaction temperature is 200° C. to 280° C., the hydrogen pressure is 6 to 8 MPa, and the reaction time is 24 h to 48 h.

6. A JP-10 fuel, characterized in that: The JP-10 fuel is prepared by the synthesis method for efficiently preparing JP-10 fuel from cyclopentanone as described in any one of claims 1 to 5.

Images