Method for preparing suberic acid from 5-formyl furoic acid and malonic acid

Abstract

The invention discloses a method for preparing suberic acid from 5-formyl furoic acid and malonic acid. The preparation method comprises any one of the following steps 1)-4): 1) S1 and S5; 2) S1 and S6; 3) S1, S2 and S3; 4) S1, S2 and S4; the preparation method comprises the following steps: S1, carrying out condensation reaction on 5-formyl furoic acid and malonic acid in a solvent A to obtain an intermediate 1; s2, reacting the intermediate 1 with hydrogen under the action of a catalyst B to obtain an intermediate 2; s3, reacting the intermediate 2 with hydrogen under the action of a catalyst C to obtain suberic acid; s4, reacting the intermediate 2 with hydrogen under the action of acid and a catalyst D to obtain suberic acid; s5, reacting the intermediate 1 with hydrogen under the action of a catalyst C to obtain suberic acid; and S6, reacting the intermediate 1 with hydrogen under the action of acid and a catalyst D to obtain suberic acid. The raw materials used in the method are derived from biomass, H2 is used as a reducing agent, a heterogeneous catalyst is adopted, the reaction process is green, and byproducts harmful to the environment cannot be generated.

Description

Technical Field

[0001] The invention relates to a method for preparing suberic acid from 5-formylfuroic acid and malonic acid, and belongs to the field of preparation of chemical raw materials. Background Art

[0002] Suberic acid is an important polymer monomer and can be used to synthesize plastics, fibers and adhesives. At present, the main production process of suberic acid is that butadiene undergoes cyclodimerization, hydrogenation and oxidation reactions in sequence. In addition, suberic acid can be synthesized by carbonylation reaction of hexylene glycol and oxirane. However, these reactions require the use of a large amount of organic solvents, homogeneous catalysts that are difficult to recycle, and stoichiometric and expensive reagents. Therefore, the synthesis of suberic acid through the process of catalytic conversion using renewable biomass that exists in large quantities in nature as raw materials has attracted people's attention. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing suberic acid from 5-formyl furoic acid and malonic acid. The 5-formyl furoic acid and malonic acid raw materials used can be derived from renewable biomass, and the preparation process is environmentally friendly and green without pollution.

[0004] The preparation method of suberic acid provided by the present invention comprises any one of the following steps 1) to 4): 1) S1, S5; 2) S1, S6; 3) S1, S2, S3; 4) S1, S2, S4; S1, 5-formyl furoic acid and malonic acid are subjected to condensation reaction in solvent A to obtain intermediate 1; S2, under the action of catalyst B, the intermediate 1 is reacted with hydrogen to obtain intermediate 2; S3, under the action of catalyst C, the intermediate 2 and hydrogen are subjected to a hydrodeoxygenation reaction to obtain suberic acid; S4, under the action of acid and catalyst D, the intermediate 2 is subjected to a hydrodeoxygenation reaction with hydrogen to obtain suberic acid; S5. Under the action of catalyst C, the intermediate 1 is subjected to a hydrodeoxygenation reaction with hydrogen to obtain suberic acid; S6. Under the action of acid and catalyst D, the intermediate 1 is reacted with hydrogen through hydrodeoxygenation to obtain suberic acid.

[0005] Malonic acid has been reported to be identified as one of the 30 most valuable biomass-based chemicals. Bio-based malonic acid can be produced by fermentation of sugars; 5-hydroxymethylfurfural can undergo selective oxidation to produce 5-formylfurfural.

[0006] In the preparation method of the present invention, in step S1, the solvent A is an alkaline solvent, selected from at least one of pyridine, piperidine, pyrrole and pyrrolidine, preferably pyridine; The mass ratio of the solvent A to the 5-formyl furoic acid is 100%-1000%; The molar ratio of malonic acid to 5-formyl furoic acid is 200%-100%; The reaction temperature of the condensation reaction is 60-120° C., and the reaction time is 0.5-24 h.

[0007] In the preparation method of the present invention, in step S2, the catalyst B is a metal supported by a carrier, wherein the carrier is at least one of TiO2, SiO2, ZrO2 and activated carbon, and the metal is at least one of Pd, Pt, Rh and Ru, and the loading amount thereof is 0.5-5%, preferably Pd / activated carbon; The mass ratio of the catalyst B to the intermediate 1 is 10-200%; The reaction temperature of the hydrogenation reaction is 20-60°C, the reaction time is 0.5-12 h, and the H2 pressure is 0.5-4 MPa.

[0008] In the preparation method of the present invention, in steps S3 and S5, the catalyst C is at least one of a metal-supported mixed catalyst and a carrier-supported oxide mixed catalyst, and a metal-and-oxide catalyst co-supported by MoO3 and an acidic carrier; The acidic carrier is at least one of HZSM-5, Hβ, HY molecular sieve and sulfonic acid resin, the carrier is at least one of TiO2, SiO2, ZrO2 and activated carbon, the metal is at least one of Pd, Pt, Rh and Ru, and the loading amount is 1-15%, the oxide is ReO x and / or MoO x , with a loading of 1-15%, preferably a mechanically mixed catalyst of Pd / HZSM-5 and MoOx / TiO2.

[0009] In the preparation method of the present invention, in steps S4 and S6, the catalyst D is at least one of a mixed catalyst of a metal supported by a carrier and an oxide supported by a carrier, and a metal and oxide catalyst co-supported by MoO3 and a carrier; The carrier is at least one of TiO2, SiO2, ZrO2 and activated carbon, the metal is at least one of Pd, Pt, Rh and Ru, and the loading amount is 1-15%, and the oxide is ReO x and / or MoO x , with a loading of 1-15%.

[0010] In the preparation method of the present invention, in steps S4 and S6, the acid is at least one of hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, methanesulfonic acid and p-toluenesulfonic acid, preferably hydrochloric acid; The molar ratio of the acid to the intermediate 1 or the intermediate 2 is 30-500%, preferably 100%.

[0011] In the preparation method of the present invention, in steps S3 and S4, the mass ratio of the catalyst C and the catalyst D to the intermediate 2 is 50-500%; In steps S5 and S6, the mass ratio of the catalyst C and the catalyst D to the intermediate 1 is 50-500%.

[0012] In the preparation method of the present invention, in steps S3-S6, the reaction temperature of the hydrodeoxygenation reaction is 190-240°C, the reaction time is 2-48 h, and the H2 pressure is 1-5 MPa; The reaction solvent of the hydrodeoxygenation reaction can be H2O, methanol or ethanol, preferably H2O.

[0013] Compared with the prior art, the present invention has the following advantages: The raw materials used in the present invention are derived from biomass, H2 is used as a reducing agent, and a heterogeneous catalyst is adopted. The reaction process is green and no by-products harmful to the environment are generated. DETAILED DESCRIPTION

[0014] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments.

[0015] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0016] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0017] In the following examples, the preparation of the specific catalyst is as follows: 1. Preparation of supported Pd / HZSM-5 catalyst The preparation of a Pd / HZSM-5 catalyst with a loading of 1% is taken as an example for non-limiting description.

[0018] Add 1 mL of [Pd(NH3)4](NO3)2 aqueous solution (Pd concentration is 10 mg / mL) and 10 mL of deionized water to a 100 mL round-bottom flask with a stirrer and stir evenly. Then add 1 g of HZSM-5 to the solution and stir at room temperature at 600 rpm for 6 h. After evaporating the water, dry the solid sample in an oven at 110 °C for 12 h to obtain a catalyst precursor. Transfer the catalyst precursor to a quartz tube and place it in a flowing air tube at 500 °C.o C was calcined for 3 h, and then calcined at 300 °C for 2 h in 20% H2 / N2 to obtain a supported 1% Pd / HZSM-5 catalyst.

[0019] 2. Supported MoO x Preparation of TiO2 catalyst The Mo loading amount was 5% MoO x The preparation of / TiO2 catalyst is given as an example for non-limiting explanation.

[0020] Add 2.5 mL of (NH4)6Mo7O to a 100 mL round-bottom flask with a stirrer. 24 Aqueous solution (Mo concentration is 20 mg / mL) and 10 mL of deionized water were mixed and stirred evenly. Then 1 g of TiO2 was added to the solution and stirred at room temperature at 600 rpm for 6 h. After evaporating the water, the solid sample was dried in an oven at 110 °C for 12 h to obtain a catalyst precursor. The catalyst precursor was transferred to a quartz tube and heated at 500 °C in flowing air. o C was calcined for 3 h to obtain supported 5% MoO x / TiO2 catalyst.

[0021] 3. Loaded Pd-MoO x Preparation of HZSM-5 catalyst Pd-MoO with Pd and Mo loadings of 1% and 5%, respectively x The preparation of 2-HZSM-5 catalyst is taken as an example for non-limiting explanation.

[0022] Add 2.5 mL of (NH4)6Mo7O to a 100 mL round-bottom flask with a stirrer. 24 1 mL of aqueous solution (Mo concentration is 20 mg / mL), 1 mL of [Pd(NH3)4](NO3)2 aqueous solution (Pd concentration is 10 mg / mL) and 10 mL of deionized water were stirred evenly. Then 1 g of HZSM-5 was added to the solution and stirred at room temperature for 6 h at a speed of 600 rpm. After evaporating the water, the solid sample was dried in an oven at 110 ° C for 12 h to obtain a catalyst precursor. The catalyst precursor was transferred to a quartz tube and heated at 500 ° C in flowing air. o C was calcined for 3 h, and then calcined at 300 °C for 2 h in 20% H2 / N2 to obtain supported Pd-MoO x / HZSM-5 catalyst, in which Pd and MoO x The loading amounts were 1% and 5%, respectively.

[0023] 4. Preparation of supported Pd / activated carbon catalyst The preparation of Pd / activated carbon catalysts with a Pd loading of 2% is taken as an example for non-limiting description.

[0024] Add 2 mL of [Pd(NH3)4](NO3)2 aqueous solution (Pd concentration is 10 mg / mL) and 10 mL of deionized water to a 100 mL round-bottom flask with a stirrer and stir evenly. Then add 1 g of activated carbon to the solution and stir at room temperature at 600 rpm for 6 hours. After evaporating the water, dry the solid sample in an oven at 110°C for 12 hours to obtain a catalyst precursor. The catalyst precursor is transferred to a quartz tube and calcined at 300°C in 20% H2 / N2 for 2 hours to obtain a loaded Pd / activated carbon catalyst, in which the Pd loading is 2%.

[0025] In the following examples, the yields of different products and the conversion rates of different raw materials were determined as follows: The concentrations of reactants and products were determined by high performance liquid chromatography (HPLC, Shimadzu LC-20A) with a Shodex Sugar-SH1011 column, a differential refractometer detector, a 0.1 wt % sulfuric acid solution as the mobile phase, and a flow rate of 0.8 mL / min.

[0026] Example: 1. 5-Formyl furoic acid and malonic acid are converted into intermediate 1 Pyridine solvent is used as an example for non-limiting explanation.

[0027] In a 50 mL reactor, add 2.9 g of 5-formyl furoic acid, 2.6 g of malonic acid, and 21 mL of pyridine, the mass ratio of pyridine to 5-formyl furoic acid is 0.14, and the molar ratio of malonic acid to 5-formyl furoic acid is 1.2. After sealing the reactor, place the reactor in a heating furnace and heat it to 80 o C, control the stirring rate of the reactor to 600rpm. After 8h, stop heating and cool to room temperature. The reaction solution is fixed to 1L, and the reaction product is analyzed by high performance liquid chromatography. The substrate 5-formyl furoic acid and malonic acid are completely converted, and the yield of intermediate 1 reaches 98%. Then filter, separate and acidify to obtain intermediate 1 brown powder for the next step of reaction.

[0028] 2. Intermediate 1 is converted into intermediate 2 A Pd / activated carbon catalyst (Pd particle size of 2.7 nm) with a Pd loading of 2% is used as an example for non-limiting explanation. In a 50mL autoclave, 0.2g of intermediate 1, 20mL of deionized water, and 60mg of Pd / activated carbon catalyst were added in sequence. After the reactor was sealed, 1MPa of H2 was flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 was filled in, and the reactor was placed in a heating furnace and heated to 40°C. The stirring rate of the reactor was controlled to be 600rpm. After 3h, the heating was stopped, and the H2 in the reactor was released after cooling to room temperature. The reaction solution and the catalyst were separated by vacuum filtration. The filtrate was fixed to 100mL, and the reaction product was analyzed by high performance liquid chromatography. The conversion rate of intermediate 1 was 100%, and the yield of intermediate 2 was 99%. The obtained intermediate 2 solution was directly used for the next reaction.

[0029] 3. Intermediate 2 is converted into suberic acid The Pd loading is 1% for Pd / HZSM-5 and the Mo loading is 5% for MoO x / TiO2 mixed catalyst is used as an example for non-limiting explanation In a 50 mL autoclave, 20 mL of the hydrogenation reaction solution of intermediate 1 (i.e., intermediate 2), 0.2 g of Pd / HZSM-5 catalyst, and 0.2 g of MoO x / TiO2 catalyst, wherein the mass ratio of the catalyst to the intermediate 1 is 2. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 2 is 100%, and the yield of suberic acid is 90%.

[0030] 4. Intermediate 2 is converted into suberic acid The Pd loading is 1% of Pd / TiO2, the Mo loading is 5% of MoO x / TiO2 mixed catalyst and hydrochloric acid are used as an example for non-limiting explanation In a 50mL autoclave, 20mL of the hydrogenation reaction solution of intermediate 1 (i.e., intermediate 2), 89uL of concentrated hydrochloric acid, 0.2g of Pd / TiO2 catalyst, and 0.2g of MoO x / TiO2 catalyst, wherein the mass ratio of the catalyst to the intermediate 1 is 2, and the molar ratio of concentrated hydrochloric acid to the intermediate 2 is 1. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 2 is 100%, and the yield of suberic acid is 88%.

[0031] 5. Intermediate 2 is converted into suberic acid Pd-MoO with a Pd loading of 1% and a Mo loading of 5% x / HZSM-5 catalyst is used as an example for non-limiting explanation In a 50 mL autoclave, 20 mL of the hydrogenation reaction solution of intermediate 1 (i.e. intermediate 2), 0.2 g of Pd-MoO x / HZSM-5 catalyst, wherein the mass ratio of the catalyst to the intermediate 2 is 1. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 2 is 100%, and the yield of suberic acid is 81%.

[0032] 6. Intermediate 2 is converted into suberic acid Pd-MoO with a Pd loading of 1% and a Mo loading of 5% x / TiO2 catalyst and hydrochloric acid are used as non-limiting examples In a 50mL autoclave, 20mL of the hydrogenation reaction solution of intermediate 1 (i.e., intermediate 2), 89uL of concentrated hydrochloric acid, 0.2g of Pd-MoO x / TiO2 catalyst, wherein the mass ratio of the catalyst to the intermediate is 1, and the molar ratio of concentrated hydrochloric acid to intermediate 2 is 1. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 2 is 100%, and the yield of suberic acid is 82%.

[0033] 7. Intermediate 1 is directly converted into suberic acid The Pd loading is 1% for Pd / HZSM-5 and the Mo loading is 5% for MoO x / TiO2 mixed catalyst is used as an example for non-limiting explanation In a 50 mL autoclave, 0.2 g of intermediate 1, 20 mL of deionized water, 0.2 g of Pd / HZSM-5 catalyst and 0.2 g of MoO were added in sequence. x / TiO2 catalyst, wherein the mass ratio of the catalyst to the intermediate 1 is 2. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 1 is 100%, and the yield of suberic acid is 78%.

[0034] 8. Intermediate 1 is directly converted into suberic acid The Pd loading is 1% of Pd / activated carbon, the Mo loading is 5% of MoO x / TiO2 mixed catalyst and hydrochloric acid are used as an example for non-limiting explanation In a 50 mL autoclave, 0.2 g of intermediate 1, 20 mL of deionized water, 89 uL of concentrated hydrochloric acid, 0.2 g of Pd / activated carbon catalyst and 0.2 g of MoO were added in sequence. x / TiO2 catalyst, wherein the mass ratio of the catalyst to the intermediate 1 is 2, and the molar ratio of concentrated hydrochloric acid to the intermediate 1 is 1. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 1 is 100%, and the yield of suberic acid is 80%.

[0035] 9. Intermediate 1 is directly converted into suberic acid Pd-MoO with a Pd loading of 1% and a Mo loading of 5% x / HZSM-5 catalyst is used as an example for non-limiting explanation In a 50 mL autoclave, 0.2 g of intermediate 1, 20 mL of deionized water, and 0.2 g of Pd-MoO x / HZSM-5 catalyst, wherein the mass ratio of the catalyst to the intermediate 1 is 1. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 1 is 100%, and the yield of suberic acid is 74%.

[0036] 10. Intermediate 1 is directly converted into suberic acid Pd-MoO with a Pd loading of 1% and a Mo loading of 5% x / TiO2 catalyst and hydrochloric acid are used as non-limiting examples In a 50mL autoclave, 0.2g of intermediate 1, 20mL of deionized water, 89uL of concentrated hydrochloric acid, 0.2g of Pd-MoO x / TiO2 catalyst, wherein the mass ratio of the catalyst to the intermediate 1 is 1, and the molar ratio of concentrated hydrochloric acid to the intermediate 1 is 1. After the reactor is sealed, 1MPa of H2 is flushed in to replace the air in the reactor. After repeated inflation and deflation three times, 2MPa of H2 is filled in, and the reactor is placed in a heating furnace and heated to 220°C, and the stirring rate of the reactor is controlled to be 600rpm. After 16h, the heating is stopped, and the reactor is cooled to room temperature to release the H2 in the reactor. The reaction solution and the catalyst are separated by vacuum filtration. The filtrate is fixed to 100mL, and the reaction product is analyzed by high performance liquid chromatography. The conversion rate of intermediate 1 is 100%, and the yield of suberic acid is 76%.

[0037] The reaction effects of the above embodiment and other different reaction conditions are shown in Table 1.

[0038] Table 1 Conditions and reaction effects under different conditions

[0039] According to the above results, with 5-formyl furoic acid and malonic acid as raw materials, after two or three steps of reaction, the total yield of suberic acid is 55-90%. The method of the invention is an effective method for synthesizing suberic acid.

Claims

1. A method for preparing suberic acid, comprising any one of the following steps 1) to 4): 1) S1, S5; 2) S1, S6; 3) S1, S2, S3; 4) S1, S2, S4; S1, 5-formyl furoic acid and malonic acid are subjected to condensation reaction in solvent A to obtain intermediate 1; S2, under the action of catalyst B, the intermediate 1 is reacted with hydrogen to obtain intermediate 2; S3, under the action of catalyst C, the intermediate 2 and hydrogen are subjected to a hydrodeoxygenation reaction to obtain suberic acid; S4, under the action of acid and catalyst D, the intermediate 2 is subjected to a hydrodeoxygenation reaction with hydrogen to obtain suberic acid; S5. Under the action of catalyst C, the intermediate 1 is subjected to a hydrodeoxygenation reaction with hydrogen to obtain suberic acid; S6. Under the action of acid and catalyst D, the intermediate 1 is reacted with hydrogen through hydrodeoxygenation to obtain suberic acid.

2. The preparation method according to claim 1, characterized in that: In step S1, the solvent A is an alkaline solvent selected from at least one of pyridine, piperidine, pyrrole and pyrrolidine; The mass ratio of the solvent A to the 5-formyl furoic acid is 100%-1000%; The molar ratio of malonic acid to 5-formyl furoic acid is 200%-100%; The reaction temperature of the condensation reaction is 60-120° C., and the reaction time is 0.5-24 h.

3. The preparation method according to claim 1 or 2, characterized in that: In step S2, the catalyst B is a metal supported by a carrier, wherein the carrier is at least one of TiO2, SiO2, ZrO2 and activated carbon, and the metal is at least one of Pd, Pt, Rh and Ru, and the loading amount thereof is 0.5-5%; The mass ratio of the catalyst B to the intermediate 1 is 10-200%; The reaction temperature of the hydrogenation reaction is 20-60°C, the reaction time is 0.5-12 h, and the H2 pressure is 0.5-4 MPa.

4. The preparation method according to any one of claims 1 to 3, characterized in that: In steps S3 and S5, the catalyst C is at least one of a metal-supported mixed catalyst and a carrier-supported oxide mixed catalyst, and a metal-and-oxide catalyst co-supported by MoO3 and an acidic carrier; The acidic carrier is at least one of HZSM-5, Hβ, HY molecular sieve and sulfonic acid resin, the carrier is at least one of TiO2, SiO2, ZrO2 and activated carbon, the metal is at least one of Pd, Pt, Rh and Ru, and the loading amount is 1-15%, the oxide is ReO x and / or MoO x , with a loading of 1-15%.

5. The preparation method according to any one of claims 1 to 4, characterized in that: In steps S4 and S6, the catalyst D is at least one of a carrier-supported metal and a carrier-supported oxide mixed catalyst, and a metal and oxide catalyst co-supported by MoO3 and a carrier; The carrier is at least one of TiO2, SiO2, ZrO2 and activated carbon, the metal is at least one of Pd, Pt, Rh and Ru, and the loading amount is 1-15%, and the oxide is ReO x and / or MoO x , with a loading of 1-15%.

6. The preparation method according to any one of claims 1 to 5, characterized in that: In steps S4 and S6, the acid is at least one of hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, methanesulfonic acid and p-toluenesulfonic acid; The molar ratio of the acid to the intermediate 1 or the intermediate 2 is 30-500%.

7. The preparation method according to any one of claims 1 to 6, characterized in that: In steps S3 and S4, the mass ratio of the catalyst C and the catalyst D to the intermediate 2 is 50-500%; In steps S5 and S6, the mass ratio of the catalyst C and the catalyst D to the intermediate 1 is 50-500%.

8. The preparation method according to any one of claims 1 to 7, characterized in that: In steps S3-S6, the reaction temperature of the hydrodeoxygenation reaction is 190-240°C, the reaction time is 2-48 h, and the H2 pressure is 1-5 MPa; The reaction solvent of the hydrodeoxygenation reaction is H2O, methanol or ethanol.

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