CN109852441B - Polycyclic high-density biomass liquid fuel and preparation method and application thereof - Google Patents
Polycyclic high-density biomass liquid fuel and preparation method and application thereof Download PDFInfo
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- CN109852441B CN109852441B CN201910017003.9A CN201910017003A CN109852441B CN 109852441 B CN109852441 B CN 109852441B CN 201910017003 A CN201910017003 A CN 201910017003A CN 109852441 B CN109852441 B CN 109852441B
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Abstract
The invention discloses a polycyclic high-density biomass liquid fuel and a preparation method and application thereof. The method comprises the steps of taking a cyclic ketone substance and vanillin as reaction raw materials, and carrying out aldol condensation reaction on the reaction raw materials and a first solvent under the action of an acid catalyst to obtain a primary product; wherein the cyclic ketone compound is at least one of cyclopentanone and cyclohexanone; the primary product is directly subjected to hydrodeoxygenation reaction in a second solvent by a supported metal catalyst to obtain a product with a carbon chain of C19And/or C20The polycyclic alkanes form the polycyclic high-density biomass liquid fuel. The polycyclic high-density biomass liquid fuel can be used as an aerospace fuel or an aerospace fuel additive. The yield of the polycyclic high-density biomass liquid fuel prepared by the method is over 90 percent, and the polycyclic biomass liquid fuel can be directly used as high-quality aerospace fuel or an additive of the aerospace fuel.
Description
Technical Field
The invention belongs to the technical field of biomass energy, and particularly relates to a polycyclic high-density biomass liquid fuel, and a preparation method and application thereof.
Background
Aerospace technology is an important embodiment of national technology level and scientific research strength, and aerospace vehicles comprise airplanes, missiles, rockets, airships, satellites and the like. The range, speed and load performance of an aircraft are highly dependent on the heat released by the combustion of the fuel. The high-density hydrocarbon fuel has the advantages of common liquid fuel, and also has larger mass density and volume heating value. The range, speed and payload of an aircraft can be greatly increased by using a high density hydrocarbon fuel with a given volume of the aircraft fuel tank. Under the condition of keeping the flight performance unchanged, the volume of the fuel tank can be obviously reduced by using the high-density hydrocarbon fuel, the space is reserved for other purposes, and the miniaturization of the aircraft is realized. Thus, the use of high density hydrocarbon fuels both meets the propulsion requirements of new aircraft and improves the propulsion performance of existing aircraft. In order to meet the use requirements, the high-density hydrocarbon fuel also has the characteristics of low freezing point, proper flash point, low viscosity, storage stability, low toxicity and the like.
The biomass high-density liquid fuel is a renewable novel fuel. In chinese patents with application numbers 201310231662.5, 201410736866.9, and 201710130759.5, respectively, lignocellulose-based platform compounds are used as raw materials to obtain oxygenated compounds in the polycyclic diesel range through aldol condensation, and the compounds are directly hydrodeoxygenated to obtain hydrocarbons in the highly diesel range. Utilizing cyclopentanone condensation or cyclopentanol to generate bicyclo (C) through Guerbet reaction10) And tricyclic ring (C)15) (C) prepared by selective hydrocondensation of an oxygen-containing compound and a cyclopentanone dimer20) Then hydrodeoxygenation to produce bicyclo (C)10) Tricyclic ring (C)15) And tetracyclic (C)20) High density cyclic hydrocarbon fuel.
Disclosure of Invention
The invention aims to provide a polycyclic high-density biomass liquid fuel.
The invention also aims to provide a preparation method of the polycyclic high-density biomass liquid fuel.
The invention further aims to provide application of the polycyclic high-density biomass liquid fuel.
The invention is realized in such a way that a preparation method of a polycyclic high-density biomass liquid fuel comprises the following steps:
(1) taking a cyclic ketone substance and vanillin as reaction raw materials, and carrying out aldol condensation reaction on the reaction raw materials and a first solvent under the action of an acid catalyst to obtain a primary product; wherein the cyclic ketone compound is at least one of cyclopentanone and cyclohexanone;
(2) directly carrying out hydrodeoxygenation reaction on the primary product prepared in the step (1) in a second solvent by using a supported metal catalyst to obtain a product with a carbon chain of C19And/or C20The polycyclic alkanes form the polycyclic high-density biomass liquid fuel.
Preferably, in the step (1), the mass concentration of the reaction raw material in the first solvent is 5-90%; the molar ratio of the cyclic ketone compound to the vanillin is 1 (1-4); the mass ratio of the acid catalyst to the cyclic ketone compound is (1-20): 100, respectively; the aldol condensation reaction time is 0.5-24 h, and the reaction temperature is 40-100 ℃;
in the step (2), the mass concentration of the primary product in the second solvent is 1-60%; the mass ratio of the supported metal catalyst to the primary product is (1-20): 100, respectively; the hydrodeoxygenation reaction is carried out in a batch type kettle reactor, wherein the reaction conditions in the kettle reactor are as follows: the reaction temperature is 150-400 ℃, the reaction time is 6-48 h, and the hydrogen pressure is 0.5-10.0 MPa.
Preferably, in the step (1), the mass concentration of the reaction raw material in the first solvent is 30-60%; the molar ratio of cyclopentanone to vanillin is 1: 2; the mass ratio of the acid catalyst to the cyclic ketone compound is (5-10): 100, respectively; the aldol condensation reaction time is 4-12 h, and the reaction temperature is 60-90 ℃;
in the step (2), the mass concentration of the primary product in the second solvent is 3-20%; the mass ratio of the supported metal catalyst to the primary product is (5-10): 100, respectively; the reaction conditions in the kettle reactor are as follows: the reaction temperature is 240-350 ℃, the reaction time is 12-24 h, and the hydrogen pressure is 2.0-6.0 MPa.
Preferably, in step (1), the acid catalyst is a solid acid or a liquid acid; the first solvent is at least one of ethanol, methanol and Tetrahydrofuran (THF);
in the step (2), the carrier of the supported metal catalyst comprises activated carbon and SiO2、SiO2/Al2O3H-ZSM-5, H-beta molecular sieve, H-Y molecular sieve and montmorillonite K10, wherein at least one of noble metals Pt, Pd, Ru and Ir is loaded on the carrier; the second solvent is at least one of cyclohexane, normal hexane, normal octane, tridecane and decalin.
Preferably, the solid acid is at least one of Nafion resin, Amberlyst15, Amberlyst36 and Amberlyst 70; the liquid acid is at least one of sulfuric acid, nitric acid, trifluoroacetic acid, phosphoric acid and p-toluenesulfonic acid.
Preferably, the preparation of the supported metal catalyst comprises the following steps: adding activated carbon treated by nitric acid into a noble metal solution with the mass concentration of 1-10%; calcining the carrier at 500 ℃ for 4h, soaking the calcined carrier in the noble metal solution in the same volume, standing the calcined carrier for 24h, drying the calcined carrier at 80-120 ℃ for 6-24 h, reducing the dried carrier with hydrogen at 200-600 ℃ for 1-10 h, and introducing nitrogen with the oxygen-containing volume concentration of 1% to passivate the carrier for more than 4h after the temperature is reduced to room temperature.
The invention further discloses the polycyclic high-density biomass liquid fuel prepared by the method.
The invention further discloses application of the polycyclic high-density biomass liquid fuel in the aspect of serving as an aerospace fuel.
The invention further discloses application of the polycyclic high-density biomass liquid fuel in the aspect of serving as an aerospace fuel additive.
The invention overcomes the defects of the prior art and provides a polycyclic high-density biomass liquid fuel, a preparation method and application thereof, wherein a cyclic ketone substance and vanillin are used as reaction raw materials, and the reaction raw materials and a first solvent are subjected to aldol condensation reaction under the action of an acid catalyst to obtain a primary product; wherein the cyclic ketone compound is at least one of cyclopentanone and cyclohexanone; the primary product is directly subjected to hydrodeoxygenation reaction in a second solvent by a supported metal catalyst to obtain a product with a carbon chain of C19And/or C20The polycyclic alkane is used for forming the high-density biomass liquid fuel. Wherein, when the cyclic ketone compound is cyclopentanone, the preparation method isThe primary product obtained is 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone and finally results in a product with a carbon chain of C19The high-density biomass liquid fuel (the density is 0.9261g/mL, the freezing point temperature is-31.8 ℃) formed by the polycyclic alkane specifically comprises the following steps:
when the cyclic ketone is cyclohexanone, the obtained primary product is 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone, and the final product with a carbon chain of C is obtained20The high-density biomass liquid fuel (the density is 0.9312g/mL, the freezing point temperature is-32.1 ℃) formed by the polycyclic alkane specifically comprises the following steps:
when the cyclic ketone compound is a mixture of cyclopentanone and cyclohexanone, the primary product obtained is a mixture of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone and 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone, and finally a mixture of cyclopentanone and cyclohexanone having a carbon chain of C is obtained19、C20The polycyclic alkane is used for forming the high-density biomass liquid fuel.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects: the invention provides a new route for preparing polycyclic high-density biomass liquid fuel, the yield reaches more than 90%, and the polycyclic biomass liquid fuel can be directly used as high-quality aerospace fuel or an additive of the aerospace fuel.
Drawings
FIG. 1 is a H-NMR chart of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone according to the invention;
FIG. 2 is a H-NMR chart of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone in accordance with the present invention;
FIG. 3 is a gas chromatogram of the hydrodeoxygenation product of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone;
FIG. 4 is a gas chromatogram of a hydrodeoxygenated product of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone;
FIG. 5 is a mass spectrum of 1, 3-bis (cyclohexylmethyl) cyclopentane;
FIG. 6 is a mass spectrum of 1, 3-bis (cyclohexylmethyl) cyclohexane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Preparation of catalyst
(1) Preparation of acid catalyst
Acid catalysts sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, trifluoroacetic acid, Nafion resin, Amberlyst15, Amberlyst36, Amberlyst70, and the like are commercially available.
(2) Preparation of supported metal catalyst
Preparing 10% by mass of palladium chloride, ruthenium chloride, chloroplatinic acid and chloroiridic acid, adding one or more than two metal salt solutions into nitric acid solution according to a metering ratio, treating in a water bath at 80 ℃ for 12 hours (adding 250mL of 33% nitric acid solution into 50g of activated carbon), filtering, washing to neutrality by deionized water, and drying in an oven at 120 ℃ for 12 hours2、SiO2/Al2O3H-ZSM-5, H-beta molecular sieve or montmorillonite K10, standing for 24 hr, drying at 80 deg.C overnight, reducing with hydrogen at 500 deg.C for 2 hr, cooling to room temperature, and introducing 1% O2And (3) passivating the nitrogen for 2 hours, and preparing the supported metal catalyst of single metal or double metals.
TABLE 1 Supported Metal catalysts
| Examples | Carrier | Metal and its carrying capacity | Examples | Carrier | Metal and its |
| 1 | AC | 0.5% |
16 | SiO2 | 5% |
| 2 | AC | 1% Pd | 17 | SiO2/Al2O3 | 5% Pt |
| 3 | AC | 2% Pd | 18 | H-ZSM-5 | 5% |
| 4 | AC | 5% Pd | 19 | H-beta molecular sieve | 5% Pt |
| 5 | AC | 10% |
20 | Montmorillonite K10 | 5% |
| 6 | AC | 5% Ru | 21 | HY | 5% Pt |
| 7 | AC | 5% Pt | 22 | Fly ash based carrier | 5% |
| 8 | AC | 5% Ir | 23 | HY | 5% Ir |
| 9 | SiO2 | 5% Pd | 24 | SiO2 | 5% |
| 10 | SiO2/Al2O3 | 5% |
25 | SiO2/Al2O3 | 5% Ru |
| 11 | H-ZSM-5 | 5% Pd | 26 | H-ZSM-5 | 5% Ru |
| 12 | H-beta molecular sieve | 5% Pd | 27 | H-beta molecular sieve | 5% Ru |
| 13 | Montmorillonite K10 | 5% Pd | 28 | Montmorillonite K10 | 5% |
| 14 | HY | 5% Pd | 29 | HY | 5% |
| 15 | Fly ash based carrier | 5% Pd | 30 | Fly ash based carrier | 5% Ru |
Preparation of biomass liquid fuel
(1) Adding a certain amount of cyclopentanone, vanillin, a first solvent and an acid catalyst into a 100mL round-bottom flask or a stainless steel reaction kettle, reacting for a certain time under stirring in a constant-temperature water bath or oil bath at a set temperature, cooling to room temperature after the reaction is finished, and performing rotary evaporation on the first solvent. If liquid acid is used as a catalyst, a proper amount of deionized water and a proper amount of absolute ethyl alcohol are added to sequentially wash out the acid and the unreacted raw material product. If solid acid is used as a catalyst, adding a proper amount of tetrahydrofuran to dissolve the product, filtering and filtering the catalyst, carrying out rotary evaporation on an organic phase to remove a first solvent, and adding a proper amount of deionized water and a proper amount of absolute ethyl alcohol to sequentially wash out the acid and the product of unreacted raw materials.
TABLE 2 cyclopentanone and vanillin reaction parameters and results thereof
| Examples | Cyclopentanone/g | Vanillin/g | Acid catalyst/g | First solvent/mL | Temperature/. degree.C | Time/h | Yield/%) |
| 31 | 0.84 | 3.04 | 0.05g sulfuric acid | 6ml of ethanol | 80 | 8 | 92.4 |
| 32 | 0.84 | 3.04 | 0.05g nitric acid | 6ml of ethanol | 80 | 8 | 50.8 |
| 33 | 0.84 | 3.04 | 0.05g of phosphoric acid | 12ml of ethanol | 80 | 8 | 64.7 |
| 34 | 0.84 | 3.04 | 0.05g of p-toluenesulfonic acid | 12ml of ethanol | 80 | 8 | 85.8 |
| 35 | 0.84 | 3.04 | 0.05g trifluoroacetic acid | 6ml of ethanol | 80 | 8 | 72.8 |
| 36 | 0.84 | 3.04 | 0.05gNafion | 6ml of ethanol | 80 | 10 | 58.8 |
| 37 | 0.84 | 3.04 | 0.05g Amberlyst15 | 6ml of ethanol | 80 | 10 | 45.5 |
| 38 | 0.84 | 3.04 | 0.05gAmberlyst36 | 6ml of ethanol | 80 | 10 | 48.8 |
| 39 | 0.84 | 3.04 | 0.05gAmberlyst70 | 6ml of ethanol | 80 | 10 | 42.7 |
| 40 | 0.84 | 3.04 | 0.05g sulfuric acid | 6ml of ethanol | 60 | 6 | 82.7 |
| 41 | 0.84 | 3.04 | 0.05g sulfuric acid | 6ml of methanol | 60 | 4 | 62.5 |
| 42 | 0.84 | 3.04 | 0.05g nitric acid | 6ml of methanol | 60 | 6 | 32.6 |
| 43 | 0.84 | 3.04 | 0.05g of phosphoric acid | 6ml of methanol | 60 | 10 | 48.8 |
| 44 | 0.84 | 3.04 | 0.05g of p-toluenesulfonic acid | 6ml of methanol | 60 | 10 | 78.9 |
| 45 | 0.84 | 3.04 | 0.05g trifluoroacetic acid | 6ml of methanol | 60 | 8 | 65.7 |
| 46 | 0.84 | 3.04 | 0.05gNafion | 20ml of methanol | 60 | 12 | 58.7 |
| 47 | 0.84 | 3.04 | 0.05g Amberlyst15 | 20ml of methanol | 60 | 6 | 43.8 |
| 48 | 0.84 | 3.04 | 0.05gAmberlyst36 | 20ml of methanol | 60 | 10 | 38.9 |
| 49 | 0.84 | 3.04 | 0.05gAmberlyst70 | 12ml of methanol | 60 | 10 | 39.4 |
| 50 | 0.84 | 3.04 | 0.05g sulfuric acid | 6ml of methanol | 40 | 10 | 64.2 |
| 51 | 0.84 | 3.04 | 0.05g sulfuric acid | 6ml THF | 40 | 4 | 88.5 |
| 52 | 0.84 | 3.04 | 0.05g nitric acid | 6ml THF | 40 | 6 | 40.6 |
| 53 | 0.84 | 3.04 | 0.05g of phosphoric acid | 6ml THF | 40 | 10 | 78.8 |
| 54 | 0.84 | 3.04 | 0.05g of p-toluenesulfonic acid | 6ml THF | 100 | 10 | 89.9 |
| 55 | 0.84 | 3.04 | 0.05g trifluoroacetic acid | 4ml THF | 100 | 12 | 87.7 |
| 56 | 0.84 | 3.04 | 0.05gNafion | 6ml THF | 100 | 8 | 88.9 |
| 57 | 0.84 | 3.04 | 0.05g Amberlyst15 | 6ml THF | 100 | 12 | 75.8 |
| 58 | 0.84 | 3.04 | 0.05gAmberlyst36 | 6ml THF | 100 | 12 | 77.8 |
| 59 | 0.84 | 3.04 | 0.05gAmberlyst70 | 6ml THF | 100 | 12 | 79.4 |
| 60 | 0.84 | 1.52 | 0.05g sulfuric acid | 4ml THF | 80 | 8 | 42.8 |
TABLE 3 Cyclohexanone reaction parameters with vanillin and results thereof
| Examples | Cyclopentanone/g | Vanillin/g | Acid catalyst/g | First solvent/mL | Temperature/. degree.C | Time/h | Yield/%) |
| 61 | 0.98 | 3.04 | 0.05g sulfuric acid | 6ml of ethanol | 80 | 8 | 92.5 |
| 62 | 0.98 | 3.04 | 0.05g sulfuric acid | 6ml THF | 80 | 10 | 91.2 |
| 63 | 0.98 | 3.04 | 0.05g of phosphoric acid | 6ml of ethanol | 80 | 12 | 92.5 |
| 64 | 0.98 | 3.04 | 0.05gP-toluenesulfonic acid | 6ml of ethanol | 80 | 12 | 91.6 |
| 65 | 0.98 | 3.04 | 0.05g trifluoroacetic acid | 6ml of ethanol | 80 | 10 | 88.4 |
| 66 | 0.98 | 3.04 | 0.05gNafion | 6ml of ethanol | 80 | 10 | 70.5 |
| 67 | 0.98 | 3.04 | 0.05g Amberlyst15 | 6ml of ethanol | 80 | 8 | 60.8 |
| 68 | 0.98 | 3.04 | 0.05gAmberlyst36 | 6ml of ethanol | 80 | 12 | 50.8 |
| 69 | 0.98 | 3.04 | 0.05gAmberlyst70 | 6ml of ethanol | 80 | 12 | 96.7 |
| 70 | 0.98 | 3.04 | 0.05g sulfuric acid | 6ml THF | 80 | 8 | 95.8 |
From the isolated yields of the target product 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone given in examples 31 to 60 in table 2, it can be seen that cyclopentanone reacts with vanillin aldol condensation in the presence of different acid catalysts: the product is produced in certain yield by at least one of Nafion resin, Amberlyst15, Amberlyst36, Amberlyst70, sulfuric acid, nitric acid, trifluoroacetic acid and p-toluenesulfonic acid. FIG. 1 is a H-NMR chart of an aldol condensation product, and it is confirmed that 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone was synthesized as a target product.
From the isolated yields of the target product 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone given in examples 61 to 70 in table 3, it can be seen that the condensation reaction of cyclohexanone with vanillin was carried out in the presence of different acid catalysts: the product is produced in certain yield by at least one of Nafion resin, Amberlyst15, Amberlyst36, Amberlyst70, sulfuric acid, nitric acid, trifluoroacetic acid and p-toluenesulfonic acid. FIG. 2 is a H-NMR chart of an aldol condensation product, demonstrating that the target product synthesized is 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone.
(2) In a 100mL hydrogenation kettle type reactor, a certain amount of aldol condensation reaction product, a catalyst and a second solvent are filled into a reaction kettle, and after hydrogen is filled into the reactor to replace air in the kettle, certain pressure is filled. The reaction is carried out under the conditions of set temperature and time. In this step, the hydrodeoxygenation reaction results of parameters such as different catalysts, different solvents, different reaction times, different reaction pressures, different reaction temperatures, and the like are shown in table 4 below:
TABLE 42, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone (X)2Cp) results of hydrodeoxygenation reactions under different experimental conditions
| Examples | X2Cp/g | Catalyst/g | Second solvent/g | Temperature/. degree.C | pressure/MPa | Time/h | C19Naphthene yield/%) |
| 71 | 1.00 | Pd/C | Cyclohexane | 350 | 2.0 | 12 | 92.5 |
| 72 | 1.00 | Pd/C | Cyclohexane | 350 | 4.0 | 12 | 91.8 |
| 73 | 1.00 | Pd/C | Cyclohexane | 350 | 6.0 | 12 | 90.4 |
| 74 | 1.00 | Pt/C | Cyclohexane | 350 | 2.0 | 8 | 78.3 |
| 75 | 1.00 | Pt/C | Cyclohexane | 350 | 2.0 | 10 | 85.2 |
| 76 | 1.00 | Pt/C | Cyclohexane | 350 | 2.0 | 18 | 90.9 |
| 77 | 1.00 | Ru/C | Cyclohexane | 350 | 2.0 | 10 | 82.7 |
| 78 | 1.00 | Ru/C | Cyclohexane | 350 | 4.0 | 10 | 85.6 |
| 79 | 1.00 | Ru/C | N-hexane | 350 | 4.0 | 24 | 75.5 |
| 80 | 1.00 | Ir /C | N-hexane | 350 | 2.0 | 5 | 90.5 |
| 81 | 1.00 | Ir /C | N-hexane | 350 | 4.0 | 10 | 90.6 |
| 82 | 1.00 | Ir /C | N-hexane | 350 | 2.0 | 30 | 90.5 |
| 83 | 1.00 | Pd /SiO2 | N-octane | 310 | 1.0 | 12 | 91.3 |
| 84 | 1.00 | Pd /SiO2 | N-octane | 310 | 2.0 | 12 | 91.2 |
| 85 | 1.00 | Pd /SiO2 | N-octane | 310 | 1.0 | 24 | 92.5 |
| 86 | 1.00 | Pd /SiO2/Al2O3 | N-octane | 300 | 2.0 | 12 | 94.3 |
| 87 | 1.00 | Pd /SiO2/Al2O3 | Tridecane | 300 | 2.0 | 10 | 92.7 |
| 88 | 1.00 | Pd /SiO2/Al2O3 | Tridecane | 300 | 6.0 | 8 | 89.8 |
| 89 | 1.00 | Pd /H-ZSM-5 | Tridecane | 280 | 4.0 | 12 | 89.8 |
| 90 | 1.00 | Pd /H-ZSM-5 | Tridecane | 280 | 4.0 | 24 | 88.9 |
| 91 | 1.00 | Pd /H-ZSM-5 | Decahydronaphthalene | 300 | 2.0 | 15 | 87.5 |
| 92 | 1.00 | Pd /H-β | Decahydronaphthalene | 300 | 2.0 | 5 | 88.8 |
| 93 | 1.00 | Pd /H-β | Decahydronaphthalene | 300 | 3.0 | 10 | 89.5 |
| 94 | 1.00 | Pd /H-β | Decahydronaphthalene | 300 | 4.0 | 24 | 89.9 |
| 95 | 1.00 | Pd/montmorillonite K10 | Decahydronaphthalene | 280 | 3.0 | 12 | 91.6 |
| 96 | 1.00 | Pd/montmorillonite K10 | Decahydronaphthalene | 280 | 4.0 | 10 | 91.2 |
| 97 | 1.00 | Pd/montmorillonite K10 | Decahydronaphthalene | 280 | 2.0 | 24 | 92.0 |
| 98 | 1.00 | Pd /H-β | Cyclohexane | 260 | 2.0 | 12 | 90.1 |
| 99 | 1.00 | Pd /H-β | Cyclohexane | 250 | 2.0 | 10 | 88.2 |
| 100 | 1.00 | Pd /H-β | Cyclohexane | 240 | 7.0 | 24 | 84.1 |
TABLE 52, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone (X)2He) results of hydrodeoxygenation reactions under different experimental conditions
| Examples | X2He/g | Catalyst/g | Second solvent/g | Temperature/. degree.C | pressure/MPa | Time/h | C20Naphthene yield/%) | |
| 101 | 1.00 | Pd/C | Cyclohexane | 350 | 2.0 | 12 | 91.5 | |
| 102 | 1.00 | Pt/C | Cyclohexane | 350 | 2.0 | 18 | 90.5 | |
| 103 | 1.00 | Ru/C | Cyclohexane | 350 | 2.0 | 10 | 83.9 | |
| 104 | 1.00 | Ir /C | N-hexane | 350 | 4.0 | 10 | 89.7 | |
| 105 | 1.00 | Pd /SiO2 | N-octane | 310 | 1.0 | 24 | 90.1 | |
| 106 | 1.00 | Pd /SiO2/Al2O3 | N- |
300 | 2.0 | 12 | 91.3 | |
| 107 | 1.00 | Pd /SiO2/Al2O3 | Tridecane | 300 | 2.0 | 10 | 91.6 | |
| 108 | 1.00 | Pd /H-ZSM-5 | |
280 | 4.0 | 24 | 89.8 | |
| 109 | 1.00 | Pd /H-ZSM-5 | |
300 | 2.0 | 15 | 88.6 | |
| 110 | 1.00 | Pd /H- | Decahydronaphthalene | 300 | 2.0 | 5 | 90.8 | |
| 111 | 1.00 | Pd/ | Decahydronaphthalene | 280 | 3.0 | 12 | 90.6 | |
| 112 | 1.00 | Pd /H- | Cyclohexane | 260 | 2.0 | 12 | 92.5 | |
| 113 | 1.00 | Pd /H-β | Cyclohexane | 250 | 4.0 | 10 | 90.2 | |
| 114 | 1.00 | Pd /H- | Cyclohexane | 240 | 7.0 | 24 | 85.2 |
As can be seen from Table 4, the product C of hydrodeoxygenation of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone in examples 71-100 was obtained at a temperature of 240-350 ℃19The yield of the polycyclic hydrocarbon can reach 92.7 percent. The density and freezing point of the product were 0.926g/mL and-31.8 deg.C, respectively. The gas chromatogram of the 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclopentanone hydrodeoxygenation product and the mass spectrogram of the main product 1, 3-bis (cyclohexylmethyl) cyclopentane are respectively shown in FIG. 3 and FIG. 5; the additive can be directly used as an aerospace fuel or added into the existing aerospace fuel in a certain proportion as an additive for improving the cetane number.
As can be seen from Table 5, the hydrodeoxygenated products C of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone from examples 101 to 114 at temperatures of 240 to 350 ℃20The yield of the polycyclic hydrocarbon can reach 92.5 percent. The density and freezing point of the product were 0.931g/mL and-32.1 deg.C, respectively. Gas chromatogram of 2, 6-bis (4-hydroxy-3-methoxybenzylidene) cyclohexanone hydrodeoxygenation product andthe mass spectra of the main product 1, 3-bis (cyclohexylmethyl) cyclohexane are shown in FIGS. 4 and 6, respectively. Can be directly used as aviation kerosene and high-quality diesel oil, or can be used as an additive for improving the cetane number and added into the existing aviation kerosene and diesel oil in a certain proportion for use.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A preparation method of a polycyclic high-density biomass liquid fuel is characterized by comprising the following steps:
(1) taking a cyclic ketone substance and vanillin as reaction raw materials, and carrying out aldol condensation reaction on the reaction raw materials and a first solvent under the action of an acid catalyst to obtain a primary product; wherein the cyclic ketone compound is at least one of cyclopentanone and cyclohexanone;
(2) directly carrying out hydrodeoxygenation reaction on the primary product prepared in the step (1) in a second solvent by using a supported metal catalyst to obtain a product with a carbon chain of C19And/or C20The polycyclic alkane is used for forming polycyclic high-density biomass liquid fuel;
in the step (1), the mass concentration of the reaction raw material in the first solvent is 5-90%; the molar ratio of the cyclic ketone compound to the vanillin is 1 (1-4); the mass ratio of the acid catalyst to the cyclic ketone compound is (1-20): 100, respectively; the aldol condensation reaction time is 0.5-24 h, and the reaction temperature is 40-100 ℃; the first solvent is at least one of ethanol, methanol and tetrahydrofuran;
in the step (2), the mass concentration of the primary product in the second solvent is 1-60%; the mass ratio of the supported metal catalyst to the primary product is (1-20): 100, respectively; the hydrodeoxygenation reaction is carried out in a batch type kettle reactor, wherein the reaction conditions in the kettle reactor are as follows: the reaction temperature is 150-400 ℃, the reaction time is 6-48 h, and the hydrogen pressure is 0.5-10.0 MPa; the second solvent is at least one of cyclohexane, normal hexane, normal octane, tridecane and decalin.
2. The preparation method of the polycyclic high-density biomass liquid fuel as claimed in claim 1, wherein in the step (1), the mass concentration of the reaction raw material in the first solvent is 30-60%; the molar ratio of the cyclic ketone compound to the vanillin is 1: 2; the mass ratio of the acid catalyst to the cyclic ketone compound is (5-10): 100, respectively; the aldol condensation reaction time is 4-12 h, and the reaction temperature is 60-90 ℃;
in the step (2), the mass concentration of the primary product in the second solvent is 3-20%; the mass ratio of the supported metal catalyst to the primary product is (5-10): 100, respectively; the reaction conditions in the kettle reactor are as follows: the reaction temperature is 240-350 ℃, the reaction time is 12-24 h, and the hydrogen pressure is 2.0-6.0 MPa.
3. The method for preparing the polycyclic high-density biomass liquid fuel according to claim 1, wherein in the step (1), the acid catalyst is a solid acid or a liquid acid;
in the step (2), the carrier of the supported metal catalyst comprises activated carbon and SiO2、SiO2/Al2O3H-ZSM-5, H-beta molecular sieve, H-Y molecular sieve and montmorillonite K10, wherein at least one of noble metals Pt, Pd, Ru and Ir is loaded on the carrier.
4. The method for preparing the polycyclic high-density biomass liquid fuel according to claim 3, wherein the solid acid is at least one of Nafion resin, Amberlyst15, Amberlyst36 and Amberlyst 70; the liquid acid is at least one of sulfuric acid, nitric acid, phosphoric acid and p-toluenesulfonic acid.
5. The method for preparing the polycyclic high-density biomass liquid fuel according to claim 3, wherein the preparation of the supported metal catalyst comprises the following steps: adding activated carbon treated by nitric acid into a noble metal solution with the mass concentration of 1-10%; calcining the carrier at 500 ℃ for 4h, soaking the calcined carrier in the noble metal solution in the same volume, standing the calcined carrier for 24h, drying the calcined carrier at 80-120 ℃ for 6-24 h, reducing the dried carrier with hydrogen at 200-600 ℃ for 1-10 h, and introducing nitrogen with the oxygen-containing volume concentration of 1% to passivate the carrier for more than 4h after the temperature is reduced to room temperature.
6. The polycyclic high-density biomass liquid fuel prepared by the method of any one of claims 1 to 5.
7. Use of the polycyclic high density biomass liquid fuel of claim 6 as an aerospace fuel.
8. Use of the polycyclic high density biomass liquid fuel of claim 6 as an aerospace fuel additive.
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