A solid heterogeneous catalyst for conversion of carbohydrate compounds and preparation method thereof

Abstract

The present invention relates to a multifunctional solid heterogeneous catalyst, its preparation method, and application. More specifically, it relates to a multifunctional solid heterogeneous catalyst for the direct conversion of saccharide compounds to produce hexanedione compounds, and its preparation method. The multifunctional solid heterogeneous catalyst comprises a metal component and an acidic organic ligand polymer, wherein the metal component is one or more of Pd, Ni, Mo, Cu, or Fe, and the acidic organic ligand polymer is a polymer having a large specific surface area and a multi-level pore structure generated by solvent thermal copolymerization of a vinyl-functionalized phosphine ligand monomer, and then post-modified. The metal component and the acidic sites can be highly dispersed on the carrier, allowing dehydration and hydrogenation reactions to be carried out in series on the same heterogeneous catalyst. As a result, the multifunctional solid heterogeneous catalyst of the present invention has excellent catalytic reaction performance and stability, and the catalyst is easily separated from the reactants and products, thus having broad industrial application prospects.

Description

Technical Field

[0001] The invention relates to a multifunctional solid heterogeneous catalyst for the direct conversion of saccharide compounds to produce hexanedione compounds and a preparation method thereof, belonging to the technical field of heterogeneous catalysis. Background Art

[0002] Biomass energy is the only renewable carbon resource that can replace fossil energy and be converted into liquid and gaseous fuels, as well as other chemical feedstocks or products. Converting biomass into high-value-added fine chemicals has become a top priority for both academia and industry, not only to create diversity but also to obtain chemicals with similar or superior properties to fossil-derived chemicals. In this context, hexanediones, including 2,5-hexanedione (HD) and 1-hydroxy-2,5-hexanedione (HHD), represent an attractive class of platform compounds. They are high-value-added intermediates for use as surfactants, polymers, and solvents. Numerous high-value-added derivatives can be produced from hexanediones, such as polyols, amines, tetrahydrofuran, and lactones. Over the past decade, extensive research has focused on the catalytic conversion of 5-hydroxymethylfurfural (a hexose-derived platform compound) into hexanediones. 5-Hydroxymethylfurfural can be produced by dehydration of glucose and fructose. After purification, 5-Hydroxymethylfurfural can be derived into hexanediones. Currently, limited research has been conducted on the direct conversion of hexanediones from sugars. Furthermore, the direct conversion of sugars to hexanediones primarily occurs in homogeneous reactions. The development of cost-effective catalytic systems for the direct production of hexanediones from sugars using highly active, multifunctional heterogeneous catalysts without the addition of homogeneous acid catalysts is a promising future for biorefining processes, but remains a significant challenge. Based on our understanding of the reaction process, the direct conversion of sugars to hexanediones requires a multifunctional catalyst possessing both acidic and metal active sites.

[0003] In summary, the plan is to leverage the ease of modification of porous organic polymers to prepare multifunctional solid heterogeneous catalysts through post-modification. This simplifies the reaction process, avoids the separation and purification of platform compounds, and directly completes the conversion of sugars to the final product. The development of efficient, recyclable, green, and clean catalysts is a major research direction in this field. Summary of the Invention

[0004] In order to solve the above problems, the object of the present invention is to provide a multifunctional solid heterogeneous catalyst for the direct conversion of saccharide compounds to hexanedione compounds and a preparation method thereof.

[0005] To this end, the present invention provides a multifunctional solid heterogeneous catalyst for the direct conversion of saccharide compounds to hexanedione compounds, characterized in that the multifunctional solid heterogeneous catalyst comprises a metal component and an acidic organic ligand polymer, wherein the metal component is one or more of Pd, Ni, Mo, Cu, or Fe, and the acidic organic ligand polymer is a polymer having a large specific surface area and a multi-level pore structure generated by solvent thermal polymerization of a vinyl-functionalized phosphine ligand monomer, followed by post-modification. The post-modification comprises reacting the P atom with 1,3-propane sultone to quaternize the P atom, converting it from a trivalent phosphine to a pentavalent phosphine, thereby enabling acid loading. The vinyl-functionalized monomer is a phosphine ligand with strong coordination ability. The metal component forms a coordination bond with the P atom in the acidic organic ligand polymer backbone, resulting in a highly dispersed and stable presence on the acidic organic ligand polymer support.

[0006] In a preferred embodiment, the vinyl-functionalized phosphine ligand monomer is selected from one or more of the following:

[0007]

[0008] In a preferred embodiment, the metal component accounts for 0.01-10.0%, preferably 0.1-5.0%, of the total weight of the multifunctional solid heterogeneous catalyst.

[0009] In a preferred embodiment, the specific surface area of ​​the acidic organic ligand polymer is 100-3000 m 2 / g, pore volume of 0.1-5.0cm 3 / g, pore size distribution is 0.1-100.0nm.

[0010] In a preferred embodiment, the preparation method of the multifunctional solid heterogeneous catalyst comprises the following preparation steps: a) adding a free radical initiator to a solvent containing a vinyl functionalized phosphine ligand monomer at 273-473K (preferably 293-333K) and an inert gas protective atmosphere, and stirring for 0.5-100 (preferably 0.5-12) hours; b) placing the solution of step a) in a hydrothermal autoclave at 333-473K (preferably 353-393K) and an inert gas protective atmosphere for 0.5-100 (preferably 24-48) hours to carry out a solvent thermal polymerization reaction; c) ) after the reaction is completed, the solvent is removed in vacuo at a temperature of 273-473K (preferably 333-393K) to obtain the organic ligand polymer; d) placing the organic ligand polymer in a solvent containing 1,3-propane sultone, stirring for 0.5-100 (preferably 24-48) hours at 273-473K (preferably 363-393K) under an inert gas protective atmosphere, and then dropwise adding a solvent containing an acid at a temperature of 223-373K (preferably 253-273K), stirring for 0.5-100 (preferably 24-48) hours under an inert gas protective atmosphere, filtering, and washing with a solvent. Then, the mixture is dried at 323-423K (preferably 333-353K) to obtain an acidic organic coordination polymer; e) the acidic organic ligand polymer is placed in a solvent containing an active metal component, stirred at 273-473K (preferably 298-333K) and an inert gas protective atmosphere for 0.5-100 (preferably 24-48) hours, and then dried at 313-423K (preferably 333-373K) to obtain the multifunctional solid heterogeneous catalyst.

[0011] In a preferred embodiment, the solvent used in steps a), d) and e) of the catalyst preparation method is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water; the free radical initiator used in step a) is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile; the acid used in step d) is one or more of trifluoromethanesulfonic acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, sulfuric acid, silicotungstic acid, trifluoroacetic acid, and p-toluenesulfonic acid, and the amount of acid loaded is 0.1-2.4 mmol / g, preferably 1.2-1.8 mmol / g.

[0012] In a preferred embodiment, the weight ratio of the free radical initiator to the phosphine ligand monomer in the catalyst preparation method is 1:500-1:5 (preferably 1:100-1:25).

[0013] In a preferred embodiment, the molar ratio of the 1,3-propane sultone to the phosphine ligand monomer in the catalyst preparation method is 1:500-5:1 (preferably 1:10-1:2).

[0014] In a preferred embodiment, the molar ratio of the acid to the phosphine ligand monomer in the catalyst preparation method is 1:500-5:1 (preferably 1:10-1:2).

[0015] In a preferred embodiment, the multifunctional solid heterogeneous catalyst is used to cause the carbohydrate compound raw material and H2 to carry out the direct conversion reaction in a tank reactor in the presence of the multifunctional solid heterogeneous catalyst, wherein the reaction temperature is 293-573K (preferably 373-433K), the reaction pressure is 0.05-20.0MPa (preferably 0.5-6.0MPa), the molar ratio of the carbohydrate compound raw material to H2 is 1:1-1:200 (preferably 1:10-1:50), and the molar ratio of the carbohydrate compound to the metal component in the catalyst is 100:1-3000:1 (preferably 200:1-1000:1).

[0016] In a preferred embodiment, the inert gas protective atmosphere is one or more of nitrogen, argon, neon, and helium.

[0017] In a preferred embodiment, the carbohydrate compound is selected from one or more of monosaccharides, disaccharides or polysaccharides, wherein the monosaccharide is selected from: fructopyranose, glucose, galactose; the disaccharide is selected from: sucrose, lactose, maltose; the polysaccharide is selected from: cellulose, starch.

[0018] The beneficial effects of the present invention include but are not limited to the following aspects:

[0019] Compared with existing catalysts for direct conversion of carbohydrates, the solid heterogeneous catalyst of the present invention has a simple catalyst preparation method; the metal component and the P atoms in the polymer carrier are stably present on the carrier due to coordination; and the acidic sites are anchored to the carrier by the quaternized phosphinated P atoms in the polymer carrier. The polymer carrier has a large specific surface area and a multi-level pore structure, allowing the metal component and the acidic sites to be highly dispersed on the carrier, thereby endowing the multifunctional solid heterogeneous catalyst of the present invention with excellent catalytic reaction performance, enabling the direct conversion of carbohydrates to produce hexanedione compounds. Furthermore, the catalyst of the present invention is a heterogeneous catalyst on a macroscopic scale, and therefore has significant advantages in terms of recycling and separation from reactants and products, and has broad prospects for industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic diagram of the synthesis route of the multifunctional solid heterogeneous catalyst of the present invention.

[0021] Figure 2 It is a graph showing the N2 adsorption-desorption isotherm and pore size distribution curve of the multifunctional solid heterogeneous catalyst of the present invention. DETAILED DESCRIPTION

[0022] To better illustrate the preparation method of the catalyst of the present invention and its application in the direct conversion of sugars to hexanedione compounds, the following examples illustrate the preparation of several catalyst samples and their application in the reaction process. However, the present invention is not limited to these examples. Unless otherwise specified, "percentages" used in this application are based on weight.

[0023] Example 1

[0024] At 298K under an argon atmosphere, 10.0g of tri(4-vinylphenyl)phosphine ligand was dissolved in 100ml of tetrahydrofuran solvent. 0.25g of azobisisobutyronitrile (a free radical initiator) was added to the solution and stirred for 0.5 hours. The stirred solution was transferred to a hydrothermal autoclave and solvothermally polymerized at 383K under an argon atmosphere for 24 hours. After cooling to room temperature, the solvent was removed in vacuo at 333K to obtain a porous organic polymer containing phosphine.

[0025] At 373K and an argon protective atmosphere, 0.17 grams of 1,3-propane sultone was weighed and dissolved in 40 ml of toluene solvent, 1.0 grams of the above-prepared porous organic polymer containing phosphine was added, and stirred for 24 hours. Subsequently, at a temperature of 273K, 10 ml of a toluene solution containing 0.21 grams of trifluoromethanesulfonic acid was added dropwise and stirred for 24 hours. Filtered and washed 3 times with toluene solvent. At 353K, the solvent was vacuum removed to obtain an acidic organic ligand polymer. At 298K and an argon protective atmosphere, 0.0105 grams of palladium acetate was weighed and dissolved in 40 ml of tetrahydrofuran solvent, 1.0 grams of the above-prepared acidic porous organic polymer was added, stirred for 24 hours, and at 353K, the solvent was vacuum removed to obtain a multifunctional solid heterogeneous catalyst loaded with 0.5 wt% metal components and loaded with 1.6 mmol / g acid. The schematic diagram of the solid heterogeneous catalyst synthesis route of the present invention is shown in Figure 1 The N2 adsorption-desorption isotherm and pore size distribution curve of the solid heterogeneous catalyst of the present invention are shown in FIG. Figure 2 The results showed that the specific surface area of ​​the catalyst was 823m 2 / g, pore volume is 1.637cm 3 / g, micropore volume 0.126cm 3 / g, mesopore volume 1.511cm 3 / g.

[0026] 0.030 g of the solid heterogeneous catalyst prepared above was charged into an autoclave reactor, followed by 0.1 g of fructopyranose and 15 ml of tetrahydrofuran solvent. After displacing the autoclave atmosphere three times with 1 MPa of H₂, the reactor was sealed and filled with H₂ to a pressure of 1 MPa. The temperature was slowly raised to 120°C using a temperature controller and the reaction was continued for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed by gas chromatography using an HP-7890N equipped with an HP-5 capillary column and an FID detector, yielding 35% hexanedione compounds, including 15% 2,5-hexanedione and 20% 1-hydroxy-2,5-hexanedione.

[0027] Example 2

[0028] In Example 2, except that 0.13 g of hydrochloric acid was weighed instead of 0.21 g of trifluoromethanesulfonic acid, the rest of the catalyst preparation process was the same as that of Example 1, and the acid loading was 1.6 mmol / g.

[0029] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 15%, of which the yield of 2,5-hexanedione was 12% and the yield of 1-hydroxy-2,5-hexanedione was 3%.

[0030] Example 3

[0031] In Example 3, except that 0.13 g of phosphoric acid was weighed instead of 0.21 g of trifluoromethanesulfonic acid, the rest of the catalyst preparation process was the same as that of Example 1, and the acid loading was 1.6 mmol / g.

[0032] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 18%, of which the yield of 2,5-hexanedione was 16% and the yield of 1-hydroxy-2,5-hexanedione was 2%.

[0033] Example 4

[0034] In Example 4, except that 0.015 g of nickel acetate was weighed instead of 0.0105 g of palladium acetate, the rest of the catalyst preparation process was the same as that of Example 1, and 0.5 wt% of the metal component was loaded.

[0035] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 23%, of which the yield of 2,5-hexanedione was 12% and the yield of 1-hydroxy-2,5-hexanedione was 11%.

[0036] Example 5

[0037] In Example 5, except that 0.012 g of molybdenum acetate was weighed instead of 0.0105 g of palladium acetate, the rest of the catalyst preparation process was the same as that of Example 1, and 0.5 wt % of the metal component was loaded.

[0038] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 25%, of which the yield of 2,5-hexanedione was 10% and the yield of 1-hydroxy-2,5-hexanedione was 15%.

[0039] Example 6

[0040] In Example 6, the polymer synthesis process was the same as that of Example 1 except that dichloromethane was used as the solvent instead of tetrahydrofuran. The rest of the catalyst preparation process was the same as that of Example 1.

[0041] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 32%, of which the yield of 2,5-hexanedione was 13% and the yield of 1-hydroxy-2,5-hexanedione was 19%.

[0042] Example 7

[0043] In Example 7, the polymer synthesis process was the same as that of Example 1 except that the stirring was performed for 12 hours instead of 0.5 hours. The rest of the catalyst preparation process was the same as that of Example 1.

[0044] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 34%, of which the yield of 2,5-hexanedione was 12% and the yield of 1-hydroxy-2,5-hexanedione was 22%.

[0045] Example 8

[0046] In Example 8, the catalyst preparation process was the same as that in Example 1, except that 0.25 g of dibenzoyl peroxide was used as the free radical initiator instead of 0.25 g of azobisisobutyronitrile.

[0047] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 34%, of which the yield of 2,5-hexanedione was 13% and the yield of 1-hydroxy-2,5-hexanedione was 21%.

[0048] Example 9

[0049] In Example 9, the catalyst preparation process was the same as that in Example 1, except that 0.1 g of azobisisobutyronitrile as a free radical initiator was weighed instead of 0.25 g of azobisisobutyronitrile.

[0050] Catalyst Evaluation The reaction process was the same as that in Example 1. The yield of the reactant hexanedione compounds was 30%, of which the yield of 2,5-hexanedione was 12% and the yield of 1-hydroxy-2,5-hexanedione was 18%.

[0051] Example 10

[0052] In Example 10, the catalyst preparation process is the same as that in Example 1.

[0053] In Example 10, except that 0.1 g of glucose was weighed instead of 0.1 g of fructopyranose, the other catalyst evaluation procedures were the same as in Example 1. The yield of hexanedione compounds was 29%, of which the yield of 2,5-hexanedione was 14% and the yield of 1-hydroxy-2,5-hexanedione was 15%.

[0054] Example 11

[0055] In Example 11, the catalyst preparation process is the same as that of Example 1.

[0056] In Example 11, except that 0.1 g of sucrose was weighed instead of 0.1 g of fructopyranose, the other catalyst evaluation procedures were the same as in Example 1. The yield of hexanedione compounds was 24%, of which the yield of 2,5-hexanedione was 9% and the yield of 1-hydroxy-2,5-hexanedione was 15%.

[0057] Example 12

[0058] In Example 12, the catalyst preparation process is the same as that of Example 1.

[0059] In Example 12, except that 0.1 g of cellulose was used instead of 0.1 g of fructopyranose, the other catalyst evaluation procedures were the same as in Example 1. The yield of hexanedione compounds was 21%, of which the yield of 2,5-hexanedione was 8% and the yield of 1-hydroxy-2,5-hexanedione was 13%.

[0060] Comparative Example 1

[0061] The catalyst preparation process is the same as that in Example 1, except that 0.0130 g of ruthenium chloride is used instead of 0.0105 g of palladium acetate in the catalyst preparation. The metal loading is 0.5 wt %.

[0062] 0.030 g of the solid heterogeneous catalyst prepared above was charged into an autoclave reactor, followed by 0.10 g of fructopyranose and 15 ml of tetrahydrofuran. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to the autoclave system, maintaining a pressure of 1 MPa. The temperature was slowly raised to 120°C using a temperature controller and the reaction was continued for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed by gas chromatography using an HP-7890N equipped with an HP-5 capillary column and an FID detector, with the addition of dodecane as an internal standard. The reaction yielded 3% hexanedione compounds, 1% 2,5-hexanedione, and 2% 1-hydroxy-2,5-hexanedione.

[0063] Comparative Example 2

[0064] The catalyst preparation process is the same as that in Example 1, except that 0.0083 g of iridium chloride is used instead of 0.0105 g of palladium acetate in the catalyst preparation. The metal loading is 0.5 wt %.

[0065] 0.030 g of the solid heterogeneous catalyst prepared above was charged into an autoclave reactor, followed by 0.10 g of fructopyranose and 15 ml of tetrahydrofuran. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to the autoclave system, maintaining a pressure of 1 MPa. The temperature was slowly raised to 120°C using a temperature controller and the reaction was continued for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed by gas chromatography using an HP-7890N equipped with an HP-5 capillary column and an FID detector, with the addition of dodecane as an internal standard. The reaction yields were 4% for hexanedione compounds, 2% for 2,5-hexanedione, and 2% for 1-hydroxy-2,5-hexanedione.

[0066] Comparative Example 3

[0067] The preparation process of the catalyst is the same as that of Example 1, except that the catalyst was not modified by quaternary phosphine and acid was not loaded during the preparation process. The metal loading was 0.5 wt %.

[0068] 0.030 g of the solid heterogeneous catalyst prepared above was charged into an autoclave reactor, followed by 0.10 g of fructopyranose and 15 ml of tetrahydrofuran. The reactor was sealed and the atmosphere was replaced three times with 1 MPa of H₂. H₂ was then introduced to the autoclave system, maintaining a pressure of 1 MPa. The temperature was slowly raised to 120°C using a temperature controller and the reaction was continued for 4 hours. After the reaction, the reactor was cooled to room temperature, the excess reaction gas was slowly released, and the catalyst was separated by filtration. The resulting product was analyzed by gas chromatograph using an HP-7890N equipped with an HP-5 capillary column and an FID detector, confirming the absence of 2,5-hexanedione and 1-hydroxy-2,5-hexanedione.

[0069] Comparative Examples 1, 2, and 3 provide reaction data for the direct conversion of fructose to hexanedione compounds using catalysts loaded with Ru or Ir and unloaded with acid. The catalyst preparation processes for Comparative Examples 1, 2, and 3 are different from those in Example 1, but the other conditions are the same. When the metal component is Ru (Comparative Example 1), the yield of hexanedione compounds is only 3%. When the metal component is Ir (Comparative Example 2), the yield of hexanedione compounds is only 4%. When the catalyst is unmodified and unloaded with acid (Comparative Example 3), no 2,5-hexanedione and 1-hydroxy-2,5-hexanedione are detected. When the catalyst-loaded metal is Pd and loaded with acid (Example 1), the yield of hexanedione compounds can reach 35%. In summary, it can be seen that the multifunctional solid heterogeneous catalyst prepared by the present invention can directly complete the conversion of sugars to obtain high-yield end-product hexanedione compounds, simplify the reaction process, and avoid the separation and purification of platform compounds. The method of the present invention can shorten the fructose conversion reaction process, effectively simplify the reaction process steps and industrial reaction energy consumption, and has significant economic benefits and practical application value.

[0070] While the present invention has been described in detail above, the present invention is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that other modifications and variations may be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.

Claims

1. A multifunctional solid heterogeneous catalyst for the direct conversion of saccharides to produce hexanedione compounds, characterized in that: The direct conversion reaction of the saccharide compound raw material and H2 is carried out in a tank reactor in the presence of a multifunctional solid heterogeneous catalyst, wherein the reaction temperature is 293-573K, the reaction pressure is 0.05-20.0MPa, the molar ratio of the saccharide compound raw material to H2 is 1:1-1:200, and the molar ratio of the saccharide compound to the metal component in the catalyst is 100:1-3000:

1. The multifunctional solid heterogeneous catalyst is composed of a metal component and an acidic organic ligand polymer, wherein the metal component is one or more of metals selected from Pd, Ni, and Mo, and the acidic organic ligand polymer is a polymer obtained by copolymerizing a vinyl-functionalized phosphine ligand monomer, which is then quaternized and loaded with an acid. The metal component forms a coordination bond with the P atoms on the polymer surface and is dispersed on the surface of the organic ligand polymer. The vinyl functionalized phosphine ligand monomer is selected from: .

2. The use according to claim 1, characterized in that: The loaded acid is one or more of trifluoromethanesulfonic acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, sulfuric acid, silicotungstic acid, trifluoroacetic acid, and p-toluenesulfonic acid.

3. The use according to claim 1, characterized in that: The metal component accounts for 0.01-10.0% of the total weight of the multifunctional solid heterogeneous catalyst, and the amount of acid loaded in the catalyst is 0.1-2.4 mmol / g.

4. The use according to claim 3, characterized in that: The metal component accounts for 0.1-5.0% of the total weight of the multifunctional solid heterogeneous catalyst, and the amount of acid loaded in the catalyst is 1.2-1.8 mmol / g.

5. The use according to claim 1, characterized in that: The specific surface area of ​​the acidic organic ligand polymer is 100-3000m 2 / g, pore volume of 0.1-5.0cm 3 / g, pore size distribution is 0.1-100.0nm.

6. The use according to claim 1, characterized in that: The preparation method of the multifunctional solid heterogeneous catalyst comprises: a) adding a free radical initiator to a solvent containing a vinyl-functionalized phosphine ligand monomer at 273-473 K under an inert gas atmosphere and stirring for 0.5-100 hours; b) placing the solution from step a) in a hydrothermal autoclave at 333K-473K under an inert gas atmosphere for 0.5-100 hours to perform a solvothermal polymerization reaction; c) after step b), the solvent is removed in vacuo at a temperature of 273-473 K to obtain the organic ligand polymer; d) placing the organic ligand polymer in a solvent containing 1,3-propane sultone, stirring at 273-473 K under an inert gas atmosphere for 0.5-100 hours, then dropwise adding a solvent containing an acid at 223-373 K, stirring under an inert gas atmosphere for 0.5-100 hours, filtering, washing with a solvent, and then drying at 323-423 K to obtain an acidic organic ligand polymer; e) placing the acidic organic ligand polymer in a solvent containing an active metal component, stirring at 273-473 K under an inert gas atmosphere for 0.5-100 hours, and then drying at 313-423 K to obtain the multifunctional solid heterogeneous catalyst.

7. The use according to claim 6, characterized in that: The preparation method of the multifunctional solid heterogeneous catalyst comprises: a) adding a free radical initiator to a solvent containing a vinyl-functionalized phosphine ligand monomer at 293-333K under an inert gas atmosphere and stirring for 3-12 hours; b) placing the solution from step a) in a hydrothermal autoclave at 353-393 K under an inert gas atmosphere for 24-48 hours to perform a solvothermal polymerization reaction; c) after step b), the solvent is removed in vacuo at a temperature of 333-393 K to obtain the organic ligand polymer; d) placing the organic ligand polymer in a solvent containing 1,3-propane sultone, stirring at 363-393 K under an inert gas atmosphere for 24-48 hours, then dropwise adding a solvent containing an acid at 253-273 K, stirring under an inert gas atmosphere for 24-48 hours, filtering, washing with a solvent, and then drying at 333-353 K to obtain an acidic organic ligand polymer; e) placing the acidic organic ligand polymer in a solvent containing an active metal component, stirring the mixture at 298-333 K under an inert gas atmosphere for 24-48 hours, and then drying the mixture at 333-373 K to obtain the multifunctional solid heterogeneous catalyst.

8. The use according to claim 6 or 7, characterized in that: The weight ratio of the free radical initiator to the phosphine ligand monomer is 1:500-1:5; the molar ratio of the 1,3-propane sultone to the phosphine ligand monomer is 1:500-5:1; and the molar ratio of the acid to the phosphine ligand monomer is 1:500-5:

1.

9. The use according to claim 8, characterized in that: The weight ratio of the free radical initiator to the phosphine ligand monomer is 1:100-1:25; the molar ratio of the 1,3-propane sultone to the phosphine ligand monomer is 1:10-1:2; and the molar ratio of the acid to the phosphine ligand monomer is 1:10-1:

2.

10. The use according to claim 6 or 7, characterized in that: The solvent used in steps a), d) and e) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane, dichloroethane or deionized water; The free radical initiator used in step a) is one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile; The acid used in step d) is one or more of trifluoromethanesulfonic acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, sulfuric acid, silicotungstic acid, trifluoroacetic acid, and p-toluenesulfonic acid; In steps a), b), d) and e), the inert gas is one or more of nitrogen, argon, neon and helium.

11. The use according to claim 1, characterized in that: The reaction temperature is 373-433K, the reaction pressure is 0.5-6.0MPa, the molar ratio of the sugar compound raw material to H2 is 1:10-1:50, and the molar ratio of the sugar compound to the metal component in the catalyst is 200:1-1000:

1.

12. The use according to claim 1, characterized in that: The carbohydrate compound includes one or more of monosaccharides, disaccharides or polysaccharides, wherein the monosaccharide is selected from: fructopyranose, glucose, galactose; the disaccharide is selected from: sucrose, lactose, maltose; the polysaccharide is selected from: cellulose, starch; The hexanedione compound is 2,5-hexanedione and / or 1-hydroxy-2,5-hexanedione.

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