CN104711007A - Preparation method of aviation kerosene or diesel oil scope liquid alkane - Google Patents

Abstract

A synthesis route of aviation kerosene (or diesel) liquid alkane fuel that uses lignocellulose-based platform compounds as raw materials and is completely independent of fossil energy. The obtained liquid fuel can be used as a substitute for aviation kerosene (or diesel). The method is divided into two parts: 1) Under the action of alkali catalysis, lignocellulose-based furfural compounds (including furfural, methylfurfural, chloromethylfurfural or 5-hydroxymethylfurfural, etc.) and ketone compounds (including acetone , butanone, 2-pentanone, 2-heptanone, cyclopentanone, mesityl oxide, methyl isobutyl ketone (MIBK), sodium levulinate or levulinate, etc.) by aldol condensation reaction Oxygen-containing precursors with a carbon chain length of 9-16; 2) Using a supported metal A/X type bifunctional catalyst, the precursor produced in step 1 is subjected to a one-step hydrodeoxygenation reaction under low temperature and solvent-free conditions to obtain carbon Aviation kerosene (or diesel) long-chain liquid alkanes with a chain length of 9 to 16.

Description

A kind of preparation method of aviation kerosene or diesel oil range liquid alkane

technical field

The present invention relates to lignocellulose-based furfural compounds (including furfural, methylfurfural, chloromethylfurfural or 5-hydroxymethylfurfural) and ketone compounds (including acetone, butanone, 2-pentanone, 2-heptanone Ketone, cyclopentanone, mesityl oxide, methyl isobutyl ketone (MIBK), sodium levulinate or levulinic acid ester, etc.) as raw materials, aviation kerosene or diesel long-chain liquid alkanes completely independent of fossil energy The synthetic route specifically includes two steps: 1) furfurals and ketones undergo an aldol condensation reaction to generate oxygenates with a carbon chain length of 9-16; Hydrodeoxygenation to obtain liquid alkanes with a carbon chain length of 9-16. Compared with the work that has been reported internationally, this work is the first to use acetone, butanone, 2-pentanone, 2-heptanone, cyclopentanone, mesityl oxide, methyl isobutyl ketone (MIBK), Sodium levulinate or levulinate is used as raw materials to synthesize C9-C16 alkanes through aldol condensation and direct hydrodeoxygenation with furfural compounds under solvent-free conditions. Utilizing the dissolving effect of aldol condensation products with low freezing point on aldol condensation products with high freezing point, it overcomes the existing work in the world that the aldol condensation products are solid, and the process of aldol condensation and hydrodeoxygenation needs to add solvents to help mass transfer and process. More complex and other disadvantages.

Background technique

At present, the commonly used liquid fuels in the world are mainly made of petroleum as raw materials, and are prepared by rectification, cracking, reforming and other processes. They are non-renewable and face the dual pressures of energy shortage and environmental degradation. In recent years, the preparation of liquid fuels from biomass has attracted widespread attention from the international community due to its renewable raw materials and the characteristics of carbon dioxide neutrality in the preparation and use process. As a transportation fuel with huge demand, aviation fuel is a country's strategic material. Aviation kerosene is generally composed of alkanes with carbon numbers between 6 and 16. Currently, Jet-A and JP-8 are commonly used, and the composition of JP-8 ^[2] is as follows: C8-C15 straight-chain alkanes account for 35%, C8-C15 branched-chain alkanes account for 35%, C7-C10 aromatic Hydrocarbons account for 18%, and C6-C10 naphthenes account for 7%. From three aspects of environmental protection, national energy security and potential economic value, it is necessary to vigorously develop aviation kerosene preparation technology using renewable biomass as raw material.

The route of preparing liquid fuels from biomass has been developed for a certain period of time. The first generation of biomass fuel is based on starch, animal and vegetable oils as raw materials. The cost of this route of using edible biomass as raw material is too high, and it is not suitable for the national conditions of our country with many people and little land. Therefore, the second-generation biomass fuel based on lignocellulose, which is the main component of agricultural and forestry waste, has received more attention in recent years. Among them, the small molecular platform substances obtained from lignocellulose through chemical and biological treatment (including hydrolysis, fermentation, selective hydrogenation, etc.) are used as raw materials, and oxygen-containing organic compounds with aviation kerosene chain length are obtained through carbon-carbon coupling , followed by hydrodeoxygenation of these oxygenated organic compounds to produce liquid alkanes is a promising new route for biomass fuels. The process has the advantages of relatively mild conditions and flexible synthetic routes.

At present, the methods for preparing aviation kerosene from lignocellulose derivatives in the existing international technologies include:

Dumesic et al. reported in the patent [US7,671,246] that hydroxymethylfurfural or furfural and acetone undergo alkali-catalyzed aldol condensation reaction, and then undergo steps such as low-temperature hydrogenation and hydrodeoxygenation to prepare liquid alkanes in the C8-C15 range. They used Pt/SiO2-Al2O3 as the hydrodeoxygenation catalyst in a fixed-bed four-phase flow reactor. During the reaction process, hexadecane needs to be added to the raw materials, and the process is relatively complicated (Science, 2005, 308, 1446-1450). To solve this problem, the patent [US7,880,049] uses phosphorylated niobium oxide as a carrier, which can achieve good results without using hexadecane, thus simplifying the process (ChemSusChem, 2008, 1, 417-424). But there are following problems in this route: 1) the aldol condensation product of furfural (or hydroxymethylfuran) and acetone is solid and has very low solubility in water, so organic solvents must be used in the aldol condensation and hydrodeoxygenation process, resulting in Reduced equipment efficiency and increased operating costs. 2) The process is complicated: the synthesis of long-chain alkanes from furfural and acetone requires three steps of aldol condensation-low-temperature hydrogenation-hydrodeoxygenation.

Corma et al reported the acid-catalyzed alkylation reaction between methyl furan and butyraldehyde, 5-methylfurfural, 5-hydroxymethylfurfural and the trimerization reaction of methyl furan itself, and prepared aviation kerosene or diesel oil Oxygenated organic compounds in the chain length range, and then they obtained a series of aviation kerosene branched hydrocarbons with lower freezing points by hydrodeoxygenating these compounds (Angew.Chem.Int.Ed.2011,50,1- 5). However, using sulfuric acid and toluenesulfonic acid as catalysts in this method will cause corrosion to equipment and pollution to the environment.

In the previous work of our research group [Chinese patent: application number: 201110346501.1; 201210169817.2; 20121043947.9], a series of aviation kerosene chains with lignocellulose-based platform compounds were obtained through alkylation reaction or aldol condensation reaction Long-range oxygen-containing organic compounds, through direct hydrodeoxygenation of these organic compounds to obtain low freezing point branched chain hydrocarbons with aviation kerosene chain length range. At the same time, a nickel-promoted tungsten carbide catalyst has also been developed, which can replace noble metals for hydrodeoxygenation reactions. However, these methods still require high reaction temperature (350°C) in the hydrodeoxygenation step.

Furfural is an important chemical obtained from the hydrolysis-dehydration reaction of hemicellulose in various agricultural and forestry wastes. It is a renewable and green chemical product. Methylfurfural is the dehydration-partial hydrogenation product of biomass such as cellulose and Jerusalem artichoke; chloromethylfurfural is the dehydration product of biomass such as cellulose and Jerusalem artichoke under the catalysis of hydrochloric acid; hydroxymethylfurfural is the product of biomass such as cellulose and Jerusalem artichoke Dehydration products; 2-pentanone and 2-heptanone are acetone, butanol and ethanol obtained by lignocellulose fermentation method (Acetone-Butanol-Ethanol Fermentation), and a series of chain lengths obtained by alkylation reaction under palladium catalysis Short linear ketones (Nature, 2012, 491, 235-239). Acetone is the main product obtained by Acetone-Butanol-Ethanol Fermentation. Mesityl oxide is an aldol condensation product of acetone itself. Methyl isobutyl ketone is a partial hydrogenation product of mesityl oxide. Cyclopentanone is a selective hydrogenation product of furfural. Levulinic acid or levulinate is the dehydration (or dehydration-esterification) product of six carbon sugars, a product of cellulose hydrolysis. Butanone can be obtained from the partial oxidation of 2-butanol, a biomass fermentation product, or the catalytic decarboxylation of levulinic acid. The alkanes obtained after hydrodeoxygenation of these ketones have relatively short chain lengths and are not suitable for use as aviation kerosene. The work of the present invention carries out carbon-carbon coupling of these ketone compounds and furfural and other compounds through aldol condensation, realizes carbon chain growth, and obtains oxygenated compounds with aviation kerosene (or diesel) chain length with high selectivity, and through these Direct hydrodeoxygenation of oxygenates under mild conditions to obtain long-chain liquid alkanes in the range of aviation kerosene or diesel chain lengths. In addition, the present invention uses the dissolution effect of aldol products with low freezing point on aldol condensation products with high freezing point for the first time to obtain a liquid mixed oxygen-containing precursor, which overcomes the fact that aldol condensation products with high freezing points are solid at room temperature, and solvents need to be added to carry out the aldol condensation process. The shortcomings of aldehyde condensation and hydrodeoxygenation get rid of the dependence of the reaction system on organic solvents, simplify the process and reduce the cost.

Contents of the invention

The purpose of the present invention is to provide a novel synthetic route for preparing long-chain liquid alkanes in the range of C9-C16 aviation kerosene or diesel oil starting from lignocellulose-based platform compounds.

The present invention is achieved through the following technical solutions:

The first step is to prepare oxygen-containing organic compounds with a carbon chain length between 9 and 16 by alkali-catalyzed aldol condensation reaction between lignocellulosic furfural compounds and ketone compounds;

Furfural compounds are: one or more mixtures of furfural, methylfurfural, chloromethylfurfural or 5-hydroxymethylfurfural; ketone compounds are: acetone, methyl ethyl ketone, 2-pentanone, 2- One or more mixtures of heptanone, cyclopentanone, mesityl oxide, methyl isobutyl ketone (MIBK), sodium levulinate or levulinate; the base catalyst is mineral base, organic base or solid base. Including hydroxides or oxides of alkali metals and alkaline earth metals such as NaOH, MgO, CaO, SrO, BaO, etc., hydrotalcite compounds such as magnesium aluminum hydrotalcite, lithium aluminum hydrotalcite, cobalt aluminum hydrotalcite, etc., KF/Al ₂ One or a mixture of two or more of O ₃ , MgO-ZrO ₂ , organic amines, quaternary ammonium salts, basic molecular sieves, basic ion exchange resins, etc.

This step uses a batch tank reactor. The molar ratio of lignocellulose-based furfurals to ketones is 10:1 to 1:10, preferably 1:3, unreacted raw materials can be removed by distillation and recycled; the reaction temperature is between 50-200°C, preferably 130-150°C; the reaction time is 1-12h, preferably 4-6h; the reaction can be carried out without solvent.

For some aldol condensation products that are solid, two or more ketones and furfural compounds can be used to undergo aldol condensation reactions at the same time, and the aldol condensation product with a low freezing point can be used to dissolve the aldol condensation product with a high freezing point, so that the final product obtained is Liquid, can be directly used in hydrodeoxygenation reaction.

In the second step, a supported metal catalyst is used to directly hydrodeoxygenate the liquid product obtained by the aldol condensation to obtain long-chain liquid alkanes in the range of aviation kerosene or diesel oil with a carbon chain length of 9-16.

The hydrodeoxygenation reaction is carried out in a fixed-bed reactor under liquid-state solvent-free conditions. The aldol condensation product is purified by vacuum distillation and directly enters the fixed-bed reactor.

The conditions of the fixed bed reactor are as follows: the temperature is between 150 and 400°C, the reaction pressure is between 0.1 and 20.0 MPa, the reactant/catalyst mass space velocity is between 0.1 and 20.0 h ^-1 , and the molar ratio of H ₂ to substrate is 20~1500. The preferred conditions are: temperature 230-260°C, hydrogen pressure 4-10 MPa, mass space velocity of reaction raw material/catalyst 0.3-2h ^-1 , and molar ratio of hydrogen to reaction raw material 200-800.

In the supported metal A/X type catalyst, the active component A is one or a mixture of two or more of Pt, Pd, Ru, Ir, Ni, Cu, Fe, and the carrier X is aluminum oxide, silicon oxide, silicon-aluminum composite One or more mixtures of carrier, molecular sieve (HZSM-5 type, Hβ molecular sieve, HY type, HMOR type), activated carbon, metal phosphate, metal oxide;

The supported metal catalyst is prepared by an equal-volume impregnation method, and the mass fraction of the active component A is 1-10%. Add the soluble salt solution of A to the medium-volume preformed carrier X for impregnation, let it stand for 6 hours and then dry it at 80°C, then reduce it with hydrogen at 300-600°C for 3-5 hours, and pass it after the temperature drops to room temperature. passivation by nitrogen gas containing 1% O ₂ by volume.

Through the above steps, a relatively high yield (90%) of long-chain liquid alkanes in the range of aviation kerosene (or diesel) with a carbon chain length of C9 to C16 has been obtained, and the preparation of aviation kerosene (or diesel) using lignocellulose derivatives as raw materials has been realized. Diesel) a new and simple synthetic route.

Description of drawings

The ¹³ C-NMR figure of Fig. 1 furfural and 2-pentanone condensation product A;

The ¹ H-NMR figure of Fig. 2 furfural and 2-pentanone condensation product A;

Fig. 3 The ¹³ C-NMR figure of condensation product B of furfural and 2-heptanone;

Fig. 4 ¹ H-NMR chart of condensation product B of furfural and 2-heptanone.

Detailed ways

The present invention will be described below with specific examples, but the protection scope of the present invention is not limited to these examples.

Examples 1-13

1. Preparation of catalyst:

1) Preparation of solid base catalyst: Alkaline earth oxides (MgO, CaO, SrO, BaO) were obtained by calcination of corresponding nitrates under N ₂ atmosphere for 8 h. Magnesium aluminum hydrotalcite is a solution of Mg(NO ₃ ) ₂ 6H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O mixed in a certain molar ratio is added dropwise to a mixed solution of NaOH and NaCO ₃ in a water bath at 70°C ( [CO ₃ ]/[Al]+[Mg]=0.53, [OH]/[Al]+[Mg]=2.33), after the dropwise addition, continue to stir and age overnight, filter and wash, dry at 80°C overnight, and calcined at 450°C 8h, the mixed oxide of magnesium and aluminum was obtained. Lithium aluminum hydrotalcite is made by adding Al(NO ₃ ) ₃ 9H ₂ O solution dropwise to the mixed solution of LiOH and Na ₂ CO ₃ at room temperature, aged in a water bath at 75°C overnight, filtered and washed, dried overnight at 80°C, and calcined at 450°C 8h, lithium aluminum mixed oxide was obtained. Cobalt aluminum hydrotalcite Add Co(NO ₃ ) ₂ 6H ₂ O and Al(NO ₃ ) ₃ 9H ₂ O solutions in a certain molar ratio dropwise to the mixed solution of NaOH and NaCO ₃ in a water bath at 25°C, the pH Controlled at 10-11, aged overnight in a water bath at 80°C, dried overnight at 80°C after filtering and washing, and calcined at 300°C for 8 hours to obtain a cobalt-aluminum mixed oxide.

KF/Al ₂ O ₃ Immersed γ-Al ₂ O ₃ in KF solution for 12 hours by equal volume impregnation method, and dried at 80℃ to obtain KF/γ-Al ₂ O ₃ with a theoretical loading of 23%. MgO-ZrO ₂ Add 25% NaOH solution dropwise to Mg(NO ₃ ) ₂ .6H ₂ O and ZrO(NO ₃ ) ₂ solution mixed in a certain molar ratio to pH=10, age at room temperature for 72h, filter and wash, 80℃ Dry overnight and calcined at 600°C for 8h. All solid base catalysts should be pretreated in _N2 atmosphere for 2h before use.

3) Preparation of hydrodeoxygenation catalyst:

Prepare a solution with a mass fraction of 10% chloroplatinic acid, palladium chloride, ruthenium chloride, iridium chloride, and nickel nitrate, dilute it according to the saturated water absorption of the carrier, add one or more of them to the silica carrier to impregnate the same volume, and let stand Overnight, dry at 80°C, roast at 500°C for 2 hours, reduce with hydrogen at 500°C for 2 hours, passivate with volume ratio of 1% O ₂ /N ₂ after the temperature drops to room temperature, and prepare supported single metal or alloy catalysts (see Table 1, Examples 1-6).

Prepare a palladium chloride solution with a mass ratio of 10%, dilute it according to the saturated water absorption of the carrier, add alumina, silicon oxide, silicon-aluminum composite carrier, molecular sieve, activated carbon, zirconium phosphate, and then let it stand for 2 hours. Drying overnight, roasting in air at 500°C for 2h, reducing with hydrogen at 500°C for 2h, passing through passivation with a volume ratio of 1% O ₂ /N ₂ after the temperature is lowered to room temperature, palladium catalysts supported on different supports can be prepared (see Table 1 , Examples 7-13). The activated carbon used in the present invention is all mixed with nitric acid with a mass concentration of 20-50% in a mass ratio of 1:15, and soaked at 80°C for 24 hours for pretreatment. Filter and wash with hot water at 80°C until neutral and then dry. Zirconium phosphate (ZrP) catalyst is mixed with 1mol/L zirconium oxychloride and ammonium dihydrogen phosphate aqueous solution at a volume ratio of 2:1, and the obtained precipitate is washed and filtered repeatedly, dried at 120°C for 10h, and then dried at 400°C Under roasting 4h. HZSM-5 molecular sieves, Hβ molecular sieves, HY type molecular sieves, and HMOR molecular sieves are commercial catalysts purchased directly.

Table 1 Supported metal A/X type bifunctional catalyst

Example carrier Precious metals and their loadings Example 1 SiO ₂ 5%Pt Example 2 SiO ₂ 5%Pd Example 3 SiO ₂ 5%Ru Example 4 SiO ₂ 5%Ir Example 5 SiO ₂ 5%Ni Example 6 SiO ₂ 4%Ni1%Pt Example 7 Al ₂ O ₃ 5%Pd Example 8 SiO ₂ 5%Pd Example 9 SiO ₂ -Al ₂ O ₃ 5%Pd Example 10 HZSM-5 molecular sieve 5%Pd Example 11 H-beta molecular sieve 5%Pd Example 12 activated carbon 5%Pd Example 13 Zirconium phosphate 5%Pd

Examples 14-26

2. Aldol condensation reaction: Add 1.92g furfural, 5.16g 2-pentanone (or lignocellulose-based furfural compounds and ketone compounds with a molar ratio of 1:3), 0.36g catalyst (catalyst ratio 10wt%), stirred in an oil bath at 130°C for 6h. The reaction results are shown in Table 2.

Table 2 Aldol condensation reaction and its results

Table 3 Aldol condensation target product structural formula

It can be seen from Table 2 that under the action of different solid base catalysts, aldol condensation products are produced in a certain yield. Among them, CaO has the best activity. Figures 1-4 are the ¹³ C-HMR and ¹ H-NMR charts of product A and product B respectively, which prove that these products can be synthesized by aldol condensation reaction.

Examples 27-31

Taking CaO as an example, the amount of catalyst is kept at 10wt%, and the optimization of reaction conditions is explored.

1) The effect of different reaction substrate ratios on the yield of furfural-2-pentanone system

Table 4. Effect of different reaction substrate ratios on A yield

It can be seen from Table 4 that the excess of 2-pentanone is beneficial to obtain the target product in high yield. Considering the operating cost and environmental factors, the suitable reaction conditions were selected with a substrate ratio of 1:3.

Examples 32-35

2) Effect of different reaction temperatures on the yield of furfural-2-pentanone system

Table 5. Effect of different reaction temperature ratios on A yield

As can be seen from Table 5, the yield of product A is the highest when the reaction temperature is 130°C.

Examples 36-39

3) Effect of different reaction time on the yield of furfural-2-pentanone system

Table 6. Effect of different reaction temperature ratios on A yield

As can be seen from Table 6, when the reaction time is 6h, the yield of product A is basically stable.

Examples 40-42

In order to overcome the shortcomings of some furfural compounds and ketone compounds reacting to form solid products that are not conducive to mass transfer and the next direct hydrodeoxygenation reaction, furfural compounds and two mixed ketones are used as reaction substrates, because one of them has The lower freezing point can dissolve the high freezing point aldol condensation product, so the obtained product is a liquid mixed precursor.

Taking the furfural-2-pentanone-2-heptanone system as an example, the reaction conditions were optimized.

1) Effect of different reaction substrate ratios on the yield of furfural-2-pentanone-2-heptanone system

Table 7. Effects of different reaction substrate ratios on the yields of A and B

It can be seen from Table 7 that when the molar ratio of furfural, 2-pentanone, and 2-heptanone is 1:2:1, the total yield can reach up to 94%.

Examples 43-46

2) Effect of different reaction temperatures on the yield of furfural-2-pentanone-2-heptanone system

Table 8. Effects of different reaction temperatures on the yields of A and B

It can be seen from Table 8 that when the reaction temperature is 130-150° C., the total yield of products A and B is ideal.

Examples 47-58

3. Hydrodeoxygenation reaction: In a fixed bed reactor, put 2g of catalyst into the reaction tube, keep the pressure in the reactor at 6.0MPa, the temperature at 260°C, and the hydrogen flow rate at 120mL/min. The aldol condensation product A (Example 16) was pumped into the reactor at 0.04 mL/min with a high-performance liquid chromatography pump. The reaction results are shown in Table 9.

Table 9. Effects of different A/X-type bifunctional catalysts on the activity of hydrodeoxygenation reactions

Example catalyst C9～C16 Alkanes Yield Example 47 Pt/SiO ₂ 65% Example 48 Pd/SiO ₂ 67% Example 49 Ru/ _SiO2 60% Example 50 Ir/ _SiO2 66% Example 51 Ni/SiO ₂ 61% Example 52 Pd/Al ₂ O ₃ 81% Example 53 Pd/SiO ₂ -Al ₂ O ₃ 75% Example 54 Pd/HZSM-5 82% Example 55 Pd/H-β 88% Example 56 Pd/HMOR 88% Example 57 Pd/C 50% Example 58 Pd/ZrP 84%

It can be seen from Table 9 that when the raw material does not add any solvent, it is easier to realize the complete hydrogenation and hydrodeoxygenation of the raw material on the acidic carrier supported by metal A, and obtain a long-chain liquid state within the range of aviation kerosene with an ideal yield. alkanes.

Examples 59-71

1) In a fixed-bed reactor, see Table 10 for the effects of different hydrogen pressures, reaction temperatures, mass space velocities of reaction raw materials and catalysts, and hydrogen flow rates on the hydrodeoxygenation reaction. The starting material is the purified product A in Example 16, catalyst Pd/H-β.

Table 10. Effects of temperature, pressure, mass space velocity, and hydrogen flow rate on hydrodeoxygenation reaction activity

It can be seen from Table 10 that when the temperature is greater than 260°C, the mass space velocity is less than 1h ^-1 , the reaction pressure is greater than 6MPa, and the hydrogen flow rate is greater than 60mL/min, an ideal yield of long-chain liquid alkanes in the aviation kerosene or diesel range can be obtained .

Example 72

2) In a fixed bed reactor, the pressure in the reactor is 6.0MPa, the temperature is 260°C, and the hydrogen flow rate is 120mL/min. Aldol condensation products A and B (Example 40) that have been purified by vacuum distillation The phase chromatography pump is pumped into the reactor at 0.04mL/min, and the catalyst is Pd/H-β.

Table 11. Effect of different feed substrate hydrodeoxygenation reactivity

It can be seen from Table 11 that when the fixed bed feed is a mixed aldol condensation substrate, not only a solvent-free process is realized, but also an ideal alkane yield can be obtained.

Through the above examples, the detailed process of the preparation of a series of supported metal A/X type catalysts has been described in detail, and the impact of alkali catalysis on the aldol condensation reaction activity between lignocellulose-based furfurals and ketones (embodiment 1- 46), and discussed the hydrodeoxygenation reactivity of A/X-type bifunctional catalysts for lignocellulosic-based aviation kerosene precursors. Under the conditions given above (Examples 47-72), a single yield of 88% of C10 linear hydrocarbons or a combined yield of 90% of C10+C12 linear hydrocarbons (products C and D) were obtained. They can be used directly as a new type of liquid hydrocarbon fuel or added to existing aviation kerosene or diesel in a certain proportion.

Claims (7)

1. a preparation method of aviation kerosene or diesel oil range liquid alkane, characterized in that: 1) Lignocellulose-based furfural compounds and ketone compounds are used as raw materials, and oxygen-containing compound precursors with carbon chain lengths between 9 and 16 are prepared through alkali-catalyzed aldol condensation reactions; 2) Using a supported metal catalyst to directly hydrodeoxygenate the product obtained by aldol condensation, so as to obtain long-chain liquid alkanes in the aviation kerosene (or diesel) range with a carbon chain length between 9 and 16. 2. according to the preparation method described in claim 1, it is characterized in that: In step 1), the base catalyst can be a mineral base, an organic base or a solid base; The alkali catalysts include alkali metal hydroxides, alkali metal oxides, alkaline earth metal hydroxides or alkaline earth metal oxides, hydrotalcite compounds, KF/Al ₂ O ₃ , MgO-ZrO ₂ , organic amines , quaternary ammonium salt, basic molecular sieve, basic ion exchange resin or a mixture of two or more. 3. according to the preparation method described in claim 1, it is characterized in that: Lignocellulose-based furfural compounds are: one or more mixtures of furfural, 5-methylfurfural, chloromethylfurfural or 5-hydroxymethylfurfural; Lignocellulose-based ketones are: acetone, butanone, 2-pentanone, 2-heptanone, cyclopentanone, mesityl oxide, methyl isobutyl ketone (MIBK), sodium levulinate, acetylacetone One or a mixture of two or more of acid esters, etc. 4. according to the preparation method described in claim 1, it is characterized in that: In step 1), a batch tank reactor is used; the molar ratio of furfural compounds to ketones is 10:1 to 1:10, and unreacted raw materials can be removed from the reaction system by distillation or rectification and recycled ; The reaction temperature is 50-200° C., and the reaction time is 1-12 hours; the reaction can be carried out in liquid state without solvent. 5. according to the preparation method described in claim 1, it is characterized in that: In step 2), the supported metal bifunctional A/X type catalyst is used to directly hydrodeoxygenate the aldol condensation product; the active component A is one of Pt, Pd, Ru, Ir, Ni, Cu, Fe or Two or more, the carrier X is one or more of alumina, silicon oxide, silicon-aluminum composite carrier, molecular sieve (HZSM-5 type, Hβ type, HY type, HMOR type, etc.), activated carbon, metal phosphate, metal oxide a mixture of two or more; The supported metal catalyst is prepared by equal-volume impregnation. The soluble salt solution of A is added to the pre-formed carrier X for medium-volume impregnation according to the metering ratio. After standing for 6 hours, it is dried at 80°C, and then heated with hydrogen at 300-600°C. Reduction for 3 to 5 hours, pass through nitrogen passivation after the temperature drops to room temperature; the content of active metal in the catalyst is 1 to 10%. 6. according to the preparation method described in claim 1 or 5, it is characterized in that: In step 2), the hydrodeoxygenation catalytic reaction of the aldol condensation product can be realized under mild conditions. A fixed bed reactor is used, and no solvent is added to the reaction system; the conditions of the fixed bed reactor are: the temperature is between 150 and 400 ° C, The reaction pressure is between 0.1-20.0 MPa, the reactant/catalyst mass space velocity is 0.1-20.0 h ^-1 , and the molar ratio of H ₂ to substrate is 20-1500. 7. according to the preparation method described in claim 1, it is characterized in that: In step 1), the product of the aldol condensation reaction can be a solid product or a liquid product at room temperature; for the reaction in which the aldol condensation product is a solid, a method of mixing furfural compounds with two or more ketone compounds is used to ensure that the step 1) The product contains at least one product that is liquid at normal temperature; the liquid aldol condensation product is used to dissolve the solid aldol condensation product, so as to ensure that the obtained product is liquid at the use temperature.