CN112062649A - Alkyl-substituted polycyclic biomass high-density aviation fuel and preparation method thereof - Google Patents

Alkyl-substituted polycyclic biomass high-density aviation fuel and preparation method thereof Download PDF

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CN112062649A
CN112062649A CN202010746963.1A CN202010746963A CN112062649A CN 112062649 A CN112062649 A CN 112062649A CN 202010746963 A CN202010746963 A CN 202010746963A CN 112062649 A CN112062649 A CN 112062649A
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王洪
李占超
王一卓
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Xian Jiaotong University
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Abstract

An alkyl substituted polycyclic biomass high-density aviation fuel and a preparation method thereof, wherein cyclopentanone and dimethyl carbonate are subjected to aldol condensation-methyl esterification reaction under an alkaline condition to obtain a 1, 3-dicarbonyl compound 1 with a double five-membered ring; the compound 1, the haloalkane and the cycloalkenone are subjected to two-step one-pot solvent-free nucleophilic substitution/Michael addition-hydrolysis decarboxylation reaction to synthesize an HDO precursor compound; a series of polycyclic high-density liquid hydrocarbon fuel compounds with alkyl substitution are obtained by HDO reaction at high temperature and high pressure by using Pd/C catalyst. The synthetic route of the invention has simple reaction, mild condition, high yield and wide substrate range, and the synthesized fuel has higher density, volume heat value and lower freezing point, and can be applied to various aircrafts or used as an additive to improve the flight performance of aviation fuel.

Description

Alkyl-substituted polycyclic biomass high-density aviation fuel and preparation method thereof
Technical Field
The invention belongs to the field of aerospace, relates to synthesis of alkyl substituted polycyclic high-density aviation fuels, and particularly relates to an alkyl substituted polycyclic biomass high-density aviation fuel and a preparation method thereof, which can be widely applied to the field of aerospace.
Background
In recent years, with the gradual depletion of fossil energy and the increasing of greenhouse effect, the aim of protecting the environment and realizing human society is to provideSustainable development, and the preparation of liquid hydrocarbon fuel from renewable resources, especially biomass resources, is increasingly receiving attention from people. The biomass is a complex composed of a plurality of complex natural polymer organic matters and is the only renewable resource which contains the hydrocarbon elements and can be converted into fuel. The advantages of biomass resources such as renewability and environmental friendliness indicate that the biomass resources are ideal substitutes or supplements for petroleum. On the other hand, lignocellulose represented by crop straws and forestry wastes is a renewable resource widely existing in nature, can be converted into a series of small molecular chemicals through fermentation, hydrolysis, pyrolysis, gasification and other modes, and then is converted into liquid hydrocarbon fuel through a Fischer-Tropsch synthesis method, a catalytic hydrodeoxygenation method and other methods. Therefore, the development of the technology for preparing liquid hydrocarbon fuel, especially high-density fuel from biomass resources can relieve the crisis of petroleum resources and reduce CO in the atmosphere2The concentration and the improvement of the high-value utilization of biomass resources have important significance.
Currently, the aviation kerosene commonly used internationally is prepared from crude oil by processes of rectification, cracking, reforming and the like, mainly contains saturated straight-chain, branched-chain alkane and cycloparaffin of C6-C16, but has lower volume heat value (VNHOC <34MJ/L) which is the most important performance, and cannot meet the use requirement of a high-performance aerospace craft. The high-density aviation fuel is a liquid hydrocarbon fuel with high density and high volume heat value, and can effectively improve the performance of the aerospace craft, such as voyage, speed, load and the like. The performance of an aircraft depends to a large extent on the basic properties of the fuel used, the most important of which are the volumetric combustion calorific value and the density of the fuel. For a spacecraft, under the condition that the volume of a fuel tank of the spacecraft is fixed and the mass combustion heat value of fuel is basically unchanged, the higher the density of the fuel is, the larger the volume combustion heat value of the fuel is, so that the flight performance of the spacecraft, such as voyage, navigational speed, load and the like, can be effectively improved; under the condition of certain driving force, the higher the density of the fuel, the smaller the volume of the fuel tank occupied by the fuel is, and the space volume of the aircraft can be effectively reduced. Therefore, increasing the density or volumetric heat of combustion of the fuel is one of the important methods to improve the propulsion performance of aerospace vehicles. Therefore, the synthesis of high-density aviation fuel has great value and significance.
The preparation of liquid fuels from biomass resources has been developed from the initial preparation of grain crops such as starch and corn as raw materials to the preparation of liquid hydrocarbon fuels from lignocellulose as a main raw material by chemical and biological methods (fermentation, degradation, etc.) to obtain platform molecules, then synthesizing HDO precursor compounds with oxygen atoms by C-C bond coupling reaction, and finally preparing liquid hydrocarbon fuels by HDO reaction. There have been many reports on this aspect, for example, yangjinfan et al report that furfural and 2-pentanone and 2-heptanone are subjected to aldol condensation reaction under the catalysis of solid base CaO and under the solvent-free condition at a molar ratio of 3:1 and at a temperature of 130 ℃ for 6 hours to obtain oxygenates with yields of 86.7% and 75.3%, and finally, a Pd/H-ZSM-5 catalyst is used to realize the HDO reaction of solvent-free at a temperature of 280 ℃ to obtain the chain hydrocarbon fuel of C9-C12 with a total carbon yield of 80%. (Green chem.,2014,16,4879-4884) Guingyi Li et al report that 2-methylfuran and furan aldehyde underwent hydroxyalkylation/alkylation reaction at 50 ℃ for 2 hours under the catalysis of solid super acid Nafion-212 to obtain an oxygen-containing compound of C15 with a yield of 67%; finally, C15 oxygenate was first hydrogenated by Pd/C, and then HDO product was obtained at 350 ℃ with 94% carbon yield using Pt/ZrP catalyst, where C is15The yield of long-chain alkane component was 75% (ChemSusChem,2012,5, 1958-1966). However, the chain alkane fuel has low density and low volume combustion heat, and cannot be effectively utilized in the field of aerospace. As is clear from the structure-activity relationship, since the density of hydrocarbons gradually increases with the increase in the number of carbons and the ring structure, the synthesis of compounds having a polycyclic structure has become an important research point in the field of high-density fuel synthesis.
In recent years, the synthesis of cyclopentanone from furan aldehyde has been reported. Hronec et al reported that furan aldehydes were present at 160 ℃ and 3MPa H in the presence of 5% Pt/C2The yield of cyclopentanone in the aqueous phase reached 76.5% (Applied Catalysis A: General,2012,437-438, 104-111). Yanhua Liu et al report the use of Ru/CNTs catalyst supported on carbon nanotubes in aqueous phase at 1MPa H2160 ℃, 500rpm, 5h, with 99% conversion and 91% yield to efficiently obtain ringsPentanone. Studies have shown that furan aldehyde concentration, reaction temperature, hydrogen pressure, stirring rate and reaction time all have a large effect on yield (ACS sustamable chem. eng.,2017,5, 744-751). Yong Cao et al report furan aldehydes on Au/TiO2Under the catalysis of-A, 160 ℃ and 4MPa H2Under the condition, the yield of cyclopentanone in the water phase reaches 99% (Green chem.,2016,18, 2155-2164). Therefore, cyclopentanone can be used as a biomass platform molecule which can be widely utilized to synthesize high-density aviation fuel compounds. For example, Tao Zhang et al reported that cyclopentanone was formed into 2-cyclopentylidenecyclopentanone by a solvent-free aldol condensation reaction, followed by reaction on Ni-SiO2C10 dicyclopentane (density: 0.866 g/cm) was synthesized in 80% yield by HDO reaction under catalysis3(ii) a Mass combustion heat value: 42.42 MJ/kg; volume heat of combustion: 36.7MJ/L, freezing point: -38 ℃ (chem. commun.,2014,50, 2572). Similarly, cyclopentanone, catalyzed by Pd-MgAl-HT, first formed 2, 5-dicyclopentylcyclopentanol, which was then HDO catalyzed by Ni-H β -DP catalyst, finally produced C15 tricyclopentane (density: 0.91 g/cm) in 80% yield3) (AIChE Journal,2016,8, 2754-2761). Wei Wang et al reported that a tetracyclopentane compound was synthesized in 70% yield via a three-step reaction using cyclopentanone. The first step is as follows: the reaction was carried out in one pot under Raney Co and 1.25mol/L KOH catalysis at 80 ℃ for 8h in a hydrogen atmosphere to obtain 2-cyclopentylcyclopentanone in 83.3% yield. The second step is that: the 2-cyclopentyl-5- (2' -cyclopentylidene) cyclopentanone compound was obtained in 95.5% carbon yield by self-condensation of 2-cyclopentylcyclopentanone with KOH catalysis at 150 ℃ under vacuum, solvent-free conditions and 1 h. The third step: under the conditions of 260 ℃ and 6MPa, in the presence of Ni-SiO2The HDO reaction was catalyzed to give the tetracyclopentane compound in 88.5% carbon yield. The compound density reached 0.943g/mL and the freezing point was-39.5 deg.C (ACS Sustainable chem. Eng.,2017,5, 1812-one 1817). The presence of alkyl substituents on the ring structure has a significant effect on freezing point depression of compounds having higher densities compared to the dicyclopentane and tricyclopentane compounds. The above-mentioned processes only allow the synthesis of non-alkyl-substituted cyclopentane compounds, which, although having a higher densityBut due to the freezing point>-40 ℃ and therefore cannot be used directly as fuel, and must be used in combination with fuels having a low freezing point. And the alkyl substituent in the molecular structure can greatly reduce the freezing point and the low-temperature performance of the compound, so that the synthesized polycyclic compound with alkyl substitution has greater potential utilization value.
Disclosure of Invention
The invention aims to provide an alkyl substituted polycyclic biomass high-density aviation fuel and a preparation method thereof from a lignocellulose platform compound cyclopentanone.
In order to realize the purpose, the invention is realized by the following technical scheme:
a preparation method of an alkyl substituted polycyclic biomass high-density aviation fuel comprises the following steps:
1) performing aldol condensation-methyl esterification reaction on cyclopentanone and dimethyl carbonate under an alkaline condition to obtain a 1, 3-dicarbonyl compound 1 with a double five-membered ring;
2) under the solvent-free condition, a 1, 3-dicarbonyl compound 1 with a double five-membered ring, alkyl halide and cycloenone undergo nucleophilic substitution or Michael addition reaction under the catalysis of alkali and a PTC catalyst to obtain an addition product; adding a solvent and alkali into the addition product, and performing hydrolysis decarboxylation reaction to obtain an HDO precursor compound;
3) the high-density aviation fuel of the alkyl substituted polycyclic biomass is obtained by using a Pd/C catalyst and through HDO reaction at high temperature and high pressure.
The invention is further improved in that the specific process of the step 1) is as follows: according to the proportion of alkali: cyclopentanone: the molar ratio of dimethyl carbonate is 1-3: 1: 1-3, adding alkali, cyclopentanone and dimethyl carbonate into a reactor, then adding a solvent, and reacting at 80-120 ℃ for 1-12 h to obtain the 1, 3-dicarbonyl compound 1.
The invention is further improved in that the alkali is one of inorganic alkali and organic alkali; the reaction solvent is toluene; the cyclic olefin ketone is cyclopentenone, cyclohexenone or cycloheptenone.
The invention further improves that the inorganic base is NaH or KH, and the organic base is one of n-butyl lithium, LDA and LiHMDS.
The invention is further improved in that the specific process of the step 2) is as follows:
according to the proportion of 1, 3-dicarbonyl compound 1: alkali: the molar ratio of the alkyl halide is 1: 1: 1-1.5, adding a 1, 3-dicarbonyl compound 1, alkali and alkyl halide into a reactor, and reacting at 50-90 ℃ for 0.5-24 h to obtain an addition product; or according to the formula 1, 3-dicarbonyl compound 1: alkali: PTC: the cyclic ketene molar ratio is 1: 0.01-0.1: 0.01-0.1: 1, adding a 1, 3-dicarbonyl compound 1, PTC, alkali and cyclic ketene into a reactor, and reacting for 5-60 min at room temperature to obtain an addition product;
then, the reaction is carried out according to the following formula of 1, 3-dicarbonyl compound 1: the molar ratio of the alkali is 1: and 2, adding a solvent and alkali into the addition product, and reacting for 3 hours at the temperature of 50-90 ℃ to obtain the HDO precursor compound.
The invention further improves the method that in the step 2), the alkali is one or two of inorganic alkali and organic alkali; the alkyl halide is one or two of alkyl bromide and alkyl iodide; the PTC catalyst is one of tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium iodide;
the solvent is one of methanol, ethanol, water and tetrahydrofuran.
The invention is further improved in that the inorganic base is NaOH, KOH, Ba (OH)2And K3PO4·3H2One or two of O, and the organic base is sodium ethoxide; the alkyl in the alkyl bromide and alkyl iodide is straight-chain alkane, branched alkane, unsaturated alkane or cyclane.
The invention is further modified in that the carbon atoms of the straight-chain alkane and the branched-chain alkane are C1-C5, the unsaturated alkane is allyl bromide or 3, 3-dimethyl allyl bromide, and the cycloalkane is cyclopentane or cycloheptane.
The invention is further improved in that the specific process of the step 3) is as follows: according to the molar ratio of the HDO precursor compound to Pd in Pd/C of 1: 0.005-0.01, adding an HDO precursor compound and Pd/C into a reactor, then adding a solvent, filling hydrogen to 4MPa, and then reacting for 12-24 h at 200-250 ℃ to obtain the alkyl substituted polycyclic biomass high-density aviation fuel; wherein the reaction solvent is cyclohexane.
An alkyl substituted polycyclic biomass high-density aviation fuel, which has the following structural formula:
Figure BDA0002608701060000051
Figure BDA0002608701060000052
wherein R' is CH3、CH2CH3、CH2CH2CH3、CH2CH(CH3)2、CH2CH2CH2CH3、CH2CH2CH2CH2CH3Or CH2CH2CH(CH3)2(ii) a n is 1, 2 or 3; and m is 1 or 2.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a simple novel method for synthesizing alkyl-substituted polycyclic biomass high-density aviation fuel by using cyclopentanone as a raw material. The synthetic route is divided into three steps: 1) performing aldol condensation-methyl esterification reaction on cyclopentanone and dimethyl carbonate under an alkaline condition to obtain a 1, 3-dicarbonyl compound 1 with a double five-membered ring; 2) the compound 1, the haloalkane and the cycloalkenone are subjected to two-step one-pot solvent-free nucleophilic substitution/Michael addition-hydrolysis decarboxylation reaction to synthesize an HDO precursor compound; 3) a series of polycyclic high-density liquid hydrocarbon fuel compounds with alkyl substitution are obtained by HDO reaction at high temperature and high pressure by using Pd/C catalyst. The synthetic route has the advantages of simple reaction, mild condition, high yield and wide substrate range.
The invention relates to a new route for synthesizing alkyl-substituted polycyclic high-density aviation fuel by using a lignocellulose platform compound cyclopentanone as a raw material. The synthetic route has the advantages of simple reaction, mild condition, high yield and wide substrate range. The invention can realize the synthesis of polycyclic high-density fuels with different alkyl structures, and the synthesized fuel has higher density, volume heat value and lower freezing point, and can be applied to various aircrafts or used as an additive to improve the flight performance of aviation fuels.
Drawings
FIG. 1 is a synthetic route diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
Referring to fig. 1, cyclopentanone is used as a raw material, and the polycyclic high-density aviation fuel compound substituted by alkyl is simply and efficiently synthesized through three simple reactions. Firstly, cyclopentanone is taken as a raw material to synthesize a compound 1 with dimethyl carbonate under a strong alkaline condition; then, a series of polycyclic HDO precursor compounds are synthesized in two steps and one pot through nucleophilic substitution/Michael addition reaction-hydrolysis decarboxylation reaction of solvent-free; finally, a series of saturated hydrocarbons are obtained by implementing the hydrodeoxygenation reaction at high temperature and high pressure by using a Pd/C catalyst.
Wherein, the compounds are represented by compounds 3-3 and 3-12 (C13: density 0.8542 g/cm)3(20 ℃ C.), kinematic viscosity of 2.29mm2Freezing point at 25 ℃ C<-80 ℃, 38.12MJ/L volumetric heat of combustion; c16 density 0.9066g/cm3(20 ℃ C.), kinematic viscosity of 9.92mm2The specific heat energy of the aircraft can be effectively increased, and the requirements of high navigational speed, range and large load can be met. Therefore, the fuel can be used as a high-density fuel in the aerospace field.
The invention provides a method for synthesizing alkyl substituted polycyclic high-density aviation fuel by using cyclopentanone as a raw material, which comprises the following steps:
1) performing aldol condensation-methyl esterification reaction on cyclopentanone and dimethyl carbonate under a strong alkaline condition to obtain a 1, 3-dicarbonyl compound 1 with a double five-membered ring;
wherein the strong base is one of inorganic base and organic base; the inorganic base is NaH or KH; the organic base is butyl alkyl, LDA or LiHMDS.
Specifically, according to alkali: cyclopentanone: the molar ratio of dimethyl carbonate is 1-3: 1: 1-3, adding alkali, cyclopentanone and dimethyl carbonate into a reactor, and then adding a reaction solvent (toluene); reacting for 1-12 h at 80-120 ℃; after the reaction was completed, the reaction was quenched with 1mol/L hydrochloric acid at low temperature, the aqueous layer was extracted with ethyl acetate, and the combined organic layers were washed with saturated NaCl and dried over anhydrous sodium sulfate. And then separating by distillation or chromatographic column method to obtain the 1, 3-dicarbonyl compound 1 with the double five-membered ring, wherein the yield is 70-75%, and the structural formula of the 1, 3-dicarbonyl compound 1 with the double five-membered ring is as follows:
Figure BDA0002608701060000071
the reactor in the present invention is a normal glass flask and is equipped with a condenser tube.
2) HDO precursor compounds were synthesized in two steps in one pot:
the first step is as follows: under the solvent-free condition, a 1, 3-dicarbonyl compound 1 with a double five-membered ring, alkyl halide and cycloenone undergo nucleophilic substitution/Michael addition reaction under the catalysis of alkali and PTC to obtain an addition product;
the second step is that: and adding a solvent and alkali into the addition product in the first step reactor, and performing hydrolysis decarboxylation reaction to obtain an HDO precursor compound.
Wherein the alkali is one or a mixture of more than two of inorganic alkali and organic alkali; the base is NaOH, KOH, Ba (OH)2Sodium ethoxide, K3PO4-3H2One or a mixture of two or more of O; the chemical formula of the alkyl halide is RX, and RX is one or more than two of alkyl bromide and alkyl iodide; the alkane structure R comprises straight-chain saturated alkane, branched-chain saturated alkane, unsaturated alkane and cycloalkane; the carbon atom number of the straight-chain saturated alkane and the branched-chain saturated alkane is C1-C5, the unsaturated alkane is allyl bromide or 3, 3-dimethyl allyl bromide, and the cycloalkane is cyclopentane or cycloheptane. PTC is one of tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium iodide; the cyclic olefin ketone is cyclopentenone, cyclohexenone or cycloheptenone. The second step reaction solvent is one of methanol, ethanol, water or tetrahydrofuran.
Specifically, the first step: according to the proportion of 1, 3-dicarbonyl compound 1: alkali: the molar ratio of the alkyl halide is 1: 1: 1-1.5, adding a 1, 3-dicarbonyl compound 1, alkali and alkyl halide into a reactor, and reacting for 0.5-24 hours at 50-90 ℃ under a solvent-free condition;
or according to the formula 1, 3-dicarbonyl compound 1: alkali: PTC: the mol ratio of the cyclic ketene is 1: 0.01-0.1: 0.01-0.1: 1, adding a 1, 3-dicarbonyl compound 1, PTC, alkali and cyclic ketene into a reactor, and reacting for 5-60 min at room temperature under a solvent-free condition;
the second step is that: adding a solvent and alkali (adding the alkali according to the 1: alkali molar ratio of the 1, 3-dicarbonyl compound of 1: 2) into the reaction system in the first step, reacting for 3 hours at 50-90 ℃, and adding 1mol/L hydrochloric acid to quench the reaction after the reaction is finished. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were washed with saturated NaCl and dried over anhydrous sodium sulfate. The product is separated by a chromatographic column to obtain the HDO precursor compound, and the structural formula is specifically as follows.
Figure BDA0002608701060000091
Specifically, the structural formulae of the compounds 2-8 to 2-12 are as follows:
Figure BDA0002608701060000092
the reactor in the present invention is a normal glass flask and is equipped with a condenser tube.
3) A series of polycyclic high-density liquid hydrocarbon fuel compounds with alkyl substitution are obtained by using Pd/C catalyst and through HDO reaction at high temperature and high pressure.
Specifically, the HDO precursor compounds: the Pd/C molar ratio is 1: 0.005-0.01 (pure Pd), adding an HDO precursor compound and Pd/C into a reactor, then adding cyclohexane, filling hydrogen to 4MPa, and reacting for 12-24 h at 200-250 ℃ to obtain a high-density hydrocarbon fuel compound crude product. Then obtaining pure alkyl substituted polycyclic biomass high-density aviation fuel by reduced pressure distillation.
The reactor in the invention is a high-pressure reaction kettle. The structural formula of the method for preparing the alkyl-substituted polycyclic biomass high-density aviation fuel is as follows:
Figure BDA0002608701060000101
specifically, the structural formulae of the compounds 3-8 to 3-12 are as follows:
Figure BDA0002608701060000102
the present invention is illustrated by the synthesis of compounds 3-5.
1) Synthesis of Compound 1
Figure BDA0002608701060000103
Dimethyl carbonate and a base were added to a round bottom flask, followed by addition of an appropriate amount of toluene and reflux for 1 h. And adding cyclopentanone, and continuously refluxing for 1-12 h. The reaction was monitored by TLC and quenched with 1mol/L HCl/at 0 ℃. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with saturated NaCl several times and dried over anhydrous sodium sulfate. And (4) separating by using a silica gel column to obtain a yellow liquid, wherein the yield is about 70-75%.
Compound 1 is a yellow liquid.
1H NMR(400MHz,CDCl3):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):199.1,170.4,162.3,126.4,55.5,52.0,34.5,32.6,27.2,26.5,24.9,23.8.
2) Synthesis of Compounds 2-5
Figure BDA0002608701060000111
Adding the compound 1, alkali and n-butyl iodide into a reactor, reacting for 1h at 50-90 ℃ under a solvent-free condition, and monitoring by TLC that the raw materials are basically completely reacted; and then adding alkali and a solvent, reacting for 3 hours at 50-90 ℃, and adding 1mol/L hydrochloric acid to quench the reaction after the reaction is finished. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were washed with saturated NaCl and dried over anhydrous sodium sulfate. The product was separated by chromatography to give the HDO precursor compound.
Compounds 2-5 yellow liquid
1H NMR(400MHz,CDCl3):2.78(s,2H),2.52-2.35(m,2H),2.28-2.11(m,4H),1.85-1.58(m,6H),1.33-1.22(m,5H),0.89(t,J＝6.8Hz,3H).
13C NMR(100MHz,CDCl3):208.6,158.6,128.1,49.9,34.1,32.5,29.9,29.6,27.4,26.9,26.9,25.2,22.7,21.6,14.0.
3) Synthesis of Compounds 2-9
Figure BDA0002608701060000112
Adding the compound 1, alkali, cyclohexenone and PTC into a reactor, reacting for 5min at room temperature under a solvent-free condition, and monitoring by TLC that the raw materials are basically reacted completely; and then adding alkali and a solvent, reacting for 3 hours at 50-90 ℃, and adding 1mol/L hydrochloric acid to quench the reaction after the reaction is finished. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were washed with saturated NaCl and dried over anhydrous sodium sulfate. The product was separated by chromatography to give the HDO precursor compound.
Compounds 2-9 yellow liquid
1H NMR(400MHz,CDCl3):2.71(s,2H),2.45-1.95(m,14H),1.70-1.44(m,6H).(product and its isomer)
13C NMR(100MHz,CDCl3):211.4,211.3,206.3,206.2,159.5,159.5,128.0,127.9,53.9,53.5,45.9,44.5,41.2,38.8,38.5,34.1,32.4,28.9,27.2,27.1,26.7,25.1,25.1,25.0,23.1,22.5.
4) Synthesis of Compounds 3 to 5
Figure BDA0002608701060000121
Adding the compound 2-5 into a high-pressure reaction kettle, then adding Pd/C and cyclohexane, filling hydrogen to 4MPa, heating to 200-250 ℃, and reacting for 12-24 h to obtain a high-density hydrocarbon fuel compound crude product. The pure product is then obtained by distillation under reduced pressure.
Compounds 3 to 5 colorless transparent liquids
5) Synthesis of Compounds 2-1 to 2-7 and 2-11, 2-12
The synthesis methods of the compounds 2-1 to 2-7 and 2-11, 2-12 are the same as the synthesis method of the compound 2-5. The difference is that n-butyl iodide needs to be respectively replaced by methyl alkyl halide, ethyl alkyl halide, allyl alkyl halide, isobutyl alkyl halide, n-pentyl alkyl halide and 3, 3-dimethyl allyl alkyl halide.
6) Synthesis of Compounds 2-8 and 2-10
The synthesis of compounds 2-8 and 2-10 was identical to that of compounds 2-9. The difference is that the cyclohexenone needs to be replaced by cyclopentenone and cycloheptenone, respectively.
Synthesis of Compounds 3-1 to 3-12
The synthesis of compounds 3-1 to 3-12 was identical to that of compound 3-5. Only the substrates 2-5 need to be changed to compounds 2-1 to 2-12, respectively.
The preparation of compounds 3-1 to 3-12 can be accomplished by those skilled in the art according to the above preparation procedures of compounds 3-5.
The nuclear magnetic data of the intermediates 2-1 to 2-12 are as follows:
compound 2-1 yellow liquid
1H NMR(400MHz,CDCl3):2.79(s,2H),2.51-2.13(m,6H),1.74-1.66(m,4H),1.48-1.38(m,1H)1.09(d,3H).
13C NMR(100MHz,CDCl3):208.7,158.7,127.7,44.6,34.1,32.4,29.1,27.3,26.9,25.1,14.7.
Compound 2-2 yellow liquid
1H NMR(400MHz,CDCl3):2.76(s,2H),2.50-2.07(m,6H),1.85-1.78(m,1H),1.73-1.63(m,4H),1.52-1.39(m,1H),1.33-1.22(m,1H),0.92(t,J＝7.2Hz,3H).
13C NMR(100MHz,CDCl3):208.3,158.5,128.1,51.4,34.1,32.4,27.3,26.8,26.2,25.1,23.1,11.8.
Compounds 2-3 yellow liquid
1H NMR(400MHz,CDCl3):5.82-5.71(m,1H),5.05-4.96(m,2H),2.76(s,2H),2.57-2.25(m,6H),2.15-1.97(m,2H),1.73-1.61(m,4H),1.55-1.45(m,1H).
13C NMR(100MHz,CDCl3):207.2,159.0,136.4,127.8,115.8,49.3,34.4,34.1,32.5,27.2,26.8,26.2,25.1.
Compounds 2-4 yellow liquid
1H NMR(400MHz,CDCl3):2.78(s,2H),2.52-2.01(m,6H),1.73-1.63(m,6H),1.55-1.38(m,1H),1.17-1.04(m,1H),0.90(dd,J＝15.6Hz,J＝6.0Hz,6H).
13C NMR(100MHz,CDCl3):208.9,158.5,128.0,48.2,39.4,34.1,32.5,27.4,27.4,26.9,26.0,25.2,23.5,21.6.
Compounds 2-6 yellow liquid
1H NMR(400MHz,CDCl3):2.74(s,2H),2.47-2.06(m,6H),1.78-1.60(m,5H),1.46-1.15(m,8H),0.82(t,J＝6.8Hz,3H).
13C NMR(100MHz,CDCl3):208.3,158.3,128.10,49.8,34.0,32.4,31.8,30.0,27.3,27.0,26.8,25.1,22.4,13.9.
Compounds 2-7 yellow liquid
1H NMR(400MHz,CDCl3):5.12-5.08(m,1H),2.77(s,2H),2.49-2.18(m,6H),2.12-1.96(m,2H),1.73-1.61(m,7H),1.58(s,3H),1.56-1.43(m,1H).
13C NMR(100MHz,CDCl3):207.9,158.7,132.7,128.0,121.9,50.3,34.1,32.5,28.5,27.3,26.8,26.3,25.7,25.1,17.7.
Compounds 2-8 yellow liquid
1H NMR(400MHz,CDCl3):2.76(s,2H),2.68-1.56(m,18H).(product and its isomer)
13C NMR(100MHz,CDCl3):219.4,218.9,206.5,206.6,159.7,159.8,127.8,127.8,63.7,63.0,43.4,42.0,38.1,38.5,37.6,37.4,34.2,32.6,27.2,27.7,26.8,26.9,25.1,24.5,24.4.
Compounds 2-10 yellow liquid
1H NMR(400MHz,CDCl3):2.66(s,2H),2.49-1.12(m,22H).(product and its isomer)
13C NMR(100MHz,CDCl3):213.8,213.7,206.1,128.0,127.9,55.4,55.4,48.3,46.2,43.4,43.3,35.0,35.0,34.7,33.9,32.6,32.3,29.1,28.9,26.9,26.5,24.8,24.3,24.1,22.1,21.7.
Compounds 2-11 yellow liquid
1H NMR(400MHz,CDCl3):2.75(s,2H),2.49-2.32(m,2H),2.27-2.12(m,4H),1.89-1.39(m,13H),1.25-1.18(m,1H),1.13-1.01(m,2H).
13C NMR(100MHz,CDCl3):208.5,158.4,127.9,49.4,38.1,36.4,34.0,33.2,32.0,27.3,27.3,26.8,25.1,25.1,24.9.
Compounds 2-12 yellow liquid
1H NMR(400MHz,CDCl3):2.76(s,2H),2.50-2.36(m,2H),2.34-2.11(m,4H),1.73-1.62(m,10H),1.47-1.29(m,2H),1.26-1.04(m,4H),0.98-0.79(m,2H).
13C NMR(100MHz,CDCl3):209.0,158.4,128.0,47.4,37.9,35.4,34.2,32.5,32.3,27.4,27.4,26.8,26.5,26.3,26.2,25.1.
The nuclear magnetic data of the products 3-1 to 3-12 are as follows:
compound 3-1-colorless liquid
1H NMR(400MHz,CDCl3):1.85-0.82(m,20H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.7,46.6,46.6,36.6,45.6,45.2,45.1,45.0,37.7,35.5,33.0,32.9,32.7,32.6,31.7,31.6,31.5,31.4,30.6,29.7,28.6,28.5,28.5,28.4,26.9,26.8,26.8,26.7,25.3,25.3.
Compound 3-2-colorless liquid
1H NMR(400MHz,CDCl3):1.78-0.80(m,22H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.2,44.8,41.9,40.8,39.4,37.3,32.8,32.2,31.7,31.7,31.7,31.6,31.4,30.6,29.5,29.3,25.3,25.3,13.0,13.0.
Compounds 3-3 colorless liquids
1H NMR(400MHz,CDCl3):1.79-0.86(m,24H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.2,44.8,39.8,39.8,39.2,39.0,38.7,37.6,33.2,32.2,31.7,31.7,31.6,30.5,25.3,25.3,25.3,21.7,21.7,14.4,14.3.
Compounds 3-4 colorless liquids
1H NMR(400MHz,CDCl3):1.90-1.05(m,20H),0.87-0.85(m,6H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.6,46.3,46.2,46.1,44.8,40.0,37.8,37.7,36.6,33.4,32.2,31.9,31.7,31.7,31.5,30.5,26.8,26.7,25.3,25.3,23.0,22.9,22.8,22.8.
Compounds 3-5 colorless liquids
1H NMR(400MHz,CDCl3):1.81-0.84(m,26H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.2,40.1,39.8,37.6,36.4,33.2,32.2,31.7,31.7,31.7,31.6,31.0,30.9,30.6,25.3,25.3,25.3,23.0,23.0,14.1,14.1.
Compounds 3-6 colorless liquids
1H NMR(400MHz,CDCl3):1.78-0.86(m,28H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.2,39.8,37.6,36.8,36.6,33.2,32.2,32.2,32.1,31.7,31.7,31.7,31.5,30.5,29.7,28.4,25.3,25.3,25.3,22.7,14.1.
Compounds 3 to 7 colorless liquids
1H NMR(400MHz,CDCl3):1.80-1.06(m,22H),0.88-0.86(m,6H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.6,46.2,44.8,40.3,39.9,38.2,38.1,38.0,37.7,34.6,34.4,33.3,32.3,31.8,31.7,31.7,31.6,30.6,28.2,25.3,25.3,25.3,22.7,22.7.
Compounds 3 to 8 colorless liquids
1H NMR(400MHz,CDCl3):1.89-1.05(m,26H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.6,46.2,45.1,39.0,36.5,32.5,31.7,31.7,31.5,30.7,25.3,25.3,25.3,25.3.
Compounds 3-9 colorless liquids
1H NMR(400MHz,CDCl3):1.76-0.86(m,28H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.7,46.5,46.0,45.4,45.0,43.9,43.8,37.6,35.1,32.6,32.2,32.1,32.0,31.8,31.7,31.7,31.5,31.2,30.5,29.4,26.7,26.7,26.5,26.5,25.3,25.3,25.3.
Compounds 3-10 colorless liquids
1H NMR(400MHz,CDCl3):1.72-0.83(m,30H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.7,46.7,46.6,46.1,45.6,45.2,45.1,45.0,37.8,35.5,33.0,32.9,32.7,32.7,31.7,31.6,31.5,31.4,30.6,29.7,28.6,28.5,28.5,28.4,26.9,26.8,26.8,26.7,26.4,25.3,25.3.
Compounds 3 to 11 colorless liquids
1H NMR(400MHz,CDCl3):1.90-0.82(m,28H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.6,46.1,44.7,43.3,43.1,40.0,39.2,39.1,38.0,37.7,33.5,33.0,32.9,32.9,32.9,32.2,31.9,31.7,31.7,31.5,30.5,25.3,25.3,25.3,25.1.
Compounds 3-12 colorless liquids
1H NMR(400MHz,CDCl3):1.97-0.80(m,30H).(product and its isomer)
13C NMR(100MHz,CDCl3):46.8,46.6,46.1,44.9,44.8,44.7,40.1,37.8,37.1,36.5,36.4,35.9,33.8,33.7,33.7,33.6,33.5,32.2,32.0,31.7,31.7,31.6,30.5,26.8,26.5,25.3,25.3,25.3.
TABLE 1 comparison of the Properties of Compounds 3-3, 3-12 with Dicyclopentane
Figure BDA0002608701060000171
Figure BDA0002608701060000181
As can be seen from the test data in Table 1 above, represented by compounds 3-3 and 3-12 (C13: density 0.8542 g/cm)3(20 ℃ C.), kinematic viscosity of 2.29mm2Freezing point at 25 ℃ C<-80 ℃, 38.12MJ/L volumetric heat of combustion; c16 density 0.9066g/cm3(20 ℃ C.), kinematic viscosity of 9.92mm2The specific heat energy of the aircraft can be effectively increased, and the requirements of high navigational speed, range and large load can be met. The synthesized two dicyclopentane compounds 3-3 and 3-12 with side chain substituent have higher density and lower freezing point (respectively<-80 ℃ and-58 ℃) and viscosity, and a higher volumetric heat of combustion value (38.12 MJ/L and 39.42MJ/L, respectively). Compared with the dicyclopentane compound, the viscosity is slightly increased, but the solidifying point is obviously reduced, and the volume heat value is respectively increased by 3.67 percent and 7.20 percent.
The method takes a lignocellulose platform compound cyclopentanone as a raw material, and obtains a series of alkyl-substituted polycyclic high-density liquid hydrocarbons through aldol condensation-methyl esterification reaction, two-step one-pot solution-free nucleophilic substitution/Michael addition-hydrolysis reaction and HDO reaction which are three steps in total. Specifically, cyclopentanone and dimethyl carbonate are subjected to aldol condensation-methyl esterification reaction under an alkaline condition to form a 1, 3-dicarbonyl compound 1 with a bicyclic structure; then, under the condition of solvent-free, the compound 1, alkyl halide and cyclic ketene undergo nucleophilic substitution/Michael addition-hydrolysis decarboxylation reaction to obtain an HDO precursor compound; finally, under the catalysis of Pd/C, the hydrodeoxygenation reaction is carried out, and the polycyclic high-density fuel compound with alkyl substitution is obtained. The dicyclopentany high-density fuel compound with alkyl substituent on the side chain is simply and efficiently synthesized with the yield of about 45-70 percent. Compared with the properties of dicyclopentane, the properties of two representative fuel compounds 3-3 and 3-12 show that the compounds have lower freezing points and higher volume combustion heat values, have lower viscosity, can effectively improve the performance of aircrafts, and have great potential directly as space fuel. The synthetic route has the advantages of simple reaction, mild condition, high yield and wide substrate range.

Claims (10)

1. The preparation method of the alkyl-substituted polycyclic biomass high-density aviation fuel is characterized by comprising the following steps of:
1) performing aldol condensation-methyl esterification reaction on cyclopentanone and dimethyl carbonate under an alkaline condition to obtain a 1, 3-dicarbonyl compound 1 with a double five-membered ring;
2) under the solvent-free condition, a 1, 3-dicarbonyl compound 1 with a double five-membered ring, alkyl halide and cycloenone undergo nucleophilic substitution or Michael addition reaction under the catalysis of alkali and a PTC catalyst to obtain an addition product; adding a solvent and alkali into the addition product, and performing hydrolysis decarboxylation reaction to obtain an HDO precursor compound;
3) the high-density aviation fuel of the alkyl substituted polycyclic biomass is obtained by using a Pd/C catalyst and through HDO reaction at high temperature and high pressure.
2. The preparation method of the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 1, wherein the specific process of step 1) is as follows: according to the proportion of alkali: cyclopentanone: the molar ratio of dimethyl carbonate is 1-3: 1: 1-3, adding alkali, cyclopentanone and dimethyl carbonate into a reactor, then adding a solvent, and reacting at 80-120 ℃ for 1-12 h to obtain the 1, 3-dicarbonyl compound 1.
3. The method for preparing the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 2, wherein the base is one of an inorganic base and an organic base; the reaction solvent is toluene; the cyclic olefin ketone is cyclopentenone, cyclohexenone or cycloheptenone.
4. The method for preparing the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 3, wherein the inorganic base is NaH or KH, and the organic base is one of n-butyl lithium, LDA and LiHMDS.
5. The preparation method of the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 1, wherein the specific process of step 2) is as follows:
according to the proportion of 1, 3-dicarbonyl compound 1: alkali: the molar ratio of the alkyl halide is 1: 1: 1-1.5, adding a 1, 3-dicarbonyl compound 1, alkali and alkyl halide into a reactor, and reacting at 50-90 ℃ for 0.5-24 h to obtain an addition product; or according to the formula 1, 3-dicarbonyl compound 1: alkali: PTC: the cyclic ketene molar ratio is 1: 0.01-0.1: 0.01-0.1: 1, adding a 1, 3-dicarbonyl compound 1, PTC, alkali and cyclic ketene into a reactor, and reacting for 5-60 min at room temperature to obtain an addition product;
then, the reaction is carried out according to the following formula of 1, 3-dicarbonyl compound 1: the molar ratio of the alkali is 1: and 2, adding a solvent and alkali into the addition product, and reacting for 3 hours at the temperature of 50-90 ℃ to obtain the HDO precursor compound.
6. The method for preparing the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 5, wherein in the step 2), the alkali is one or both of inorganic alkali and organic alkali; the alkyl halide is one or two of alkyl bromide and alkyl iodide; the PTC catalyst is one of tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium iodide;
the solvent is one of methanol, ethanol, water and tetrahydrofuran.
7. The method for preparing the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 6, wherein the inorganic base is NaOH, KOH, Ba (OH)2And K3PO4·3H2One or two of O, and the organic base is sodium ethoxide; the alkyl in the alkyl bromide and alkyl iodide is straight-chain alkane, branched alkane, unsaturated alkane or cyclane.
8. The method for preparing the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 7, wherein the carbon atoms of the straight-chain alkane and the branched-chain alkane are C1-C5, the unsaturated alkane is allyl bromide or 3, 3-dimethylallyl bromide, and the cycloalkane is cyclopentane or cycloheptane.
9. The preparation method of the alkyl-substituted polycyclic biomass high-density aviation fuel as claimed in claim 1, wherein the specific process of step 3) is as follows: according to the molar ratio of the HDO precursor compound to Pd in Pd/C of 1: 0.005-0.01, adding an HDO precursor compound and Pd/C into a reactor, then adding a solvent, filling hydrogen to 4MPa, and then reacting for 12-24 h at 200-250 ℃ to obtain the alkyl substituted polycyclic biomass high-density aviation fuel; wherein the reaction solvent is cyclohexane.
10. An alkyl-substituted polycyclic biomass high-density aviation fuel prepared according to the preparation method of any one of claims 1 to 9, wherein the structural formula of the alkyl-substituted polycyclic biomass high-density aviation fuel is as follows:
Figure FDA0002608701050000021
wherein R' is CH3、CH2CH3、CH2CH2CH3、CH2CH(CH3)2、CH2CH2CH2CH3、CH2CH2CH2CH2CH3Or CH2CH2CH(CH3)2(ii) a n is 1, 2 or 3; and m is 1 or 2.
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