WO2019080016A1 - Four-membered ring fuel molecule and photochemical preparation method therefor - Google Patents

Four-membered ring fuel molecule and photochemical preparation method therefor

Info

Publication number
WO2019080016A1
WO2019080016A1 PCT/CN2017/107696 CN2017107696W WO2019080016A1 WO 2019080016 A1 WO2019080016 A1 WO 2019080016A1 CN 2017107696 W CN2017107696 W CN 2017107696W WO 2019080016 A1 WO2019080016 A1 WO 2019080016A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyclohexenone
cyclopentenone
fuel
dimethyl
diethyl
Prior art date
Application number
PCT/CN2017/107696
Other languages
French (fr)
Chinese (zh)
Inventor
邹吉军
谢君健
潘伦
张香文
王莅
Original Assignee
天津大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 天津大学 filed Critical 天津大学
Priority to PCT/CN2017/107696 priority Critical patent/WO2019080016A1/en
Publication of WO2019080016A1 publication Critical patent/WO2019080016A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons

Definitions

  • the invention belongs to the field of liquid fuel propellants, and relates to a high tension four-membered ring fuel molecule and a photochemical preparation method thereof.
  • Fuel is the blood of all engines, ensuring the normal operation of the engine.
  • high-density fuels with higher densities and higher calorific values are needed.
  • the volume of the aircraft is constant, the greater the density of the fuel, the greater the mass of fuel carried by the aircraft; the higher the combustion heat value of the fuel, the greater the energy released per unit volume of fuel, and the performance of the aircraft (including the range and speed) And the payload is more advantageous; or, while keeping the aircraft performance ratio unchanged, the tank volume is reduced, and a small aircraft is developed to greatly improve the aircraft's penetration capability and flexibility.
  • High-density fuel refers to a synthetic liquid hydrocarbon fuel having a density greater than 0.8 g/cm 3 , which is composed of a single component or a mixture of a plurality of hydrocarbons.
  • the synthesis of high-density hydrocarbon fuels is divided into the direct synthesis of high-density, low-freezing, high-calorie polycyclic hydrocarbons and the addition of energetic additives to hydrocarbons.
  • a large number of experimental data show that the polycyclic structure can increase the density of hydrocarbon fuel; the intramolecular ring tension can increase the mass calorific value of the fuel.
  • freezing point and low temperature viscosity are also important indicators of fuel.
  • density increases, the freezing point and low temperature viscosity of the hydrocarbon fuel also increase. Therefore, it is a great challenge to synthesize high-density fuels with high density, high calorific value and excellent low-temperature performance.
  • a first aspect of the invention relates to a four-membered ring fuel molecule having the following structure:
  • n 1 or 2
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  • the density of the fuel molecules is 0.88-0.95 g/cm 3
  • the freezing point is not higher than -55 ° C
  • the mass calorific value is not lower than 42.5 MJ/kg
  • the freezing point is not higher than -40 ° C
  • the mass calorific value is not lower than 42.7 MJ/kg.
  • a second aspect of the present invention relates to a method for preparing the four-membered ring fuel molecule.
  • the first aspect of the present invention includes the steps of: in the presence of a photosensitizer, a cyclohexanone itself is subjected to a cycloaddition reaction to obtain a fuel precursor molecule.
  • the fuel parent molecule is then hydrodeoxygenated to obtain the four-membered ring fuel molecule.
  • n 1 or 2
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  • the second aspect of the second aspect of the present invention includes the following steps: in the presence of a photosensitizer, a cycloaddition reaction occurs between a substituted cycloketene and a substituted cycloolefin to obtain a fuel precursor molecule, and then a fuel parent molecule Hydrodeoxygenation to obtain the four-membered ring fuel molecule,
  • n 1 or 2
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  • the third aspect of the second aspect of the present invention includes the following steps: in the presence of a photosensitizer, a cycloaddition reaction of the substituted cycloolefin itself is carried out to obtain the four-membered ring fuel molecule.
  • n 1 or 2
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  • the photosensitizer is one or more of cyclopentanone, cyclohexanone, acetone, benzophenone, acetophenone, methyl ketone, tetraethyl ketone, N-methylpyrrolidone
  • the photosensitizer is added in an amount of from 1% by weight to 10% by weight of the reactant.
  • the substituted cycloketene is cyclopentenone, 3-methyl-2-cyclopentenone, 4-methyl-2-cyclopentenone, 5-methyl-2-cyclopentene Ketone, 4,4'-dimethyl-2-cyclopentenone, 3,4-dimethyl-2-cyclopentenone, 3,5-dimethyl-2-cyclopentenone, 4, 5-dimethyl-2-cyclopentenone, 3,4,4'-trimethyl-2-cyclopentenone, 3,4,5-trimethyl-2-cyclopentenone, 3- Ethyl-2-cyclopentenone, 4-ethyl-2-cyclopentenone, 5-ethyl-2-cyclopentenone, 4,4'-diethyl-2-cyclopentenone, 3,4-diethyl-2-cyclopentenone, 3,5-diethyl-2-cyclopentenone, 4,5-diethyl-2-cyclopentenone, 3,4,4 '-Triethyl-2-cyclopentenone, 3,4,5-triethyl-2-cyclopentenone, cyclohe
  • the substituted cycloolefin is cyclopentene, methylcyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 1,2-dimethylcyclopentene, 1,3 - dimethylcyclopentene, 1,4-dimethylcyclopentene, ethylcyclopentene, 3-ethylcyclopentene, 4-ethylcyclopentene, 1,2-diethylcyclopentane Alkene, 1,3-diethylcyclopentene, 1,4-diethylcyclopentene, cyclohexene, methylcyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 1,2-Dimethylcyclohexene, 1,3-dimethylcyclohexene, 1,4-dimethylcyclohexene, ethylcyclohexene, 3-ethylcyclohexene, 4-B One or more of cyclohexene, 1,2-Di
  • the cycloaddition reaction is carried out under the conditions of high pressure mercury lamp irradiation at -40 ° C to 50 ° C for 1 h to 24 h.
  • the reaction conditions of the hydrodeoxygenation of the fuel precursor molecule are: in the presence of a catalyst, the reaction temperature is 100 ° C to 200 ° C, the hydrogen pressure is 3-8 MPa, and the reaction time is 10 h to 48 h; wherein the catalyst is nickel a supported catalyst in which platinum or palladium is supported on HZSM-5, H ⁇ or HY, or a mixture of Pd/C and molecular sieves physically mixed.
  • a third aspect of the invention relates to the use of the four-membered ring structure fuel molecules for high density aerospace fuels.
  • the fuel molecule of the present invention having a high tension four-membered ring structure has both high density, high calorific value, and low freezing point, so that its volumetric calorific value is higher than that of a general liquid hydrocarbon fuel. For a spacecraft with a certain volume of fuel tank, it can effectively improve the quality of oil carrier and meet the application requirements of its long range, high speed and large load.
  • the fuel molecule having the high tension four-membered ring structure of the present invention can be obtained by normal temperature and normal pressure photochemical cycloaddition and hydrodeoxygenation, and the preparation method of the invention has high yield, no solvent, and mild reaction conditions. All kinds of substituted cycloketenes and substituted cycloolefins have good universality and high industrial application value.
  • Table 1 shows an example of a fuel precursor molecule synthesis reaction.
  • the specific reaction steps are exemplified by Examples 13 and 17 in Table 1.
  • the specific steps are as follows: in a 25 mL single-port jacketed glass reactor, 10 g of cyclopentenone and 10 g of cyclohexene (or 10 g of cyclohexenone and 10 g of cyclohexene), 1% by mass of acetone, and nitrogen are stirred. Bubbling for 0.5 h, then sealing, opening the condensed water, and irradiating the high pressure mercury lamp for 5 h. The reaction solution was analyzed by gas chromatography-mass spectrometry, and the product was qualitatively determined and the reaction yield was calculated.
  • Table 2 is an example of a hydrodeoxygenation reaction of a fuel precursor molecule.
  • the fuel parent molecular hydrodeoxygenation reaction step is exemplified by Example 29 in Table 2.
  • the specific steps are as follows: the fuel precursor molecule obtained in Example 13 and 2 g of Pd/C and 5 g of H ⁇ catalyst were placed in a 100 mL autoclave, sealed, replaced with N 2 for 3 times, then charged with 6 MPa of H 2 , and stirred to a temperature of 160 ° C. , reaction 24h.
  • the reaction solution was analyzed by gas chromatography-mass spectrometry, and the product was qualitatively determined and the reaction yield was calculated.
  • the fuel parent molecule is completely converted, and the target molecule (fuel molecule) yield is 90%.
  • the substituted cycloketene and the substituted cycloolefin can obtain a fuel molecule having a high tension four-membered ring structure in a high yield by photochemical cycloaddition and solventless hydrodeoxygenation.
  • Example 17 After measurement, the fuel precursor molecule synthesized in Example 17 was subjected to hydrodeoxygenation of Example 28 to have a density of 0.90 g/cm 3 , a freezing point of -55 ° C, and a mass calorific value of 42.5 MJ/kg; 7 The synthesized fuel precursor molecule was subjected to hydrodeoxygenation of Example 38 to produce a fuel molecule having a density of 0.89 g/cm 3 , a freezing point of -40 ° C, and a mass calorific value of 42.7 MJ/kg. Comparing these two fuels, the density and low temperature properties of the fuel molecules with methyl groups on the ring are reduced to some extent. This finding has certain guiding significance for the design and synthesis of fuel molecules in the future.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is a four-membered ring structure fuel molecule and photochemical preparation method therefor. The structure of the fuel molecule is shown as (I), wherein n=1 or 2, and R1, R2, R3, R4, R5 and R6 are independently H or -CH3 or -CH2CH3. The described fuel molecule has the excellent properties of high density, high heat value and low ice point; the described preparation method features a high yield and mild reaction conditions, and no solvent is needed.

Description

一种四元环燃料分子及其光化学制备方法Four-membered ring fuel molecule and photochemical preparation method thereof 技术领域Technical field
本发明属于液体燃料推进剂领域，涉及具有高张力四元环燃料分子及其光化学制备方法。The invention belongs to the field of liquid fuel propellants, and relates to a high tension four-membered ring fuel molecule and a photochemical preparation method thereof.
背景技术Background technique
燃料是一切发动机的血液，保证着发动机的正常运行。对于体积有限的飞机、导弹、火箭等航空航天飞行器而言，则需要更高密度和更高热值的高密度燃料。当飞行器的体积一定时，燃料的密度越大则飞行器携带的燃料质量越大；燃料的燃烧热值越高则消耗单位体积燃料所释放的能量越大，对提高飞行器的性能(包括航程、航速和有效载荷)越有利；或者在保持飞行器性能比不变的前提下，缩小油箱体积，研发小型飞行器来更大程度提高飞行器的突防能力和灵活机动性。Fuel is the blood of all engines, ensuring the normal operation of the engine. For aerospace vehicles with limited volume, such as aircraft, missiles, and rockets, high-density fuels with higher densities and higher calorific values are needed. When the volume of the aircraft is constant, the greater the density of the fuel, the greater the mass of fuel carried by the aircraft; the higher the combustion heat value of the fuel, the greater the energy released per unit volume of fuel, and the performance of the aircraft (including the range and speed) And the payload is more advantageous; or, while keeping the aircraft performance ratio unchanged, the tank volume is reduced, and a small aircraft is developed to greatly improve the aircraft's penetration capability and flexibility.
高密度燃料指人工合成的密度大于0.8g/cm3的液体碳氢燃料，其组成是单组分或者多种烃类的混合物。高密度碳氢燃料的合成分为直接合成高密度、低冰点、高热值的多环烃类和向烃类中添加含能添加剂。大量的实验数据表明，多环结构可以提高碳氢燃料的密度；分子内环张力可以提高燃料的质量热值。文献Green Chemistry，2015，17，4473以MOF包覆的磷钨酸催化环戊酮aldol缩合再加氢脱氧可以高选择性的得到双环戊烷，其密度为0.867g/cm3；文献Scientific Reports，2015，5，9565以环戊醇为原料经过Guerbet反应和加氢脱氧得到密度为0.91g/cm3的三环戊烷。尽管有大量多环烷烃类燃料分子被报道，但是含有高张力四元环结构的燃料分子报道几乎没有。除密度和热值之外，冰点和低温粘度也是燃料很重要的指标。一般情况下，随着密度的增加，碳氢燃料的冰点和低温粘度也随着增加。因而合成兼具高密度、高热值与优异低温性能的高密度燃料是一个很大的挑战。High-density fuel refers to a synthetic liquid hydrocarbon fuel having a density greater than 0.8 g/cm 3 , which is composed of a single component or a mixture of a plurality of hydrocarbons. The synthesis of high-density hydrocarbon fuels is divided into the direct synthesis of high-density, low-freezing, high-calorie polycyclic hydrocarbons and the addition of energetic additives to hydrocarbons. A large number of experimental data show that the polycyclic structure can increase the density of hydrocarbon fuel; the intramolecular ring tension can increase the mass calorific value of the fuel. Literature Green Chemistry, 2015, 17, 4473, with MOF-coated phosphotungstic acid catalyzed cyclopentanone aldol condensation and hydrodeoxygenation, can obtain bicyclopentane with high selectivity, the density is 0.867g / cm 3 ; Scientific Reports, 2015, 5,9565 was subjected to Guerbet reaction and hydrodeoxygenation using cyclopentanol as a raw material to obtain tricyclopentane having a density of 0.91 g/cm 3 . Although a large number of polycycloalkane fuel molecules have been reported, there are few reported fuel molecules containing a high tension four-membered ring structure. In addition to density and calorific value, freezing point and low temperature viscosity are also important indicators of fuel. In general, as the density increases, the freezing point and low temperature viscosity of the hydrocarbon fuel also increase. Therefore, it is a great challenge to synthesize high-density fuels with high density, high calorific value and excellent low-temperature performance.
发明内容Summary of the invention
本发明的目的在于提供一种具有高张力的四元环结构的燃料分子，开发了其光化学制备工艺，且合成的燃料分子同时具有高密度、高热值和低冰点的优异性质。 It is an object of the present invention to provide a fuel molecule having a four-membered ring structure having a high tension, and a photochemical preparation process thereof, and the synthesized fuel molecules have both excellent properties of high density, high calorific value and low freezing point.
本发明的第一方面涉及一种四元环燃料分子，具有如下结构：A first aspect of the invention relates to a four-membered ring fuel molecule having the following structure:
Figure PCTCN2017107696-appb-000001
Figure PCTCN2017107696-appb-000001
其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
优选地，当n＝1时，所述燃料分子的密度为0.88～0.95g/cm3，冰点不高于-55℃，质量热值不低于42.5MJ/kg；当n＝2时，所述燃料分子的密度为0.89～0.97g/cm3，冰点不高于-40℃，质量热值不低于42.7MJ/kg。Preferably, when n=1, the density of the fuel molecules is 0.88-0.95 g/cm 3 , the freezing point is not higher than -55 ° C, and the mass calorific value is not lower than 42.5 MJ/kg; when n=2, The density of the fuel molecules is 0.89 to 0.97 g/cm 3 , the freezing point is not higher than -40 ° C, and the mass calorific value is not lower than 42.7 MJ/kg.
本发明的第二方面涉及所述的四元环燃料分子的制备方法，技术方案一为，包括如下步骤：在光敏剂的存在下，取代环烯酮自身发生环加成反应得到燃料母体分子，然后将燃料母体分子加氢脱氧得到所述的四元环燃料分子，A second aspect of the present invention relates to a method for preparing the four-membered ring fuel molecule. The first aspect of the present invention includes the steps of: in the presence of a photosensitizer, a cyclohexanone itself is subjected to a cycloaddition reaction to obtain a fuel precursor molecule. The fuel parent molecule is then hydrodeoxygenated to obtain the four-membered ring fuel molecule.
Figure PCTCN2017107696-appb-000002
Figure PCTCN2017107696-appb-000002
其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
本发明的第二方面的技术方案二为，包括如下步骤：在光敏剂的存在下，取代环烯酮与取代环烯相互之间发生环加成反应，得到燃料母体分子，然后将燃料母体分子加氢脱氧得到所述的四元环燃料分子，The second aspect of the second aspect of the present invention includes the following steps: in the presence of a photosensitizer, a cycloaddition reaction occurs between a substituted cycloketene and a substituted cycloolefin to obtain a fuel precursor molecule, and then a fuel parent molecule Hydrodeoxygenation to obtain the four-membered ring fuel molecule,
Figure PCTCN2017107696-appb-000003
Figure PCTCN2017107696-appb-000003
Figure PCTCN2017107696-appb-000004
Figure PCTCN2017107696-appb-000004
其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
本发明的第二方面的技术方案三为，包括如下步骤：在光敏剂的存在下，取代环烯自身发生环加成反应，得到所述的四元环燃料分子，The third aspect of the second aspect of the present invention includes the following steps: in the presence of a photosensitizer, a cycloaddition reaction of the substituted cycloolefin itself is carried out to obtain the four-membered ring fuel molecule.
Figure PCTCN2017107696-appb-000005
Figure PCTCN2017107696-appb-000005
其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
优选地，所述的光敏剂为环戊酮、环己酮、丙酮、二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、N-甲基吡咯烷酮的一种或几种，所述光敏剂的加入量为反应物的1wt％～10wt％。Preferably, the photosensitizer is one or more of cyclopentanone, cyclohexanone, acetone, benzophenone, acetophenone, methyl ketone, tetraethyl ketone, N-methylpyrrolidone The photosensitizer is added in an amount of from 1% by weight to 10% by weight of the reactant.
优选地，所述的取代环烯酮为环戊烯酮、3-甲基-2-环戊烯酮、4-甲基-2-环戊烯酮、5-甲基-2-环戊烯酮、4,4’-二甲基-2-环戊烯酮、3,4-二甲基-2-环戊烯酮、3,5-二甲基-2-环戊烯酮、4,5-二甲基-2-环戊烯酮、3,4,4’-三甲基-2-环戊烯酮、3,4,5-三甲基-2-环戊烯酮、3-乙基-2-环戊烯酮、4-乙基-2-环戊烯酮、5-乙基-2-环戊烯酮、4,4’-二乙基-2-环戊烯酮、3,4-二乙基-2-环戊烯酮、3,5-二乙基-2-环戊烯酮、4,5-二乙基-2-环戊烯酮、3,4,4’-三乙基-2-环戊烯酮、3,4,5-三乙基-2-环戊烯酮、环己烯酮、2-甲基-2-环己烯酮、3-甲基-2-环己烯酮、4-甲基-2-环己烯酮、5-甲基-2-环己烯酮、6-甲基-2-环己烯酮、2,3-二甲基-2-环己烯酮、2,4-二甲基-2-环己烯酮、2,5-二甲基-2-环己烯酮、2,6-二甲基-2-环己烯酮、3,4-二甲基-2-环己烯酮、3,5-二甲基-2-环己烯酮、3,6-二甲基-2-环己烯酮、4,5-二甲基-2-环己烯酮、4,6-二甲基-2-环己烯酮、5,6-二甲基-2-环己烯酮、2-乙基-2-环己烯酮、3-乙基-2-环己烯酮、4-乙基-2-环己烯酮、5-乙基-2-环己烯酮、6-乙基-2-环己烯酮、2,3-二乙基-2-环己烯酮、2,4-二乙基-2-环己烯酮、2,5-二乙基-2-环己烯酮、2,6-二乙基-2-环己烯酮、3,4- 二乙基-2-环己烯酮、3,5-二乙基-2-环己烯酮、3,6-二乙基-2-环己烯酮、4,5-二乙基-2-环己烯酮、4,6-二乙基-2-环己烯酮、5,6-二乙基-2-环己烯酮、2,3,4-三甲基-2-环己烯酮、2,3,5-三甲基-2-环己烯酮、2,3,6-三甲基-2-环己烯酮、3,4,5-三甲基-2-环己烯酮、3,4,6-三甲基-2-环己烯酮、4,5,6-三甲基-2-环己烯酮中的一种或几种。Preferably, the substituted cycloketene is cyclopentenone, 3-methyl-2-cyclopentenone, 4-methyl-2-cyclopentenone, 5-methyl-2-cyclopentene Ketone, 4,4'-dimethyl-2-cyclopentenone, 3,4-dimethyl-2-cyclopentenone, 3,5-dimethyl-2-cyclopentenone, 4, 5-dimethyl-2-cyclopentenone, 3,4,4'-trimethyl-2-cyclopentenone, 3,4,5-trimethyl-2-cyclopentenone, 3- Ethyl-2-cyclopentenone, 4-ethyl-2-cyclopentenone, 5-ethyl-2-cyclopentenone, 4,4'-diethyl-2-cyclopentenone, 3,4-diethyl-2-cyclopentenone, 3,5-diethyl-2-cyclopentenone, 4,5-diethyl-2-cyclopentenone, 3,4,4 '-Triethyl-2-cyclopentenone, 3,4,5-triethyl-2-cyclopentenone, cyclohexenone, 2-methyl-2-cyclohexenone, 3-methyl 2-cyclohexenone, 4-methyl-2-cyclohexenone, 5-methyl-2-cyclohexenone, 6-methyl-2-cyclohexenone, 2,3-di Methyl-2-cyclohexenone, 2,4-dimethyl-2-cyclohexenone, 2,5-dimethyl-2-cyclohexenone, 2,6-dimethyl-2- Cyclohexenone, 3,4-dimethyl-2-cyclohexenone, 3,5-dimethyl-2-cyclohexenone, 3,6-dimethyl-2-cyclohexenone, 4,5-dimethyl-2-cyclohexenone, 4,6- Methyl-2-cyclohexenone, 5,6-dimethyl-2-cyclohexenone, 2-ethyl-2-cyclohexenone, 3-ethyl-2-cyclohexenone, 4 -ethyl-2-cyclohexenone, 5-ethyl-2-cyclohexenone, 6-ethyl-2-cyclohexenone, 2,3-diethyl-2-cyclohexenone, 2,4-diethyl-2-cyclohexenone, 2,5-diethyl-2-cyclohexenone, 2,6-diethyl-2-cyclohexenone, 3,4- Diethyl-2-cyclohexenone, 3,5-diethyl-2-cyclohexenone, 3,6-diethyl-2-cyclohexenone, 4,5-diethyl-2 -cyclohexenone, 4,6-diethyl-2-cyclohexenone, 5,6-diethyl-2-cyclohexenone, 2,3,4-trimethyl-2-cyclohexane Enone, 2,3,5-trimethyl-2-cyclohexenone, 2,3,6-trimethyl-2-cyclohexenone, 3,4,5-trimethyl-2-cyclo One or more of hexenone, 3,4,6-trimethyl-2-cyclohexenone, and 4,5,6-trimethyl-2-cyclohexenone.
优选地，所述的取代环烯为环戊烯、甲基环戊烯、3-甲基环戊烯、4-甲基环戊烯、1,2-二甲基环戊烯、1,3-二甲基环戊烯、1,4-二甲基环戊烯、乙基环戊烯、3-乙基环戊烯、4-乙基环戊烯、1,2-二乙基环戊烯、1,3-二乙基环戊烯、1,4-二乙基环戊烯、环己烯、甲基环己烯、3-甲基环己烯、4-甲基环己烯、1,2-二甲基环己烯、1,3-二甲基环己烯、1,4-二甲基环己烯、乙基环己烯、3-乙基环己烯、4-乙基环己烯、1,2-二乙基环己烯、1,3-二乙基环己烯、1,4-二乙基环己烯中的一种或几种。Preferably, the substituted cycloolefin is cyclopentene, methylcyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 1,2-dimethylcyclopentene, 1,3 - dimethylcyclopentene, 1,4-dimethylcyclopentene, ethylcyclopentene, 3-ethylcyclopentene, 4-ethylcyclopentene, 1,2-diethylcyclopentane Alkene, 1,3-diethylcyclopentene, 1,4-diethylcyclopentene, cyclohexene, methylcyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 1,2-Dimethylcyclohexene, 1,3-dimethylcyclohexene, 1,4-dimethylcyclohexene, ethylcyclohexene, 3-ethylcyclohexene, 4-B One or more of cyclohexene, 1,2-diethylcyclohexene, 1,3-diethylcyclohexene, and 1,4-diethylcyclohexene.
优选地，所述的环加成反应的条件为：在高压汞灯照射下，在-40℃～50℃下进行1h～24h。Preferably, the cycloaddition reaction is carried out under the conditions of high pressure mercury lamp irradiation at -40 ° C to 50 ° C for 1 h to 24 h.
优选地，所述燃料母体分子加氢脱氧的反应条件为：在催化剂存在下，反应温度为100℃～200℃，氢气压力为3～8MPa，反应时间为10h～48h；其中所述催化剂为镍、铂或钯负载在HZSM-5、Hβ或HY上的负载型催化剂，或者Pd/C和分子筛物理混合后的混合物。Preferably, the reaction conditions of the hydrodeoxygenation of the fuel precursor molecule are: in the presence of a catalyst, the reaction temperature is 100 ° C to 200 ° C, the hydrogen pressure is 3-8 MPa, and the reaction time is 10 h to 48 h; wherein the catalyst is nickel a supported catalyst in which platinum or palladium is supported on HZSM-5, Hβ or HY, or a mixture of Pd/C and molecular sieves physically mixed.
本发明第三方面涉及所述的四元环结构的燃料分子用于高密度航天燃料的用途。A third aspect of the invention relates to the use of the four-membered ring structure fuel molecules for high density aerospace fuels.
本发明的有益效果：(1)本发明的具有高张力四元环结构的燃料分子同时具有高密度、高热值、低冰点的优异性能，使得其体积热值高于一般液体碳氢燃料，对于油箱体积一定的航天飞行器而言，能有效提高载油质量，满足其远航程、高航速、大载荷的应用需求。(2)本发明的具有高张力四元环结构的燃料分子能够通过常温常压光化学环加成和加氢脱氧制得，本发明的制备方法收率高，不需要溶剂，反应条件温和，对于各类取代环烯酮和取代环烯均具有很好的普适性，具有很高工业化应用价值。Advantageous Effects of Invention: (1) The fuel molecule of the present invention having a high tension four-membered ring structure has both high density, high calorific value, and low freezing point, so that its volumetric calorific value is higher than that of a general liquid hydrocarbon fuel. For a spacecraft with a certain volume of fuel tank, it can effectively improve the quality of oil carrier and meet the application requirements of its long range, high speed and large load. (2) The fuel molecule having the high tension four-membered ring structure of the present invention can be obtained by normal temperature and normal pressure photochemical cycloaddition and hydrodeoxygenation, and the preparation method of the invention has high yield, no solvent, and mild reaction conditions. All kinds of substituted cycloketenes and substituted cycloolefins have good universality and high industrial application value.
附图说明DRAWINGS
无。 no.
具体实施方式Detailed ways
以下表格里的实施例来进一步说明本发明，实施例仅是示例性的，而非限制性的。The invention is further illustrated by the following examples, which are merely illustrative and not restrictive.
表1为燃料母体分子合成反应实施例。Table 1 shows an example of a fuel precursor molecule synthesis reaction.
表1 燃料母体分子合成反应Table 1 Fuel matrix molecular synthesis reaction
Figure PCTCN2017107696-appb-000006
Figure PCTCN2017107696-appb-000006
Figure PCTCN2017107696-appb-000007
Figure PCTCN2017107696-appb-000007
具体反应步骤以表1中的实施例13和17为例。具体步骤为：在25mL的单口夹套玻璃反应器中，加入10g环戊烯酮和10g环己烯(或10g环己烯酮和10g环己烯)，1％质量分数的丙酮，搅拌下氮气鼓泡0.5h，然后密封，开启冷凝水，高压汞灯照射5h。采用气相色谱-质谱连用分析反应液，定性产物和计算反应收率。对于环戊烯酮和环己烯的环加成反应(实施例13)，燃料母体分子的收率为 96％；对于环己烯酮和环己烯的环加成反应(实施例17)，燃料母体分子收率为97％。The specific reaction steps are exemplified by Examples 13 and 17 in Table 1. The specific steps are as follows: in a 25 mL single-port jacketed glass reactor, 10 g of cyclopentenone and 10 g of cyclohexene (or 10 g of cyclohexenone and 10 g of cyclohexene), 1% by mass of acetone, and nitrogen are stirred. Bubbling for 0.5 h, then sealing, opening the condensed water, and irradiating the high pressure mercury lamp for 5 h. The reaction solution was analyzed by gas chromatography-mass spectrometry, and the product was qualitatively determined and the reaction yield was calculated. For the cycloaddition reaction of cyclopentenone and cyclohexene (Example 13), the yield of the fuel precursor molecule is 96%; for the cycloaddition reaction of cyclohexenone and cyclohexene (Example 17), the fuel parent molecular yield was 97%.
表2为燃料母体分子加氢脱氧反应的实施例。Table 2 is an example of a hydrodeoxygenation reaction of a fuel precursor molecule.
表2 燃料母体分子加氢脱氧反应Table 2 Hydrogen deoxygenation reaction of fuel matrix
Figure PCTCN2017107696-appb-000008
Figure PCTCN2017107696-appb-000008
燃料母体分子加氢脱氧反应步骤以表2中实施例29为例。具体步骤如下：将实施例13得到的燃料母体分子以及2g Pd/C和5g Hβ催化剂加入100mL高压釜中，密封，用N2置换3次，然后充入6MPa的H2，搅拌升温至160℃，反应24h。采用气相色谱-质谱连用分析反应液，定性产物和计算反应收率。燃料母体分子完全转化，目标分子(燃料分子)收率90％。The fuel parent molecular hydrodeoxygenation reaction step is exemplified by Example 29 in Table 2. The specific steps are as follows: the fuel precursor molecule obtained in Example 13 and 2 g of Pd/C and 5 g of Hβ catalyst were placed in a 100 mL autoclave, sealed, replaced with N 2 for 3 times, then charged with 6 MPa of H 2 , and stirred to a temperature of 160 ° C. , reaction 24h. The reaction solution was analyzed by gas chromatography-mass spectrometry, and the product was qualitatively determined and the reaction yield was calculated. The fuel parent molecule is completely converted, and the target molecule (fuel molecule) yield is 90%.
由以上可知，取代环烯酮和取代环烯通过光化学环加成和无溶剂加氢脱氧可以高收率地得到具有高张力四元环结构的燃料分子。经过测量，实施例17合成出的燃料母体分子经过实施例28加氢脱氧后制备的燃料分子，其密度为0.90g/cm3，冰点-55℃，质量热值为42.5MJ/kg；实施例7合成出的燃料母体分 子经过实施例38加氢脱氧后制备的燃料分子，其密度为0.89g/cm3，冰点-40℃，质量热值为42.7MJ/kg。对比这两种燃料发现，对于环上有甲基取代的燃料分子，其密度和低温性质均有一定程度降低，此发现对今后燃料分子的设计与合成有一定指导意义。From the above, it can be seen that the substituted cycloketene and the substituted cycloolefin can obtain a fuel molecule having a high tension four-membered ring structure in a high yield by photochemical cycloaddition and solventless hydrodeoxygenation. After measurement, the fuel precursor molecule synthesized in Example 17 was subjected to hydrodeoxygenation of Example 28 to have a density of 0.90 g/cm 3 , a freezing point of -55 ° C, and a mass calorific value of 42.5 MJ/kg; 7 The synthesized fuel precursor molecule was subjected to hydrodeoxygenation of Example 38 to produce a fuel molecule having a density of 0.89 g/cm 3 , a freezing point of -40 ° C, and a mass calorific value of 42.7 MJ/kg. Comparing these two fuels, the density and low temperature properties of the fuel molecules with methyl groups on the ring are reduced to some extent. This finding has certain guiding significance for the design and synthesis of fuel molecules in the future.
实施例17-实施例28
Figure PCTCN2017107696-appb-000009
Example 17 - Example 28
Figure PCTCN2017107696-appb-000009
实施例7-实施例38
Figure PCTCN2017107696-appb-000010
Example 7 - Example 38
Figure PCTCN2017107696-appb-000010

Claims (11)

  1. 一种四元环燃料分子，其特征在于，具有如下结构：A four-membered ring fuel molecule characterized by having the following structure:
    Figure PCTCN2017107696-appb-100001
    Figure PCTCN2017107696-appb-100001
    其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  2. 根据权利要求1所述的四元环燃料分子，其特征在于，当n＝1时，所述燃料分子的密度为0.88～0.95g/cm3，冰点不高于-55℃，质量热值不低于42.5MJ/kg；当n＝2时，所述燃料分子的密度为0.89～0.97g/cm3，冰点不高于-40℃，质量热值不低于42.7MJ/kg。The four-membered ring fuel molecule according to claim 1, wherein when n=1, the density of the fuel molecules is 0.88 to 0.95 g/cm 3 , the freezing point is not higher than -55 ° C, and the mass calorific value is not It is lower than 42.5 MJ/kg; when n=2, the density of the fuel molecules is 0.89 to 0.97 g/cm 3 , the freezing point is not higher than -40 ° C, and the mass calorific value is not lower than 42.7 MJ/kg.
  3. 根据权利要求1所述的四元环燃料分子的制备方法，其特征在于，包括如下步骤：在光敏剂的存在下，取代环烯酮自身发生环加成反应得到燃料母体分子，然后将燃料母体分子加氢脱氧得到所述的四元环燃料分子，The method for preparing a four-membered ring fuel molecule according to claim 1, comprising the steps of: in the presence of a photosensitizer, a cyclohexanone itself undergoes a cycloaddition reaction to obtain a fuel precursor molecule, and then a fuel precursor Hydrodeoxygenation of the molecule to obtain the four-membered ring fuel molecule,
    Figure PCTCN2017107696-appb-100002
    Figure PCTCN2017107696-appb-100002
    其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  4. 根据权利要求1所述的四元环结构的燃料分子的制备方法，其特征在于，包括如下步骤：在光敏剂的存在下，取代环烯酮与取代环烯相互之间发生环加成反应，得到燃料母体分子，然后将燃料母体分子加氢脱氧得到所述的四元环燃料分子，The method for preparing a four-membered ring structure fuel molecule according to claim 1, comprising the steps of: forming a cycloaddition reaction between the substituted cycloketene and the substituted cycloolefin in the presence of a photosensitizer; Obtaining a fuel precursor molecule, and then hydrodeoxygenating the fuel precursor molecule to obtain the four-membered ring fuel molecule,
    Figure PCTCN2017107696-appb-100003
    Figure PCTCN2017107696-appb-100003
    Figure PCTCN2017107696-appb-100004
    Figure PCTCN2017107696-appb-100004
    其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  5. 根据权利要求1所述的四元环结构的燃料分子的制备方法，其特征在于，包括如下步骤：在光敏剂的存在下，取代环烯自身发生环加成反应，得到所述的四元环燃料分子，The method for preparing a four-membered ring structure fuel molecule according to claim 1, comprising the steps of: performing a cycloaddition reaction in place of the cycloolefin itself in the presence of a photosensitizer to obtain the four-membered ring; Fuel molecules,
    Figure PCTCN2017107696-appb-100005
    Figure PCTCN2017107696-appb-100005
    其中，n＝1或2，R1、R2、R3、R4、R5、R6各自独立为H或-CH3或-CH2CH3。Wherein n = 1 or 2, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently H or -CH 3 or -CH 2 CH 3 .
  6. 根据权利要求3、4或5所述的制备方法，其特征在于，所述的光敏剂为环戊酮、环己酮、丙酮、二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、N-甲基吡咯烷酮的一种或几种，所述光敏剂的加入量为反应物的1wt％～10wt％。The preparation method according to claim 3, 4 or 5, wherein the photosensitizer is cyclopentanone, cyclohexanone, acetone, benzophenone, acetophenone, mifeone, tetraethyl One or more of Mie's ketone and N-methylpyrrolidone, the photosensitizer is added in an amount of from 1% by weight to 10% by weight of the reactant.
  7. 根据权利要求3或4所述的制备方法，其特征在于，所述的取代环烯酮为环戊烯酮、3-甲基-2-环戊烯酮、4-甲基-2-环戊烯酮、5-甲基-2-环戊烯酮、4,4’-二甲基-2-环戊烯酮、3,4-二甲基-2-环戊烯酮、3,5-二甲基-2-环戊烯酮、4,5-二甲基-2-环戊烯酮、3,4,4’-三甲基-2-环戊烯酮、3,4,5-三甲基-2-环戊烯酮、3-乙基-2-环戊烯酮、4-乙基-2-环戊烯酮、5-乙基-2-环戊烯酮、4,4’-二乙基-2-环戊烯酮、3,4-二乙基-2-环戊烯酮、3,5-二乙基-2-环戊烯酮、4,5-二乙基-2-环戊烯酮、3,4,4’-三乙基-2-环戊烯酮、3,4,5-三乙基-2-环戊烯酮、环己烯酮、2-甲基-2-环己烯酮、3-甲基-2-环己烯酮、4-甲基-2-环己烯酮、5-甲基-2-环己烯酮、6-甲基-2-环己烯酮、2,3-二甲基-2-环己烯酮、2,4-二甲基-2-环己烯酮、2,5-二甲基-2-环己烯酮、2,6-二甲基-2-环己烯酮、3,4-二甲基-2-环己烯酮、3,5-二甲基-2-环己烯酮、3,6-二甲基-2-环己烯酮、4,5-二甲基-2-环己烯酮、4,6-二甲基-2-环己烯酮、5,6-二甲基-2-环己烯酮、2-乙基-2-环己烯酮、3-乙基-2-环己烯酮、4-乙基-2-环己烯酮、5-乙基-2-环己烯酮、6-乙基-2-环己烯酮、2,3-二乙基-2-环己烯酮、2,4-二乙基-2-环己烯酮、2,5-二 乙基-2-环己烯酮、2,6-二乙基-2-环己烯酮、3,4-二乙基-2-环己烯酮、3,5-二乙基-2-环己烯酮、3,6-二乙基-2-环己烯酮、4,5-二乙基-2-环己烯酮、4,6-二乙基-2-环己烯酮、5,6-二乙基-2-环己烯酮、2,3,4-三甲基-2-环己烯酮、2,3,5-三甲基-2-环己烯酮、2,3,6-三甲基-2-环己烯酮、3,4,5-三甲基-2-环己烯酮、3,4,6-三甲基-2-环己烯酮、4,5,6-三甲基-2-环己烯酮中的一种或几种。The process according to claim 3 or 4, wherein the substituted cycloketene is cyclopentenone, 3-methyl-2-cyclopentenone, 4-methyl-2-cyclopentane Ketone, 5-methyl-2-cyclopentenone, 4,4'-dimethyl-2-cyclopentenone, 3,4-dimethyl-2-cyclopentenone, 3,5- Dimethyl-2-cyclopentenone, 4,5-dimethyl-2-cyclopentenone, 3,4,4'-trimethyl-2-cyclopentenone, 3,4,5- Trimethyl-2-cyclopentenone, 3-ethyl-2-cyclopentenone, 4-ethyl-2-cyclopentenone, 5-ethyl-2-cyclopentenone, 4,4 '-Diethyl-2-cyclopentenone, 3,4-diethyl-2-cyclopentenone, 3,5-diethyl-2-cyclopentenone, 4,5-diethyl -2-cyclopentenone, 3,4,4'-triethyl-2-cyclopentenone, 3,4,5-triethyl-2-cyclopentenone, cyclohexenone, 2- Methyl-2-cyclohexenone, 3-methyl-2-cyclohexenone, 4-methyl-2-cyclohexenone, 5-methyl-2-cyclohexenone, 6-methyl -2-cyclohexenone, 2,3-dimethyl-2-cyclohexenone, 2,4-dimethyl-2-cyclohexenone, 2,5-dimethyl-2-cyclohexane Enone, 2,6-dimethyl-2-cyclohexenone, 3,4-dimethyl-2-cyclohexenone, 3,5-dimethyl-2-cyclohexenone, 3, 6-dimethyl- 2-cyclohexenone, 4,5-dimethyl-2-cyclohexenone, 4,6-dimethyl-2-cyclohexenone, 5,6-dimethyl-2-cyclohexene Ketone, 2-ethyl-2-cyclohexenone, 3-ethyl-2-cyclohexenone, 4-ethyl-2-cyclohexenone, 5-ethyl-2-cyclohexenone, 6-ethyl-2-cyclohexenone, 2,3-diethyl-2-cyclohexenone, 2,4-diethyl-2-cyclohexenone, 2,5-di Ethyl-2-cyclohexenone, 2,6-diethyl-2-cyclohexenone, 3,4-diethyl-2-cyclohexenone, 3,5-diethyl-2- Cyclohexenone, 3,6-diethyl-2-cyclohexenone, 4,5-diethyl-2-cyclohexenone, 4,6-diethyl-2-cyclohexenone, 5,6-diethyl-2-cyclohexenone, 2,3,4-trimethyl-2-cyclohexenone, 2,3,5-trimethyl-2-cyclohexenone, 2 , 3,6-trimethyl-2-cyclohexenone, 3,4,5-trimethyl-2-cyclohexenone, 3,4,6-trimethyl-2-cyclohexenone, One or more of 4,5,6-trimethyl-2-cyclohexenone.
  8. 根据权利要求4或5所述的制备方法，其特征在于，所述的取代环烯为环戊烯、甲基环戊烯、3-甲基环戊烯、4-甲基环戊烯、1,2-二甲基环戊烯、1,3-二甲基环戊烯、1,4-二甲基环戊烯、乙基环戊烯、3-乙基环戊烯、4-乙基环戊烯、1,2-二乙基环戊烯、1,3-二乙基环戊烯、1,4-二乙基环戊烯、环己烯、甲基环己烯、3-甲基环己烯、4-甲基环己烯、1,2-二甲基环己烯、1,3-二甲基环己烯、1,4-二甲基环己烯、乙基环己烯、3-乙基环己烯、4-乙基环己烯、1,2-二乙基环己烯、1,3-二乙基环己烯、1,4-二乙基环己烯中的一种或几种。The process according to claim 4 or 5, wherein the substituted cycloolefin is cyclopentene, methylcyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 1 ,2-dimethylcyclopentene, 1,3-dimethylcyclopentene, 1,4-dimethylcyclopentene, ethylcyclopentene, 3-ethylcyclopentene, 4-ethyl Cyclopentene, 1,2-diethylcyclopentene, 1,3-diethylcyclopentene, 1,4-diethylcyclopentene, cyclohexene, methylcyclohexene, 3-methyl Cyclohexene, 4-methylcyclohexene, 1,2-dimethylcyclohexene, 1,3-dimethylcyclohexene, 1,4-dimethylcyclohexene, ethylcyclohexane Alkene, 3-ethylcyclohexene, 4-ethylcyclohexene, 1,2-diethylcyclohexene, 1,3-diethylcyclohexene, 1,4-diethylcyclohexene One or several of them.
  9. 根据权利要求3、4或5所述的制备方法，其特征在于，所述的环加成反应的条件为：在高压汞灯照射下，在-40℃～50℃下进行1h～24h。The preparation method according to claim 3, 4 or 5, wherein the cycloaddition reaction is carried out under the conditions of a high pressure mercury lamp at -40 ° C to 50 ° C for 1 h to 24 h.
  10. 根据权利要求3或4所述的制备方法，其特征在于，所述燃料母体分子加氢脱氧的反应条件为：在催化剂存在下，反应温度为100℃～200℃，氢气压力为3～8MPa，反应时间为10h～48h；其中所述催化剂为镍、铂或钯负载在HZSM-5、Hβ或HY上的负载型催化剂，或者Pd/C和分子筛物理混合后的混合物。The preparation method according to claim 3 or 4, wherein the reaction condition of the hydrodeoxygenation of the fuel precursor molecule is: in the presence of a catalyst, the reaction temperature is from 100 ° C to 200 ° C, and the hydrogen pressure is from 3 to 8 MPa. The reaction time is from 10 h to 48 h; wherein the catalyst is a supported catalyst supported on nickel, platinum or palladium on HZSM-5, Hβ or HY, or a mixture of Pd/C and molecular sieves physically mixed.
  11. 根据权利要求1所述的四元环结构的燃料分子用于航天燃料的用途。 Use of a four-membered ring structure fuel molecule according to claim 1 for aerospace fuels.
PCT/CN2017/107696 2017-10-25 2017-10-25 Four-membered ring fuel molecule and photochemical preparation method therefor WO2019080016A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/107696 WO2019080016A1 (en) 2017-10-25 2017-10-25 Four-membered ring fuel molecule and photochemical preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/107696 WO2019080016A1 (en) 2017-10-25 2017-10-25 Four-membered ring fuel molecule and photochemical preparation method therefor

Publications (1)

Publication Number Publication Date
WO2019080016A1 true WO2019080016A1 (en) 2019-05-02

Family

ID=66246164

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/107696 WO2019080016A1 (en) 2017-10-25 2017-10-25 Four-membered ring fuel molecule and photochemical preparation method therefor

Country Status (1)

Country Link
WO (1) WO2019080016A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5220085A (en) * 1991-06-13 1993-06-15 Chung Shan Institute Of Science And Technology Preparation method of high density fuels by the addition-rearrangement of compound pentacyclo [7.5.1.O2,8.O3,7.-O10,14 ] pentadecane (C15 H22)
US5545790A (en) * 1993-12-09 1996-08-13 Mobil Oil Corporation Process for the catalytic cyclodimerization of cyclic olefins
CN102010764A (en) * 2010-12-01 2011-04-13 天津大学 Diamantine liquid hydrocarbon fuel and synthesis method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5220085A (en) * 1991-06-13 1993-06-15 Chung Shan Institute Of Science And Technology Preparation method of high density fuels by the addition-rearrangement of compound pentacyclo [7.5.1.O2,8.O3,7.-O10,14 ] pentadecane (C15 H22)
US5545790A (en) * 1993-12-09 1996-08-13 Mobil Oil Corporation Process for the catalytic cyclodimerization of cyclic olefins
CN102010764A (en) * 2010-12-01 2011-04-13 天津大学 Diamantine liquid hydrocarbon fuel and synthesis method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
BALDWIN, JOHN E.: "Thermal Isomerization of cis, anti, cis- Tricyclo[6.3. 0. 0]undec-3-ene to endo-Tricyclo[5. 2. 2. 0]undec-8-ene", ORG. LETT., vol. 7, no. 23, 19 October 2005 (2005-10-19) - 10 November 2005 (2005-11-10), pages 5195 - 5197, XP055594300, ISSN: 1523-7060, DOI: 10.1021/ol052004k *
HEATHCOCK, CLAYTON H.: "Photochemistry of 1, 6-Cyclodecadienes. I. 1-Me- thyl-(E, E)-I, 6-cyclodecadiene", J. ORG. CHEM., vol. 37, no. 23, 1 November 1972 (1972-11-01) - 31 December 1972 (1972-12-31), pages 3754, XP055594298, ISSN: 0022-3263, DOI: 10.1021/jo00796a918 *
HILL,E. ALEXANDER: "Ring Cleavage Rearrangements of 2- Bicyclo[3.2.0]heptyl and Related Grignard Reagents", J. ORG. CHEM., vol. 41, no. 7, 31 December 1976 (1976-12-31), pages 1191 - 1199, XP055594295, ISSN: 0022-3263, DOI: 10.1021/jo00869a024 *
PAN LUN ET AL.: "Synthesis Chemistry of High-Density Fuels for Aviation and Aerospace Propulsion", PROGRESS IN CHEMISTRY, vol. 27, no. 11, 3 November 2015 (2015-11-03), pages 1531 - 1541, XP055594311, DOI: 10.7536/PC150531 *
RANU,BRINDABAN C.: "Two-carbon Ring Expansion through Free Cyclo butylcar- binyl Radical Fragmentation", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1,, vol. 8, 31 December 1994 (1994-12-31), pages 921 - 922, XP009063217, ISSN: 0300-922X, DOI: 10.1039/p19940000921 *
ZOU JIJUN ET AL.: "High Density Liquid Hydrocarbon Fuels for Aerospace Propulsion : Synthesis and Application", JOURNAL OF PROPULSION TECHNOLOGY, vol. 35, no. 10, 31 October 2014 (2014-10-31), pages 1419 - 1425, XP055594307, DOI: 10.13675/j.cnki.tjjs.2014.10.018 *

Similar Documents

Publication Publication Date Title
CN108191599B (en) Four-membered ring fuel molecule and photochemical preparation method thereof
Pan et al. Supercritical pyrolysis and coking of JP-10 in regenerative cooling channels
CN109852441B (en) Polycyclic high-density biomass liquid fuel and preparation method and application thereof
Xu et al. Synthesis of high-density aviation fuels with methyl benzaldehyde and cyclohexanone
AU2020102624A4 (en) Four-Membered Ring Aerospace Fuel Synthesized by Norbornene and Norbornene Homologue and Preparation Method by Heterogeneous Photocatalytic Cyclization and Use Thereof
CN105062579A (en) Method for preparing high-density mixed hydrocarbon liquid jet fuel from dicyclopentadiene
Ryan et al. Synthesis of aviation fuel from bio-derived isophorone
CN110041158A (en) Dicyclopropyl compound, preparation method and application thereof
US10519081B1 (en) Process for the preparation of a bicyclic fused-ring alkane
WO2021143277A1 (en) Method for storing hydrogen using structure-h hydrate
CN104449818B (en) Cyclopentadiene high density liquid hydrocarbon fuel and synthetic method thereof
CN112980501B (en) One-pot preparation method of turpentine-based biomass high-energy-density fuel
Woodroffe et al. Thermal cyclodimerization of isoprene for the production of high-performance sustainable aviation fuel
Wang et al. High energy density renewable fuels based on multicyclic sesquiterpene: Synthesis and performance
WO2019080016A1 (en) Four-membered ring fuel molecule and photochemical preparation method therefor
CN107814676B (en) Preparation method of decahydronaphthalene and tetrahydronaphthalene
CN117085734A (en) Hydrocracking catalyst, application and cracking method
WO2017161780A1 (en) Method for preparing perhydrofluorene or perhydrofluorene alkyl substituent
CN111218312B (en) Method for preparing aviation fuel from biomass platform compound
US10689309B1 (en) Fused-ring alkane fuel and photocatalytic preparation process thereof
CN110923001A (en) Method for preparing special fuel with low freezing point, high density and high thermal stability by using lignocellulose biomass
CN108865298B (en) Fused ring alkane fuel and photocatalytic preparation method thereof
WO2020010494A1 (en) Fused cycloalkane fuel and photocatalytic preparation method thereof
CN113651667B (en) Cyclopropyl alkyl compound, preparation method and application thereof
CN109233890A (en) A kind of oil gas coproduction gasification process and device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17929530

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205N DATED 28.08.2020)

122 Ep: pct application non-entry in european phase

Ref document number: 17929530

Country of ref document: EP

Kind code of ref document: A1