A cyclic high-density biomass liquid fuel, its preparation method and application

Abstract

The present invention discloses a cyclic high-density biomass liquid fuel, a preparation method thereof and an application. In the present invention, isophorone and furfural react to generate compounds of C 14 and C 19 , and then through hydrodeoxygenation synthesis, a cyclic high-density biomass liquid fuel with a carbon chain length between C 14 and C 19 is obtained. This cyclic high-density biomass liquid fuel can be directly used as an aerospace fuel, or as an additive for increasing the cetane number, and is added to the existing aerospace fuel in a certain proportion to increase the combustion calorific value.

Description

Technical Field

[0001] The present invention belongs to the technical field of new energy, and particularly relates to a cyclic high-density biomass liquid fuel, a preparation method thereof, and an application thereof. Background Art

[0002] Aviation kerosene and diesel are two important transportation fuels, which are currently mainly produced from fossil resources (petroleum and coal). Petroleum and coal are non-renewable resources, and at the same time, certain pollution will be generated during the production process. Therefore, it is urgent to develop a new route to replace traditional fossil energy. To achieve this goal, it is necessary to reduce the use of fossil resources and vigorously develop renewable energy to replace existing energy. Biomass energy belongs to renewable resources, and the carbon dioxide generated during the combustion of biomass fuels can be offset by photosynthesis during the growth process of biomass. Therefore, biomass fuels are carbon dioxide-neutral during use.

[0003] Chinese Patent ZL201210689593.2 reported that oxygenated organic compounds were obtained from biomass such as isophorone, 3,3,5-trimethylcyclohexanol, 3,3,5-trimethylcyclohexanone, 2-ethyl-2-hexenal, 2-ethyl-2-hexanol, 2-ethyl-2-hexanal, fatty acids, fatty acid methyl (ethyl) esters, and biomass fatty acid triglycerides, and diesel or aviation kerosene range hydrocarbons were prepared by hydrodeoxygenation reaction. Under solvent-free and low-temperature conditions, a series of linear or cycloalkanes with diesel or aviation kerosene chain length ranges were obtained in high yield by direct hydrodeoxygenation of biomass oxygenates. In [Sci Rep 7, 6111 (2017)], isophorone, hydrogen, and a hydrogenation catalyst were used for selective hydrogenation to prepare 3,3,5-trimethylcyclohexanone, and then under the conditions of alkali metal hydroxide and water-carrying agent, self-condensation was carried out to obtain a bicyclic oxygenated compound precursor of C 18 Then, the precursor was hydrodeoxygenated on a supported metal bifunctional catalyst to obtain a bicyclic hydrocarbon-based high-density liquid fuel with a high volume calorific value and a low freezing point. Summary of the Invention

[0004] The primary object of the present invention is to provide a cyclic high-density biomass liquid fuel.

[0005] Another object of the present invention is to provide a preparation method of the above-mentioned cyclic high-density biomass liquid fuel.

[0006] Another object of the present invention is to provide an application of the above-mentioned cyclic high-density biomass liquid fuel.

[0007] The present invention is realized as follows. A preparation method of a cyclic high-density biomass liquid fuel, the method comprising the following steps:

[0008] (1) Isophorone, furfural and a solvent are subjected to aldol condensation under the action of a base catalyst to obtain 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one and (6-(furan-2-yl(hydroxy)methyl)-3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one;

[0009] (2) The 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one and 6-(furan-2-yl(hydroxy)methyl)-3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one in step (1) are directly subjected to hydrodeoxygenation reaction in a solvent by a supported metal catalyst to obtain a high-density biomass liquid fuel composed of cycloalkanes with a carbon chain of C 14 ~C 19 ;

[0010] Alternatively, the method includes the following steps:

[0011] (3) Isophorone is hydrogenated on a selective hydrogenation catalyst to obtain 3,3,5-trimethylcyclohexanone. 3,3,5-trimethylcyclohexanone, furfural and a solvent are subjected to aldol condensation under the action of a base catalyst to obtain 2-(furan-2-ylmethylene)-3,5,5-trimethylcyclohexanone and 2,6-bis(furan-2-ylmethylene)-3,3,5-trimethylcyclohexanone;

[0012] (4) The 2-(furan-2-ylmethylene)-3,5,5-trimethylcyclohexanone and 2,6-bis(furan-2-ylmethylene)-3,3,5-trimethylcyclohexanone in step (3) are directly subjected to hydrodeoxygenation reaction in a solvent by a supported metal catalyst to obtain a high-density biomass liquid fuel composed of cycloalkanes with a carbon chain of C 14 ~C 19 .

[0013] Preferably, in steps (1) and (3), the base catalyst is one of sodium hydroxide, potassium hydroxide and lithium hydroxide;

[0014] Preferably, in steps (2) and (4), the carrier of the supported metal catalyst is one or two of SiO2, boehmite, H-β zeolite, H-Y zeolite, HZSM-5 and montmorillonite K10, and the metal in the supported metal catalyst is one or two of cobalt, nickel, palladium, platinum and ruthenium;

[0015] Preferably, in steps (1) and (3), the solvent is one of ethanol, methanol, propanol, isopropanol, tetrahydrofuran and water;

[0016] Preferably, in steps (2) and (4), the solvent is cyclopentane or n-hexane.

[0017] Preferably, in step (3), the selective hydrogenation catalyst is one of palladium supported on activated carbon, calcium oxide, SiO2, boehmite, H-β zeolite, H-Y zeolite, HZSM-5 or montmorillonite K10, and the loading amount of palladium is 0.1% wt to 10% wt.

[0018] Preferably, in step (1), the molar ratio of isophorone to furfural is 1:1 to 2.5; the aldol condensation reaction time is 0.5 to 24 h, and the reaction temperature is from room temperature to 80 °C;

[0019] Preferably, in step (2), the hydrodeoxygenation reaction is carried out in a batch autoclave reactor, and the reaction conditions in the autoclave reactor are: reaction temperature 200 to 260 °C, reaction time 4 to 24 h, and hydrogen pressure 0.5 to 6 Mpa;

[0020] Preferably, in step (3), the molar ratio of 3,3,5-trimethylcyclohexanone to furfural is 1:1 to 2.5; the aldol condensation reaction time is 0.5 to 24 h, and the reaction temperature is from room temperature to 80 °C;

[0021] Preferably, in step (4), the hydrodeoxygenation reaction is carried out in a batch autoclave reactor, and the reaction conditions in the autoclave reactor are: reaction temperature 200 to 260 °C, reaction time 4 h to 24 h, and hydrogen pressure 0.5 to 6.0 Mpa.

[0022] Preferably, in step (1), the molar ratio of isophorone to furfural is 1:2.2, the reaction time is 2 h, and the reaction temperature is room temperature;

[0023] Preferably, in step (2), the reaction conditions of the autoclave reactor are: temperature 250 °C, reaction time 12 h, and hydrogen pressure 2 to 4 Mpa;

[0024] Preferably, in step (3), the molar ratio of 3,3,5-trimethylcyclohexanone to furfural is 1:2, the reaction time is 4 to 6 h, and the reaction temperature is from room temperature to 60 °C;

[0025] Preferably, in step (4), the reaction conditions of the autoclave reactor are: temperature 250 °C, reaction time 12 h, and hydrogen pressure 2 to 4 Mpa.

[0026] Preferably, the preparation of the supported metal catalyst comprises the following steps: preparing metal solutions with a mass concentration of 1-10% respectively, adding a support, calcining at 400 °C for 2 h, impregnating the metal solution and the support in an equal volume, standing for 24 h, drying at 80 °C for 24 h, then reducing with hydrogen at 400 °C for 4 h, and after the temperature is reduced to room temperature, passivating with nitrogen containing 1% O2 by volume for more than 4 h; the support is SiO2, boehmite, H-β zeolite, H-Y zeolite, HZSM-5 or montmorillonite K10.

[0027] Preferably, in steps (2) and (4), the mass concentration of the reaction raw materials in the solvent in the hydrodeoxygenation reaction system is 5%-60%.

[0028] The present invention further discloses a cyclic high-density biomass liquid fuel with a carbon chain length between C 14 and C 19 prepared by the above preparation method.

[0029] The present invention further discloses the application of the above cyclic high-density biomass liquid fuel in the preparation of diesel.

[0030] The present invention further discloses the application of the above cyclic high-density biomass liquid fuel in the preparation of diesel additives.

[0031] The present invention overcomes the deficiencies of the prior art and provides a cyclic high-density biomass liquid fuel, its preparation method and application. The present invention generates compounds of C 14 and C 19 by reacting isophorone with furfural, and then synthesizes a cyclic high-density biomass liquid fuel through hydrodeoxygenation. Specifically, it includes two routes: one is that isophorone and furfural are subjected to aldol condensation to obtain 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one (C14) and 3-(2-(furan-2-yl)vinyl)-6-(furan-2-methylmethylene)-5,5-dimethylcyclohex-2-en-1-one (C19), and then through the hydrodeoxygenation reaction of a metal-supported catalyst, a high-density biomass liquid fuel with a carbon chain length between C 14 and C 19 is obtained; the other is that isophorone is first selectively hydrogenated to form 3,3,5-trimethylcyclohexanone, and 3,3,5-trimethylcyclohexanone and furfural are subjected to aldol condensation to obtain 2-(furan-2-methylene)-3,5,5-trimethylcyclohexanone and 2,6-bis(furan-2-methylene)-3,3,5-trimethylcyclohexanone; then through the hydrodeoxygenation reaction of a supported metal catalyst on 2-(furan-2-methylene)-3,5,5-trimethylcyclohexan-1-one and 2,6-bis(furan-2-methylene)-3,3,5-trimethylcyclohexan-1-one, a high-density biomass liquid fuel with a carbon chain length between C14 to C 19 The obtained cyclic high-density biomass liquid fuel can be directly used as high-quality diesel or an additive to diesel.

[0032] Compared with the disadvantages and deficiencies of the prior art, the present invention has the following beneficial effects: The cyclic high-density biomass liquid fuel of the present invention can be directly used as an aerospace fuel, or as an additive to increase the cetane number, and is added to the existing aerospace fuel in a certain proportion to increase the combustion calorific value. Description of the Drawings

[0033] Figure 1 is the 1 H-NMR spectrum of 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one;

[0034] Figure 2 is the 1 H-NMR spectrum of 3-((E)-2-(furan-2-yl)vinyl)-6-(furan-2-methylmethylene)-5,5-dimethylcyclohex-2-en-1-one;

[0035] Figure 3 is the 1 H-NMR spectrum of 2-(furan-2-ylmethylene)-3,5,5-trimethylcyclohexanone;

[0036] Figure 4 is the 1 HMNR spectrum of 2,6-bis(furan-2-ylmethylene)-3,3,5-trimethylcyclohexanone. Detailed Embodiments

[0037] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0038] I. Preparation of the Catalyst

[0039] (1) The hydrogenation catalyst selected is palladium on carbon, and the preparation of palladium on carbon is specifically described in the preparation process of the following supported metal catalyst.

[0040] (2) Preparation of the supported metal catalyst

[0041] Prepare palladium chloride, ruthenium chloride, chloroplatinic acid, and iridium chloride in a mass ratio of 10%. Add one or more of the metal salt solutions to activated carbon (AC), SiO2, SiO2 / Al2O3, H-ZSM-5, H-Y, H-β molecular sieve, or montmorillonite K10 that has been treated with nitric acid (add 250 mL of 33% nitric acid solution to 50 g of activated carbon, treat it in a water bath at 80 °C for 12 hours, filter, wash with deionized water until neutral, and then dry in an oven at 120 °C for 12 hours) by equal-volume impregnation. Then let it stand for 24 h, dry overnight at 80 °C, reduce it with hydrogen at 500 °C for 2 h, and pass 1% O2 for passivation after the temperature drops to room temperature to prepare a supported metal catalyst of single metal or bimetal. The specific implementation parameters and reaction results of the prepared catalyst are shown in Table 1.

[0042] Table 1 Supported Metal Catalyst

[0043] Example Carrier Metal and its loading amount 1 AC 0.5% Pd 2 AC 1% Pd 3 AC 2% Pd 4 AC 5% Pd 5 AC 10% Pd 6 AC 2% Ru 7 AC 5% Ru 8 AC 2% Pt 9 AC 5% Pt 10 AC 2％Ir 11 AC 5％Ir 12 <![CDATA[SiO2]]> 2% Pd 13 <![CDATA[SiO2]]> 5% Pd 14 <![CDATA[SiO2 / Al2O3]]> 2% Pd 15 <![CDATA[SiO2 / Al2O3]]> 5% Pd 16 H-ZSM-5 2% Pd 17 H-ZSM-5 5% Pd 18 H-Y molecular sieve 2% Pd 19 H-Y molecular sieve 5% Pd 20 H-β molecular sieve 2% Pd 21 H-β molecular sieve 5% Pd 22 Montmorillonite K10 2% Pd 23 Montmorillonite K10 5% Pd

[0044] II. Preparation of Biomass Liquid Fuel

[0045] (1) Add 2.76 g of isophorone, 4.23 g of furfural, 20 mL of absolute ethanol, and 0.50 g of NaOH to a 50 mL round-bottom flask. Finally, add a magnetic stirrer. Connect the round-bottom flask to a condenser and place it in an oil bath with a magnetic stirrer set at a certain temperature for reaction. After the reaction is completed, transfer the solution in the round-bottom flask to a separatory funnel, add ethyl acetate and saturated brine for extraction. After discharging the lower aqueous phase, pour the organic phase into a conical flask, dry it with anhydrous sodium sulfate, and then rotary evaporate the solvent to obtain the product.

[0046] The yield of the product is calculated by gas chromatography analysis.

[0047]

[0048] 3-(2-(Furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one (Product 1)

[0049]

[0050] 3-((E)-2-(Furan-2-yl)vinyl)-6-(furan-2-ylmethylidene)-5,5-dimethylcyclohex-2-en-1-one (Product 2)

[0051] The specific implementation parameters and reaction results in step (1) are shown in Table 2 below:

[0052] Table 2 Reaction Parameters and Results of Isophorone and Furfural

[0053]

[0054]

[0055] The gas chromatographic yields of the target products 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one and 3-((E)-2-(furan-2-yl)vinyl)-6-(furan-2-ylmethylidene)-5,5-dimethylcyclohex-2-en-1-one given in Examples 24 - 59 in Table 2 show that isophorone undergoes aldol condensation with furfural, and products with certain yields are formed under the catalysis of different base catalysts: NaOH, KOH, and LiOH.

[0056] Figure 1 and Figure 2 The H-NMR spectra of typical products of one-pot aldol condensation of cyclopentanone with furfural and selective hydrogenation can prove that the synthesized target products are 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one and 3-((E)-2-(furan-2-yl)vinyl)-6-(furan-2-ylmethylidene)-5,5-dimethylcyclohex-2-en-1-one.

[0057] (2) Add 2.76 g of isophorone and 0.20 g of catalyst into a high-pressure reactor, fill with hydrogen at a pressure of 2.0 MPa, and react at 30 °C for 12 hours. After the reaction, the product is separated by centrifugation. In this step, the effects of different catalysts, reaction temperatures, reaction times, etc. on the hydrogenation reaction are shown in Table 3 below:

[0058] Table 3 Effects of different catalysts and reaction times on the hydrogenation reaction

[0059]

[0060]

[0061] As can be seen from Table 3, when the temperature is 25 - 60 °C, under the conditions of different catalysts, different hydrogen pressures, and different reaction times, isophorone undergoes selective hydrogenation to synthesize 3,3,5-trimethylcyclohexanone. The catalysts prepared from the products of Examples 60 - 82 have a certain effect on the selective hydrogenation of isophorone.

[0062] (3) Add 2.80 g of 3,3,5 - trimethylcyclohexanone, 3.84 g of furfural, 20 mL of absolute ethanol, and 0.20 g of NaOH into a 50 mL round - bottom flask. Finally, add a magnetic stir bar. Connect the round - bottom flask to a condenser and place it in an oil bath with magnetic stirring at a set temperature for reaction. After the reaction is completed, transfer the solution in the round - bottom flask into a separatory funnel, add ethyl acetate and saturated brine for extraction. After releasing the lower aqueous phase, pour the organic phase into a conical flask, dry it with anhydrous sodium sulfate, and then rotary evaporate the solvent to obtain the product. The yield of the product is calculated by gas chromatography analysis.

[0063]

[0064] 2 - (Furan - 2 - ylmethylene) - 3,5,5 - trimethylcyclohexanone (Product 3)

[0065]

[0066] 2,6 - Bis(furan - 2 - ylmethylene) - 3,3,5 - trimethylcyclohexanone (Product 4)

[0067] The parameters of each specific implementation method and their reaction results in step (3) are shown in Table 4 below:

[0068] Table 4 Reaction parameters and results of 3,3,5 - trimethylcyclohexanone and furfural

[0069]

[0070]

[0071] From the gas chromatography yields of the target products 2 - (furan - 2 - ylmethylene) - 3,5,5 - trimethylcyclohexanone and 2,6 - bis(furan - 2 - ylmethylene) - 3,3,5 - trimethylcyclohexanone given in Examples 83 - 118 in Table 4, it can be seen that for the aldol condensation of isophorone and furfural, under the catalysis of different base catalysts: NaOH, KOH, and LiOH, products with certain yields are formed.

[0072] Figure 3 and Figure 4 The H - NMR spectra of typical one - pot aldol condensation and selective hydrogenation products of cyclopentanone and furfural can prove that the synthesized target products are 2 - (furan - 2 - ylmethylene) - 3,5,5 - trimethylcyclohexanone and 2,6 - bis(furan - 2 - ylmethylene) - 3,3,5 - trimethylcyclohexanone.

[0073] A metal-supported aluminum phosphate catalyst was prepared by the impregnation method. 0.50 g of nickel nitrate hexahydrate was dissolved in 1.6 mL of water, 2.0 g of aluminum phosphate was added, stirred and allowed to stand for 12 h, dried at 120 °C for 4 h, then calcined at 500 °C for 4 h, and reduced in a hydrogen atmosphere at 500 °C for 2 h before use to obtain the catalyst Ni / AlPO4.

[0074] The preparation methods of Co / AlPO4, Ru / AlPO4, Pd / AlPO4, and Pt / AlPO4 are the same as those of Ni / AlPO4.

[0075] Typical reaction: 2.0 g of the isophorone-furfural condensation product a (the condensation product b of 3,3,5-trimethylcyclohexanone and furfural), 0.20 g of the catalyst, and 10 mL of cyclopentane (n-hexane) were charged into a 50 mL autoclave. After replacing the air in the autoclave with hydrogen 3 - 4 times, 5.0 MPa of hydrogen was charged. The reaction was carried out at 240 °C for 24 h. After the reaction was completed, gas chromatography was used for analysis and calculation of the yield. The results of the hydrodeoxygenation reaction for different catalysts, different reaction times, different reaction pressures, different reaction temperatures and other parameters are shown in Table 5 below:

[0076] Table 5. Influence of different reaction conditions on the activity of hydrodeoxygenation reaction

[0077]

[0078]

[0079] Note: The nickel loading is 5.0%, cyclopentane is used as the solvent, and the dosage is 10 mL each time.

[0080] Table 6. Application of different metals and different loadings in hydrodeoxygenation reaction

[0081]

[0082]

[0083] Note: n-hexane is used as the solvent, and the dosage is 10 mL each time.

[0084] As can be seen from Examples 119 - 154, the isophorone-furfural condensation product a (the condensation product b of 3,3,5-trimethylcyclohexanone and furfural) undergoes hydrodeoxygenation reaction in different catalysts, and the yield of C 14 -C 19 alkanes can reach 90.5%. This product can be used directly as an aerospace fuel, or as an additive to improve the cetane number and added to the existing aerospace fuel in a certain proportion for use.

[0085] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a cyclic high-density biomass liquid fuel, characterized in that, The method comprises the following steps: (1) Isophorone, furfural and a solvent are subjected to aldol condensation under the action of a base catalyst to obtain 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one and (6-(furan-2-yl(hydroxy)methyl)-3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one; (2) The 3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one and 6-(furan-2-yl(hydroxy)methyl)-3-(2-(furan-2-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-one in step (1) are directly subjected to hydrodeoxygenation reaction in a solvent by a supported metal catalyst to obtain a high-density biomass liquid fuel composed of cycloalkanes with a carbon chain of C 14 ~C 19 ; Alternatively, the method comprises the following steps: (3) Isophorone is hydrogenated on a selective hydrogenation catalyst to obtain 3,3,5-trimethylcyclohexanone. 3,3,5-Trimethylcyclohexanone, furfural and a solvent are subjected to aldol condensation under the action of a base catalyst to obtain 2-(furan-2-ylmethylene)-3,5,5-trimethylcyclohexanone and 2,6-bis(furan-2-ylmethylene)-3,3,5-trimethylcyclohexanone; (4) Directly carry out hydrodeoxygenation reaction on 2-(furan-2-ylmethylene)-3,5,5-trimethylcyclohexanone and 2,6-bis(furan-2-ylmethylene)-3,3,5-trimethylcyclohexanone in step (3) through a supported metal catalyst to obtain a high-density biomass liquid fuel composed of cycloalkanes with a carbon chain of C 14 ~C 19 .

2. The preparation method according to claim 1, characterized in that, In steps (1) and (3), the base catalyst is one of sodium hydroxide, potassium hydroxide and lithium hydroxide; In steps (2) and (4), the carrier of the supported metal catalyst is one or two of SiO2, boehmite, H-β zeolite, H-Y zeolite, HZSM-5 and montmorillonite K10, and the metal in the supported metal catalyst is one or two of cobalt, nickel, palladium, platinum and ruthenium; In steps (1) and (3), the solvent is one of ethanol, methanol, propanol, isopropanol, tetrahydrofuran and water; In steps (2) and (4), the solvent is cyclopentane or n-hexane.

3. The preparation method according to claim 1, characterized in that, In step (3), the selective hydrogenation catalyst is one of palladium supported on activated carbon, calcium oxide, SiO2, boehmite, H-β zeolite, H-Y zeolite, HZSM-5 or montmorillonite K10, and the loading amount of palladium is 0.1% wt to 10% wt.

4. The preparation method according to claim 1, wherein In step (1), the molar ratio of isophorone to furfural is 1:1 to 2.5; the aldol condensation reaction time is 0.5 to 24 h, and the reaction temperature is from room temperature to 80 °C; In step (2), the hydrodeoxygenation reaction is carried out in a batch autoclave reactor, and the reaction conditions in the autoclave reactor are: reaction temperature 200 to 260 °C, reaction time 4 to 24 h, and hydrogen pressure 0.5 to 6 Mpa; In step (3), the molar ratio of 3,3,5-trimethylcyclohexanone to furfural is 1:1 to 2.5; the aldol condensation reaction time is 0.5 to 24 h, and the reaction temperature is from room temperature to 80 °C; In step (4), the hydrodeoxygenation reaction is carried out in a batch autoclave reactor, and the reaction conditions in the autoclave reactor are: reaction temperature 200 to 260 °C, reaction time 4 h to 24 h, and hydrogen pressure 0.5 to 6.0 Mpa.

5. The preparation method according to claim 4, characterized in that, In step (1), the molar ratio of isophorone to furfural is 1:2.2, the reaction time is 2 h, and the reaction temperature is room temperature; In step (2), the reaction conditions of the autoclave reactor are: temperature 250 °C, reaction time 12 h, and hydrogen pressure 2 to 4 Mpa; In step (3), the molar ratio of 3,3,5-trimethylcyclohexanone to furfural is 1:2, the reaction time is 4 to 6 h, and the reaction temperature is from room temperature to 60 °C; In step (4), the reaction conditions of the autoclave reactor are: temperature 250 °C, reaction time 12 h, and hydrogen pressure 2 to 4 MPa.

6. The preparation method according to claim 1, characterized in that, The preparation of the supported metal catalyst comprises the following steps: respectively preparing a metal solution with a mass concentration of 1 to 10%, adding a support, calcining at 400 °C for 2 h, impregnating the metal solution and the support in an equal volume, standing for 24 h and then drying at 80 °C for 24 h, and then reducing with hydrogen at 400 °C for 4 h. After the temperature is lowered to room temperature, nitrogen containing 1% O2 by volume concentration is introduced for passivation for more than 4 h; the support is SiO2, boehmite, H-β zeolite, H-Y zeolite, HZSM-5 or montmorillonite K10.

7. The preparation method according to claim 1, characterized in that In steps (2) and (4), in the hydrodeoxygenation reaction system, the mass concentration of the reaction raw material in the solvent is 5% to 60%.

8. The cyclic high-density biomass liquid fuel obtained by the preparation method according to any one of claims 1 to 7.

9. Use of the cyclic high-density biomass liquid fuel according to claim 8 in the preparation of diesel.

10. Use of the cyclic high-density biomass liquid fuel according to claim 8 in the preparation of diesel additives.

Images