CN110511778A - A method of using cyclopentanone as the polycyclic high density aviation fuel of raw material controlled syntheses - Google Patents

A method of using cyclopentanone as the polycyclic high density aviation fuel of raw material controlled syntheses Download PDF

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CN110511778A
CN110511778A CN201910721411.2A CN201910721411A CN110511778A CN 110511778 A CN110511778 A CN 110511778A CN 201910721411 A CN201910721411 A CN 201910721411A CN 110511778 A CN110511778 A CN 110511778A
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cyclopentanone
density
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aviation fuel
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CN110511778B (en
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王洪
李占超
王一卓
李洋
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

A method of using cyclopentanone as the polycyclic high density aviation fuel of raw material controlled syntheses, in the case that dimethyl carbonate there are, aldol condensation-esterification reaction of organic acid occurs under alkaline condition for cyclopentanone, forms 1, the 3- dicarbonyl compound 1 with twin nuclei；Then under the conditions of solvent-free, nucleophilic substitution occurs under alkaline condition for compound 1 and various alkyl halides, has synthesized a series of high-density propellant midbody compounds；Under lewis acid/Protic Acid Catalyzed, using silicon hydrogen reagent hydrodeoxygenation reaction occurred into for midbody compound synthesize a series of there is bicyclic, tricyclic, Fourth Ring, the high-density hydrocarbons compound at five rings.The liquid carbon hydrogen fuel of this method synthesis can be used for all kinds of aircraft or improve the flying quality of aviation fuel as additive.

Description

A method of using cyclopentanone as the polycyclic high density aviation fuel of raw material controlled syntheses
Technical field
The invention belongs to aerospace fields, are related to a kind of polycyclic high density aviation fuel, and in particular to one kind is with ring penta Ketone is the method for the polycyclic high density aviation fuel of raw material controlled syntheses, can be widely applied to aerospace field.
Background technique
In recent years, along with a large amount of influences using with environmental degradation of fossil fuel, exploitation biomass etc. is novel to be held Continuous green energy resource technology has obtained the extensive concern of people.Aviation fuel has extensively as a kind of transport fuel in aviation field General application.Currently, main aviation fuel is prepared by main source of petroleum base in the world.In view of environment is protected Shield, energy security and economic value, developing biomass-based aviation fuel and just seeming is highly desirable.
Aviation kerosine is usually to be made of the saturated straight chain of C6-C16 or branched paraffin, is common aviation fuel.But Its volume calorific value is lower, is not able to satisfy the flight requirement of aircraft of new generation.High density aviation fuel is as a kind of with highly dense Degree, the liquid carbon hydrogen fuel of Gao Tiji calorific value can effectively improve the performance of aerospace craft, such as voyage, the speed of a ship or plane and load etc..Cause This, synthesis high density aviation fuel has very big value and significance.
From the point of view of molecular structure, the density of hydrocarbon increases with the increase of carbon number, and the density of alkane compared with It is low and cycloalkane density is lower.For example, the density of aviation kerosene based on alkane is 0.78g/ml, and the fire containing cycloalkane Arrow kerosene density reaches 0.83g/ml.Therefore, constructing polycyclic hydrocarbon is a research for synthesizing high density aviation fuel Hot spot.
Liquid fuel was prepared has been developed for a long time by biomass.It is initially with starch, the grains such as corn are Raw material prepares bio-ethanol, due to worrying that crisis in food can occur, so develop second generation biomass liquid fuel.Second For biomass liquid fuel using lignocellulosic as primary raw material, by chemistry, biological method (fermentation, degradation etc.) obtains platform Molecule.Then there is the midbody compound of oxygen atom by the synthesis of C-C key coupling reaction, be prepared for finally by HDO reaction Liquid carbon hydrogen fuel.The work of this respect has had many reports, first with furtural or substituted furan formaldehyde and small point Aldol reaction occurs for sub- ketone, then the liquid carbon by the HDO reaction synthesis of high temperature and pressure based on straight chain or branch Hydrogen fuel.But the density of this class A fuel A and the lower (density < 0.83g/cm of volume calorific value3；The combustion heat < 36MJ/L), Bu Nengyou The utilization of effect is in aerospace field.
Furtural has obtained extensive as a kind of important biomass plateform molecules in terms of synthesising biological matter fuel Using.But furan ring structure is reacted by HDO and is generally all reduced into chain alkane, lead to fuel density and the combustion of synthesis It heats lower.In recent years, there are many reports conducive to furtural synthesis cyclopentanone.Hronec et al. report, furtural exist In the presence of 5%Pt/C, 160 DEG C, 30 atmospheric pressure, the yield of cyclopentanone reaches 76.5% (Applied in water phase Catalysis A:General, 2012,437-438,104-111).Yong Cao et al. report, furtural is in Au/ TiO2Under-A catalysis, 160 DEG C, 40 atmospheric pressure, in water phase the yield of cyclopentanone reach 99% (Green Chem., 2016, 18,2155-2164).Therefore, cyclopentanone is a kind of biomass plateform molecules compound that can be utilized extensively.
Synthesizing high-density propellant also using the cyclopentanone being converted to by furtural has many reports, but is only limitted to cyclopentanone The product and cyclopentanone and aldehyde of self-condensation, the reduction of the high temperature and pressure of the condensation product of ketone.For example, Tao Zhang etc. People's report, cyclopentanone and butyraldehyde pass through solvent-free cross-aldol condensation first and prepare ketene compound, then exist Ni–SiO2Catalyst is reacted by HDO in 503K, 6MPa and has synthesized butyl pentamethylene and 1,3- dibutyl with~80% yield Pentamethylene mixture (density: 0.82g/cm3；Freezing point: -96 DEG C), (Ind.Eng.Chem.Res., 2015,54,11825- 11837)。
The hydroxyl of solvent-free occurs under NaOH catalysis first for Ji-Jun Zou et al. report, cyclopentanone and Furan Aldehydes Aldehyde condensation reaction, then in Pd/H beta catalyst, in 556K, it is (close that 8MPa by HDO reaction has synthesized 1,3- diamyl cyclopentane Degree: 0.815 g/cm3；Freezing point: -24.6 DEG C；Viscosity: 3.8mm2/s)。(Fuel Processing Technology,2016, 148,361–366)
Tao Zhang et al. report, cyclopentanone form 2- ring pentylidene ring by solvent-free aldol reaction Pentanone, then in Ni-SiO2Catalyst is reacted by HDO in 503K, 6MPa and has synthesized bicyclic C10 compound with 80% yield (density: 0.866g/cm3；The combustion heat: 36.77MJ/L；Freezing point: -38 DEG C；Viscosity: 1.62mm2/s)(Chem.Commun., 2014, 50,2572)。
It is reported for above synthesis, it is known that cyclopentanone self-condensation reaction can only be used to synthesize bicyclic pentane high density combustion Material.And their property is it has been reported that mistake, there is also certain disadvantages in actual use.For example, density is not high or viscous Spend larger transport and combustibility to influence fuel.And the condensation product of cyclopentanone and other ketone or aldehydes can only be used to The compound with single pentamethylene is synthesized, so that these liquid fuel density be caused to be substantially reduced, combustion heat value also obviously drops It is low.(density < 0.83g/cm3；The combustion heat < 36MJ/L) moreover, sixty-four dollar question is that HDO reaction is generally required in high temperature height (> 200 DEG C, > 6MPa) are carried out under the conditions of pressure, reaction condition is harsher, and it is more demanding for consersion unit, and in reaction process Also there can be apparent security risk, be unfavorable for mass production.
Summary of the invention
The purpose of the present invention is to provide a kind of using cyclopentanone as the side of the polycyclic high density aviation fuel of raw material controlled syntheses Method.
To achieve the above object, the present invention is achieved by the following technical solutions:
A method of using cyclopentanone as the polycyclic high density aviation fuel of raw material controlled syntheses, comprising the following steps:
1) in the case that dimethyl carbonate there are, aldol condensation-esterification reaction of organic acid occurs in the presence of a base for cyclopentanone, formed One 1,3- dicarbonyl compound 1 with twin nuclei；
2) under solvent-free conditions, nucleophilic substitution occurs in the presence of a base for 1,3- dicarbonyl compound 1 and alkyl halide, Synthesize high-density propellant midbody compound；
3) under Lewis acid catalysis, using silicon hydrogen reagent, high-density propellant midbody compound is in Bronsted acid existence condition Under have occurred hydrodeoxygenation reaction, synthesize high-density hydrocarbons compound.
A further improvement of the present invention lies in that the detailed process of step 1) are as follows: by alkali: cyclopentanone: dimethyl carbonate rubs Alkali, cyclopentanone and dimethyl carbonate are added in reactor than being 1~3:1:1~3, reaction dissolvent are then added, 80 by you 1~12h is reacted at~120 DEG C；Obtain 1,3- dicarbonyl compound 1.
A further improvement of the present invention lies in that alkali is one or more of solid base, inorganic base and organic base Mixture；Reaction dissolvent is toluene.
A further improvement of the present invention lies in that solid base CaO, MgO, one or more of MgAl-HT；It is inorganic Alkali is NaOH, NaNH2, KOH, NaH, one or more of KH；Organic base is butyl reason, LDA, LHMDS, t-BuOK One or more of mixture.
A further improvement of the present invention lies in that alkali CaO, NaOH, NaNH2, NaH, LDA, one or both of LHMDS Above mixture.
A further improvement of the present invention lies in that the detailed process of step 2) are as follows: press 1,3- dicarbonyl compound 1: alkali: halogenated Alkane molar ratio is 3:3:1~3,1,3- dicarbonyl compound 1, alkali and alkyl halide is added in reactor, at 50~90 DEG C It is lower reaction 0.5~for 24 hours, obtain high-density propellant midbody compound.
A further improvement of the present invention lies in that alkali is one of solid base, inorganic base and organic base or two in step 2) Kind or more mixture.
A further improvement of the present invention lies in that solid base CaO, MgO, one or more of MgAl-HT；It is inorganic Alkali is NaOH, KOH, Ba (OH)2One or more of；Organic base is sodium ethoxide, sodium methoxide, one of t-BuOK or Two or more mixtures；
The chemical formula of alkyl halide is RX and RX2, RX and RX2For one or both of bromoalkane, idoalkane and alkyl chloride with On；Alkane structure R includes straight chain, branch saturated alkane, unsaturated alkane and cycloalkane.
A further improvement of the present invention lies in that in step 2), alkali MgO, NaOH, sodium ethoxide, one of t-BuOK or The two or more mixtures of person；
The detailed process of step 3) are as follows: press compound intermediate: Lewis acid: Bronsted acid: silicon hydrogen reagent molar ratio is 1: High-density propellant midbody compound, Lewis acid, Bronsted acid and silicon hydrogen reagent are added 0.01~0.1:3~6:6~12 Into reactor, solvent is then added, at 25~50 DEG C react 0.5~for 24 hours, obtain high-density hydrocarbons compound；Its In, solvent is methylene chloride.
A further improvement of the present invention lies in that Lewis acid is AlCl3, FeCl3, BF3, B (C6F5)3, Zn (OTf)2In one Kind is two or more；Bronsted acid is hydrochloric acid, HF, H2SO4, one or more of HI；Silicon hydrogen reagent is diethylsilane, Polymethyl hydrogen siloxane, diphenyl silane, dimethyl ethyl silane, triethylsilane, in 1,1,3,3- tetramethyl disiloxane One or more.
Compared with prior art, the invention has the benefit that the present invention is by the way that in dimethyl carbonate, there are feelings first Under condition, aldol condensation-esterification reaction of organic acid occurs under alkaline condition for cyclopentanone, forms 1,3-, bis- carbonyl with twin nuclei Based compound 1；Then under the conditions of solvent-free, nucleophilic substitution occurs for compound 1 and alkyl halide, has synthesized one Series has the high-density propellant midbody compound of different number of rings；Finally under Lewis acid catalysis, silicon hydrogen reagent, In are utilized Under lower temperature and condition of normal pressure, hydrodeoxygenation reaction has occurred, has synthesized a series of with bicyclic, tricyclic, Fourth Ring, five rings knot The high-density propellant compound of structure.
The present invention has efficiently been synthesized by three-step reaction with a series of of multiring structure using cyclopentanone as raw material High-density propellant compound (density: 0.90~1.0g/cm3).The present invention is mother with cyclopentanone condensation-esterification compound 1 Body compound changes the steric configuration of compound by introducing different side-chain structure, regulating compound that can be purposive Physical property (such as density, viscosity, freezing point, combustion heat etc.), to obtain the height with different performance and application function Density fuel compound, these compounds can be applied to different space flight and aviation equipment.For existing biomass class high density It all needs to prepare heterogeneous catalysis in fuel synthesis, and needs to carry out the HDO reaction (> 200 DEG C, > 6MPa) of high temperature and pressure, this Invention uses the nucleophilic substitution and the acid catalyzed silicon hydrogen reduction reaction of Lewis of Solvent-free, this synthetic route Succinctly, and reaction condition is mild.In the synthetic route, the present invention not only can regulate and control chemical combination by changing side-chain structure The physical property (such as density, viscosity, freezing point, combustion heat etc.) of object, and the use of high-temperature and high-pressure conditions is avoided, it drops The risk of low reaction, convenient for industrial application.
The controlled syntheses of the high-density propellant of different structure may be implemented in the present invention, and simultaneously synthesizing fuel is with higher Density (calculated theoretical density: 0.89~1.0g/cm3；Actual density: 0.90~1.0g/cm3) and volume calorific value (theoretical calculation The combustion heat: 37~43 MJ/L), it can be widely applied to field of aerospace.
The compound density all with higher and lower viscosity synthesized using method of the invention, and it has been reported that Compound comparison, in the equirotal situation of compound density, the compound viscosity that the present invention synthesizes is lower；In viscosity size In the case where the same, the compound density that the present invention synthesizes is higher, can be used for all kinds of aircraft or improves as additive The flying quality of aviation fuel.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail.
The present invention is using cyclopentanone as raw material, and by three step simple reactions, efficiently succinct synthesis has a specific polycyclic knot The high density aviation fuel compound of structure.With 1,3- dicarbonyl compound 1 for parent compound, pass through the parent of solvent-free Core substitution reaction, has synthesized different substituted bicyclic, the tricyclics of some column, Fourth Ring, then the midbody compound at five rings utilizes silicon Hydrogen reduction agent realizes mild HDO reaction under lower temperature and normal pressure, is prepared for having bicyclic, tricyclic, Fourth Ring, five rings knot The high-density hydrocarbons compound of structure.The compound of these different number of rings can have different property according to structure difference (density, viscosity, the combustion heat, freezing point) can be adapted for different air transportation fields.Especially, highly dense for biomass class HDO reaction during degree preparation of fuel generally needs to use using high-temperature and high-pressure conditions in order to reduce the risk of reaction (silicon hydrogen H-/ Bronsted acid H+) mixing reduction system, it compared with the low temperature base of a fruit (< 50 DEG C), is being realized under condition of normal pressure efficiently, mild HDO Reaction.The exploitation of this mild HDO restoring method, can be greatly reduced the risk of reaction, be conducive to be applied In production process.
It is provided by the invention a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, including with Lower step:
1) in the case that dimethyl carbonate there are, aldol condensation-esterification reaction of organic acid occurs in the presence of a base for cyclopentanone, formed One 1,3- dicarbonyl compound 1 with twin nuclei；
Wherein, alkali used is the mixture of one or more of solid base, inorganic base and organic base；Solid base is One or more of CaO, MgO, MgAl-HT；Inorganic base is NaOH, NaNH2, KOH, NaH, one of KH or two Kind or more；Organic base is butyl reason, LDA, LHMDS, the mixture of one or more of t-BuOK.Alkali is preferably CaO, NaOH, NaNH2, NaH, LDA, the mixture of one or more of LHMDS.
Specifically, pressing alkali: cyclopentanone: the molar ratio of dimethyl carbonate is 1~3:1:1~3, by alkali, cyclopentanone and carbonic acid Dimethyl ester is added in reactor, and reaction dissolvent (toluene) then is added；1~12h is reacted at 80~120 DEG C；Reaction terminates Afterwards, it is reacted at low temperature with 1mol/L hydrochloric acid, aqueous layer with ethyl acetate extraction, combined organic layer is washed with saturation NaCl It washs, anhydrous sodium sulfate is dry.Compound 1 is isolated by distillation or chromatogram column technique, yield 70~75%.
Reactor in the present invention is simple glass flask, and is equipped with condenser pipe.
2) under the conditions of solvent-free, nucleophilic occurs in the presence of a base and takes for 1,3- dicarbonyl compound 1 and alkyl halide Generation reaction, has synthesized a series of high-density propellant midbody compounds；
Wherein, alkali used is the mixture of one or more of solid base, inorganic base and organic base；Solid base is One or more of CaO, MgO, MgAl-HT；Inorganic base is NaOH, KOH, Ba (OH)2One or both of with On；Organic base is sodium ethoxide, sodium methoxide, the mixture of one or more of t-BuOK；
Preferred alkali is MgO, NaOH, sodium ethoxide, one of t-BuOK or two or more mixtures.
The chemical formula of alkyl halide is RX and RX2, RX and RX2For one or both of bromoalkane, idoalkane and alkyl chloride with On；Alkane structure R includes full branch, alkane unsaturation alkane and cycloalkane.
Specifically, pressing 1,3- dicarbonyl compound 1: alkali: alkyl halide molar ratio is 3:3:1~3, by 1,3- dicarbapentaborane chemical combination Object 1, alkali and alkyl halide are added in reactor, at 50~90 DEG C react 0.5~for 24 hours, after reaction, be added water quenching It goes out reaction.Aqueous layer with ethyl acetate extraction, combined organic layer are washed with saturation NaCl, and anhydrous sodium sulfate is dry.Product passes through Chromatographic column is isolated.
3) under Lewis acid catalysis, using silicon hydrogen reagent, under lower temperature and condition of normal pressure, compound intermediate exists Hydrodeoxygenation reaction has occurred under Bronsted acid existence condition, has synthesized a series of with bicyclic, tricyclic, Fourth Ring, five ring structures High-density hydrocarbons compound.
Wherein, Lewis acid is AlCl3, FeCl3, BF3, B (C6F5)3, Zn (OTf)2One or more of；Proton Acid is hydrochloric acid, HF, H2SO4, one or more of HI；Silicon hydrogen reagent is diethylsilane, polymethyl hydrogen siloxane (PMHS), diphenyl silane, dimethyl ethyl silane, triethylsilane, one of 1,1,3,3- tetramethyl disiloxane or It is two or more；Solvent is methylene chloride.
Specifically, press compound intermediate: Lewis acid: Bronsted acid: silicon hydrogen reagent molar ratio be 1:0.01~0.1:3~ Compound intermediate, Lewis acid, Bronsted acid and silicon hydrogen reagent are added in reactor, then 25~50 by 6:6~12 At DEG C reaction 0.5~for 24 hours；After reaction, water quenching reaction is added.Water layer is extracted with dichloromethane, and combined organic layer is used It is saturated NaCl washing, anhydrous sodium sulfate is dry.Product is isolated by chromatographic column.
Synthetic route of the invention is shown below
It is shown below by the compound structure that the above three-step reaction obtains
Using the tricyclic high-density propellant that carbon number is 15 as representative (compound 3-7, density: 0.91g/cm in the present invention3) energy The load energy for effectively improving aircraft meets the high speed of a ship or plane, the requirement of voyage and big load.
It is illustrated by taking the synthesis of compound 3-1 as an example below.
1) synthesis of compound 1
300mmol dimethyl carbonate and 900mmol alkali are added in the round-bottomed flask containing 250ml toluene, flow back 1h. Then 300mmol cyclopentanone is added, continues 1~12h of reflux.After reaction with 1mol/L hydrochloric acid in 0 DEG C of quenching reaction.Water layer Three times with the extraction of 500ml ethyl acetate.Combined organic layer is saturated NaCl with 500ml and washs three times, and anhydrous sodium sulfate is dry.With The isolated yellow liquid product of silicagel column, yield about 72%.
Compound 1:
Yellow liquid
1H NMR(400MHz,CDCl3): δ 3.67 (s, 3H), 3.27 (t, J=7.2Hz, 1H), 2.71 (s, 2H), 2.60- 2.57 (m,1H),2.45-2.41(m,1H),2.25-2.14(m,4H),1.68-1.61(m,4H).
13C NMR(100MHz,CDCl3):δ199.1,170.4,162.3,126.4,55.5,52.0,34.5,32.6, 27.2,26.5,24.9, 23.8。
2) synthesis of compound 2-1
6mmol compound 1 and 6mmol alkali are added in round-bottomed flask, 6mmol iodomethane, 70 DEG C of stirrings are then added 1h.After fully reacting, 30ml water quenching reaction is added in TLC monitoring.Water layer is extracted three times with 30ml methylene chloride.What is merged has Machine layer is saturated NaCl with 30ml and washs three times, and anhydrous sodium sulfate is dry.With the isolated yellow liquid of silicagel column, yield is about 100%.
3) synthesis of compound 3-1
1mmol compound 2-1 is added in round-bottomed flask, 1ml methylene chloride is then added, is subsequently added into 0.05mmol Lewis acid and 12mmol silicon hydrogen reagent.Then addition 6mmol Bronsted acid, room temperature or heating stirring 0.5~for 24 hours.TLC prison Survey reaction, fully reacting.10ml water quenching reaction is added.Water layer is extracted three times with 10ml methylene chloride.Combined organic layer is used 10ml is saturated NaCl washing three times, and anhydrous sodium sulfate is dry.With the isolated colourless liquid of silicagel column, yield about 88%.
Compound 3-1:
Colourless liquid
1H NMR(400MHz,CDCl3):δ2.21-1.04(m,20H).
13C NMR(100MHz,CDCl3):δ52.45,51.89,44.84,43.01,50.52,40.38,30.77, (30.67,29.83,29.29,25.18,25.10,24.90,15.09,14.25. isomer mixture).
4) synthesis of compound 2-2,2-3,2-4,2-5,2-6,2-7,2-8
The synthetic method of compound 2-2,2-3,2-4,2-5,2-6,2-7,2-8 are consistent with the synthetic method of compound 2-1. Difference is to need to change iodomethane into ethyl alkyl halide, normal-butyl alkyl halide, allyl alkyl halide, 3,3- dimethyl respectively Allyl alkyl halide, 2- methyl-propyl alkyl halide, Cyclopentane halide and halogenated cycloheptane.
5) synthesis of compound 2-9
6mmol compound 1 and 6mmol alkali are added in round-bottomed flask, 3mmol 1,3- diiodo propane, room is then added Temperature stirring.After fully reacting, 30ml water quenching reaction is added in TLC monitoring.Water layer is extracted three times with 30ml methylene chloride.Merge Organic layer with 30ml be saturated NaCl wash three times, anhydrous sodium sulfate dry.With the isolated white solid of silicagel column, yield is about 85%.
6) synthesis of compound 2-10,2-11,2-12,2-13
The synthetic method of compound 2-10,2-11,2-12,2-13 are consistent with the synthetic method of compound 2-9.Difference exists In needing to change 1,3- diiodo propane into 1,5- dihalo pentane respectively, Isosorbide-5-Nitrae-dihalomethyl hexamethylene, 1,2- dihalo benzyl, 1,3- dihalo benzyl.
7) synthesis of compound 3-2,3-3,3-4,3-5,3-6,3-7,3-8,3-9,3-10,3-11,3-12,3-13
The synthetic method of compound 3-2,3-3,3-4,3-5,3-6,3-7,3-8,3-9,3-10,3-11,3-12,3-13 with The synthetic method of compound 3-1 is consistent.Only need for substrate 2-1 to be changed to respectively 2-2,2-3,2-4,2-5,2-6,2-7,2-8, 2-9,2-10,2-11,2-12,2-13.Nuclear magnetic data is as follows:
Compound 3-2:
Colourless liquid
1H NMR(400MHz,CDCl3):δ2.19-0.87(m,22H).
13C NMR(100MHz,CDCl3):δ53.27,52.34,51.46,49.94,40.29,40.16,30.75, 30.73,29.32,26.89,25.20,24.97,24.93,24.91,22.85,11.96,11 .71. (isomer mixture).
Compound 3-3:
Colourless liquid
1H NMR(400MHz,CDCl3):δ2.17-0.86(m,22H).
13C NMR(100MHz,CDCl3):δ53.11,52.26,50.05,48.47,40.29,40.24,30.72, (29.62,29.31,27.53,25.19,25.14,24.90,22.64,13.90. isomer mixture).
Compound 3-4:
Colourless liquid
1H NMR(400MHz,CDCl3):δ5.79-5.68(m,1H),5.06-4.98(m,2H),2.53-1.12(m, 19H).
13C NMR(100MHz,CDCl3):δ136.03,136.01,116.35,116.17,53.15,52.35,49.52, 47.82, 40.35,40.09,34.35,34.10,30.75,30.69,29.96,29.35,26.98,26.05,25.19, (25.11,24.97,24.92,24.90,24.84,24.81. isomer mixture).
Compound 3-5:
Colourless liquid
1H NMR(400MHz,CDCl3):δ5.08-5.06(m,4H),2.43-1.12(m,25H).
13C NMR(100MHz,CDCl3):δ133.01,121.45,53.18,50.33,40.28,30.68,29.28, (28.07,26.95,25.17,25.05,24.88,17.71. single compound).
Compound 3-6:
Colourless liquid
1H NMR(400MHz,CDCl3):δ2.20-0.86(m,26H).
13C NMR(100MHz,CDCl3):δ52.93,52.16,48.44,46.76,40.36,40.29,39.34, 30.75,29.96, 29.27,28.12,27.29,26.14,26.07,25.21,25.16,24.96,24.93,24.87, (24.81,23.48,23.38,21.48. isomer mixture).
Compound 3-7:
Colourless liquid
1H NMR(400MHz,CDCl3):δ2.16-1.13(m,26H).
13C NMR(100MHz,CDCl3): δ 52.52,40.18,30.73,29.99,25.06,24.99,24.84. is (single Compound).
Compound 3-8:
Colourless liquid
1H NMR(400MHz,CDCl3):δ2.10-1.13(m,30H).
13C NMR(100MHz,CDCl3):δ57.16,54.58,40.09,38.78,33.68,30.83,30.62, (29.36,28.28,27.63,27.18,25.28,25.02,24.96,22.76. single compound)
Compound 3-9:
White solid
1H NMR(400MHz,CDCl3):δ2.18-1.16(m,40H).
13C NMR(100MHz,CDCl3):δ53.07,49.87,49.80,40.27,30.70,29.80,29.63, (29.27,27.55,27.48,25.28,25.17,25.14,25.07,24.89. isomer mixture).
Compound 3-10:
White solid
1H NMR(400MHz,CDCl3):δ2.17-1.12(m,44H).
13C NMR(100MHz,CDCl3):δ53.07,52.22,50.02,49.99,48.45,48.42,40.22, 40.18,30.68, 30.06,30.03,29.90,29.80,29.76,29.52,29.49,29.46,29.24,27.48, 27.46,27.38,27.25,27.19,26.81,26.79,25.15,25.06,24.92,24 (isomers is mixed by .86,24.75. Close object).
Compound 3-11:
White solid
1H NMR(400MHz,CDCl3):δ2.18-0.80(m,48H).
13C NMR(100MHz,CDCl3):δ52.85,52.10,52.08,48.09,47.82,46.34,46.06, 40.31,40.29, 40.25,37.64,35.62,33.87,32.01,31.93,30.67,29.90,29.23,29.21, 28.16,28.12,27.65,27.40,25.15,25.11,25.09,24.90,24.86,24 .80,24.78,24.74. is (different Structure body mixture).
Compound 3-12:
Colorless gum liquid
1H NMR(400MHz,CDCl3):δ7.20-7.16(m,2H),7.12-7.06(m,3H),3.10-2.94(m,1H), 2.48-0.84(m,18H).
13C NMR(100MHz,CDCl3):δ199.1,170.4,162.3,126.4,55.5,52.0,34.5,32.6, 27.2,26.5,24.9,23.8. (isomer mixture).
Compound 3-13:
White solid
1H NMR(400MHz,CDCl3):δ7.13-7.12(m,4H),3.27-3.19(m,2H),2.55-2.44(m,2H), 2.27-1.13(m,34H).
13C NMR(100MHz,CDCl3):δ138.31,138.20,129.63,129.55,126.22,53.08,52.99, 51.75, 51.49,40.47,40.44,32.40,32.09,30.67,29.37,27.63,27.38,25.17,25.02, (24.87. isomer mixture).
The present invention, which is one, has specific polycyclic knot by raw material controlled syntheses of lignocellulosic platform chemicals cyclopentanone The variation route of the high density aviation fuel of structure, HDO reaction carry out under room temperature, normal pressure, and reaction is easy, fast, have centainly Practical value.
It is raw material controlled syntheses with specific polycyclic that the present invention relates to one kind using lignocellulosic platform chemicals cyclopentanone The variation route of the high density aviation fuel compound of structure, specifically includes three steps: 1) in the case that dimethyl carbonate there are, Aldol condensation-esterification reaction of organic acid occurs under alkaline condition for cyclopentanone, forms 1, the 3- dicarbapentaborane with twin nuclei Close object 1；2) under the conditions of solvent-free, nucleophilic substitution occurs for compound 1 and alkyl halide, has synthesized a series of tools There is the high-density propellant midbody compound of different number of rings；3) under Lewis acid catalysis, using silicon hydrogen reagent, in lower temperature Under condition of normal pressure, hydrodeoxygenation reaction has occurred, synthesized it is a series of have bicyclic, tricyclic, Fourth Ring, five ring structures it is highly dense Spend fuel compound.
It is wherein that representative has higher density and compared with low viscosity (20 DEG C) (compound with compound 3-2,3-7,3-8,3-12 3-2, density: 0.94g/cm3, viscosity: 4.083mm2/s；Compound 3-7, density: 0.91g/cm3, viscosity: 4.774mm2/s；Change Close object 3-8, density: 0.95g/cm3, viscosity: 12.749mm2/s；Compound 3-12, density: 1.00g/cm3, viscosity: 18.217mm2/ s), the load energy of aircraft can be effectively improved, the high speed of a ship or plane, the requirement of voyage and big load are met.Compound 3-12 Density reached 1.00g/cm3, it has been more than the maximum density value of all biomass class high density aviation fuel of known report.
Compared with prior art, the controlled syntheses of the high-density propellant of different structure may be implemented in the present invention, simultaneously synthesizing Fuel density with higher (calculated theoretical density: 0.89~1.0g/cm3；Actual density: 0.90~1.0g/cm3) and body Accumulated heat value (the theoretical calculation combustion heat: 37~43MJ/L), can be widely applied to field of aerospace.It is high with the tricyclic that carbon number is 15 It is representative (C15:0.91g/cm that density fuel compound, which removes 3-7,3) load energy that aircraft can be effectively improved, meet the high speed of a ship or plane, navigates The requirement of journey and big load.
Theoretical calculation part:
The calculation method of the combustion heat: Gaussion base group: B3LYP/6-31G (d)
The calculation method of density: multiple linear regression
Y=0.766238+0.052134*X1+0.026772*X2-0.00222*X3-0.03149*X4+0.005778* X5-0.46227* X6-0.00018*X7
X1:>C<；X2:CH；X3:CH2；X4:CH3；X5:H；X6:T.C.Total Connectivity；X7:W Wiener index。
It is easy using cyclopentanone as the new side of the polycyclic high density aviation fuel of raw material controlled syntheses the invention proposes one Method.Existing compound density is greater than 0.866g/cm3, some even up to 1.0g/cm3.The compound of different structure has not Same physical property.And HDO reaction is also to carry out under normal pressure and lower temperature.Reaction is simple, mild condition, yield compared with It is high.
The present invention realizes bicyclic, tricyclic, and Fourth Ring, the controlled syntheses of the high-density propellant of five ring structures, simultaneously synthesizing is more Ring aviation fuel density with higher and volume calorific value.Obvious advantage that there are two method tools of the invention, 1: can be by changing The structure for becoming compounds in side chain can orient physical property (such as density, viscosity, freezing point, the combustion heat of regulating compound Deng).2: using B (C6F5)3This is succinct for the silicon hydrogen reduction reaction of catalysis, and mild method avoids making for high-temperature and high-pressure conditions With reducing the risk of reaction.

Claims (10)

1. a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, which is characterized in that including following Step:
1) in the case that dimethyl carbonate there are, aldol condensation-esterification reaction of organic acid occurs in the presence of a base for cyclopentanone, forms one 1,3- dicarbonyl compound 1 with twin nuclei；
2) under solvent-free conditions, nucleophilic substitution occurs in the presence of a base for 1,3- dicarbonyl compound 1 and alkyl halide, synthesis High-density propellant midbody compound；
3) under Lewis acid catalysis, using silicon hydrogen reagent, high-density propellant midbody compound is issued in Bronsted acid existence condition Hydrodeoxygenation reaction has been given birth to, high-density hydrocarbons compound is synthesized.
2. it is according to claim 1 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, the detailed process of step 1) are as follows: press alkali: cyclopentanone: the molar ratio of dimethyl carbonate is 1~3:1:1~3, will Alkali, cyclopentanone and dimethyl carbonate are added in reactor, and reaction dissolvent is then added, and 1~12h is reacted at 80~120 DEG C； Obtain 1,3- dicarbonyl compound 1.
3. it is according to claim 2 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, alkali is the mixture of one or more of solid base, inorganic base and organic base；Reaction dissolvent is first Benzene.
4. it is according to claim 3 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, solid base is CaO, MgO, one or more of MgAl-HT；Inorganic base is NaOH, NaNH2, KOH, One or more of NaH, KH；Organic base is that butyl is managed, LDA, LHMDS, one or more of t-BuOK's Mixture.
5. it is according to claim 2 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, alkali is CaO, NaOH, NaNH2, NaH, LDA, the mixture of one or more of LHMDS.
6. it is according to claim 1 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, the detailed process of step 2) are as follows: press 1,3- dicarbonyl compound 1: alkali: alkyl halide molar ratio is 3:3:1~3, 1,3- dicarbonyl compound 1, alkali and alkyl halide are added in reactor, at 50~90 DEG C react 0.5~for 24 hours, obtain High-density propellant midbody compound.
7. it is according to claim 1 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, alkali is the mixture of one or more of solid base, inorganic base and organic base in step 2).
8. it is according to claim 7 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, solid base is CaO, MgO, one or more of MgAl-HT；Inorganic base is NaOH, KOH, Ba (OH)2 One or more of；Organic base is sodium ethoxide, sodium methoxide, the mixture of one or more of t-BuOK；
The chemical formula of alkyl halide is RX and RX2, RX and RX2For one or more of bromoalkane, idoalkane and alkyl chloride； Alkane structure R includes straight chain, branch saturated alkane, unsaturated alkane and cycloalkane.
9. according to claim 1 or 8 a kind of using cyclopentanone as the side of the polycyclic high density aviation fuel of raw material controlled syntheses Method, which is characterized in that in step 2), alkali MgO, NaOH, sodium ethoxide, one of t-BuOK or two or more mixtures；
The detailed process of step 3) are as follows: press compound intermediate: Lewis acid: Bronsted acid: silicon hydrogen reagent molar ratio be 1:0.01~ High-density propellant midbody compound, Lewis acid, Bronsted acid and silicon hydrogen reagent are added to reaction by 0.1:3~6:6~12 In device, solvent is then added, at 25~50 DEG C react 0.5~for 24 hours, obtain high-density hydrocarbons compound；Wherein, solvent For methylene chloride.
10. it is according to claim 9 a kind of using cyclopentanone as the method for the polycyclic high density aviation fuel of raw material controlled syntheses, It is characterized in that, Lewis acid is AlCl3, FeCl3, BF3, B (C6F5)3, Zn (OTf)2One or more of；Bronsted acid For hydrochloric acid, HF, H2SO4, one or more of HI；Silicon hydrogen reagent is diethylsilane, polymethyl hydrogen siloxane, hexichol Base silane, dimethyl ethyl silane, triethylsilane, one or more of 1,1,3,3- tetramethyl disiloxane.
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CN112062649A (en) * 2020-07-29 2020-12-11 西安交通大学 Alkyl-substituted polycyclic biomass high-density aviation fuel and preparation method thereof
CN112430473A (en) * 2020-11-13 2021-03-02 西安交通大学 Method for synthesizing biomass high-density aviation fuel by using damascenone as raw material

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CN106867565A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of preparation method of high density liquid hydrocarbon fuel

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CN106867565A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of preparation method of high density liquid hydrocarbon fuel

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CN112062649A (en) * 2020-07-29 2020-12-11 西安交通大学 Alkyl-substituted polycyclic biomass high-density aviation fuel and preparation method thereof
CN112062649B (en) * 2020-07-29 2021-05-28 西安交通大学 Alkyl-substituted polycyclic biomass high-density aviation fuel and preparation method thereof
CN112430473A (en) * 2020-11-13 2021-03-02 西安交通大学 Method for synthesizing biomass high-density aviation fuel by using damascenone as raw material
CN112430473B (en) * 2020-11-13 2021-08-13 西安交通大学 Method for synthesizing biomass high-density aviation fuel by using damascenone as raw material

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