WO2019080016A1 - Molécule de combustible cyclique à quatre éléments et son procédé de préparation photochimique - Google Patents

Molécule de combustible cyclique à quatre éléments et son procédé de préparation photochimique

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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
English (en)
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/fr
Publication of WO2019080016A1 publication Critical patent/WO2019080016A1/fr

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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

L'invention concerne une molécule de combustible à structure cyclique à quatre éléments et son procédé de préparation photochimique. La structure de la molécule de combustible est représentée comme (I), n = 1 ou 2, et R 1, R 2, R 3, R 4, R 5 et R 6 étant indépendamment H ou -CH 3 ou -CH 2CH 3. La molécule de combustible selon l'invention présente d'excellentes propriétés de densité élevée, de haute valeur thermique et de bas point de glace; le procédé de préparation fourni par l'invention présente un rendement élevé et des conditions de réaction modérées, et ne nécessite aucun solvant.
PCT/CN2017/107696 2017-10-25 2017-10-25 Molécule de combustible cyclique à quatre éléments et son procédé de préparation photochimique WO2019080016A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/107696 WO2019080016A1 (fr) 2017-10-25 2017-10-25 Molécule de combustible cyclique à quatre éléments et son procédé de préparation photochimique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/107696 WO2019080016A1 (fr) 2017-10-25 2017-10-25 Molécule de combustible cyclique à quatre éléments et son procédé de préparation photochimique

Publications (1)

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

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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 (zh) * 2010-12-01 2011-04-13 天津大学 金刚烃类液体碳氢燃料及其合成方法

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 (zh) * 2010-12-01 2011-04-13 天津大学 金刚烃类液体碳氢燃料及其合成方法

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 *

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