CN112441911B - Method for preparing 5-hydroxyvaleric acid - Google Patents

Method for preparing 5-hydroxyvaleric acid Download PDF

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CN112441911B
CN112441911B CN201910802541.9A CN201910802541A CN112441911B CN 112441911 B CN112441911 B CN 112441911B CN 201910802541 A CN201910802541 A CN 201910802541A CN 112441911 B CN112441911 B CN 112441911B
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catalyst
process according
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heteropolyacid
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CN112441911A (en
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孙乾辉
郑路凡
杜泽学
宗保宁
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a method for preparing 5-hydroxyvaleric acid, which comprises the following steps: reacting furoic acid with hydrogen in an aqueous solution in the presence of a hydrodeoxygenation catalyst to obtain the 5-hydroxyvaleric acid; wherein the hydrodeoxygenation catalyst is a mixture of a supported noble metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst. The method is green and environment-friendly, and the yield of the 5-hydroxypentanoic acid is high.

Description

Method for preparing 5-hydroxyvaleric acid
Technical Field
The invention relates to a method for preparing 5-hydroxyvaleric acid.
Background
5-hydroxyvaleric acid (CAS: 13392-69-3) is a drug synthesis intermediate which has received attention in the pharmaceutical industry in recent years, and can be used as a carbon skeleton or to increase the biocompatibility of drugs in the synthesis process of anti-tumor drugs, anti-tuberculosis drugs, drugs for treating diabetes and the like. At present, no industrial large-scale production of 5-hydroxyvaleric acid is reported in the literature, and a method for hydrolyzing delta-cyclopentanolide is adopted in a common laboratory to obtain an aqueous solution of 5-hydroxyvaleric acid. Similarly, dehydration of 5-hydroxypentanoic acid also efficiently yields delta-cyclopentanolide. Delta-cyclopentanolide is an organic intermediate which can be used for producing fibres (polyesters), pharmaceutical materials and plant protection agents. At present, the Baeyer-Villiger oxidation reaction for synthesizing delta-cyclopentanolide mainly takes cyclopentanone as a raw material is the most mature. However, cyclopentanone, a petroleum-based chemical platform compound, is bound to face the problems of insufficient raw material supply, increased production cost and the like in the route for synthesizing delta-cyclopentanone from the petroleum-based chemical platform compound under the large background of the energy crisis that fossil energy such as petroleum is increasingly depleted.
In addition to the application potential in the fields of medicine and polyester, the 1,5-glutaric acid can be obtained by oxidizing the hydroxymethyl group of 5-hydroxypentanoic acid into a carboxyl group, is used for producing polymers such as polyester, polyamide and the like, and is very useful for reducing the elasticity of the polymers; or reducing the carboxyl group to hydroxymethyl to obtain 1,5-pentanediol, which is used for polyester synthesis or plasticizer. Therefore, the method for synthesizing the 5-hydroxyvaleric acid in an environment-friendly and efficient manner from biomass-based raw materials by a heterogeneous catalysis method has very important scientific research and application values.
On the other hand, furfural is a platform molecule which is very important in the biomass conversion and utilization process. The raw materials for producing the furfural are widely available and comprise corn stalks, corn cobs and the like. Corn planting area is more than twenty hundred million acres all over the world, the total world production is about 500Mt, and a large amount of renewable raw material basis is provided for the production of furfural. Along with the development and utilization of biomass in recent years, the market price of furfural is bound to drop, and the method has very important economic significance for the development and utilization of the whole biomass.
CN106278889B discloses a two-step method for preparing 5-hydroxy methyl valerate from furfural. The method comprises the steps of firstly, catalyzing furfural, methanol and water by a dehydrogenation catalyst to obtain a reaction liquid containing methyl furoate, and then carrying out hydrogenolysis on the obtained reaction liquid containing methyl furoate and hydrogen by a hydrogenolysis catalyst to obtain a reaction liquid containing 5-hydroxy methyl valerate. Wherein, the hydrogenolysis catalyst used for the hydrogenolysis of the methyl furoate In the second step is a supported metal catalyst, the active component is Ag and/or Au, and the carrier is one or more metal oxides of Zn, in, sn, pb, sb, bi and Te. In the method, high-concentration methanol (the molar ratio of methanol/water/furfural is (2-8)/(0.01-0.1)/1) is used as a reaction solvent in the conversion process and participates in the reaction, and the methanol has the characteristics of toxicity, volatility, flammability, explosiveness and the like, so that the safety and the environmental protection value of the method are obviously reduced. And the resulting methyl 5-hydroxypentanoate product may also have the effect of unnecessarily introducing methoxy groups during its subsequent conversion.
Similar to the above method, CN108774135A and CN108929224A also disclose two kinds of branMethod for preparing methyl 5-hydroxypentanoate from methyl furoate by two-step method, wherein aldehyde is used, except that hydrogenolysis catalyst used in the two patents is Cu-La-Al 2 O 3 Catalyst and Zn-Ce-TiO 2 A catalyst. However, both methods also use methanol at high concentration and have the same problems as CN 106278889B.
It should be noted that the hydrogenolysis catalysts used in the above three methods all contain components unstable under acidic conditions, such as Zn or Cu, and therefore, none of the hydrogenolysis catalysts used in the above three methods can be used in an acidic aqueous solution.
Furoic acid is an important organic synthetic raw material, is mainly obtained by oxidizing furfural, and has wide application. The synthesis of 5-hydroxyvaleric acid from furoic acid has important significance for reducing the dependence on petroleum-based products and further improving the application value of furoic acid and 5-hydroxyvaleric acid, and no research report on the aspect is found at present.
Disclosure of Invention
The invention provides a method for preparing 5-hydroxyvaleric acid from furoic acid in an aqueous solution, which does not use methanol, is green and environment-friendly and has high yield.
The invention provides a method for preparing 5-hydroxyvaleric acid, which comprises the following steps: reacting furoic acid with hydrogen in an aqueous solution in the presence of a hydrodeoxygenation catalyst to obtain the 5-hydroxyvaleric acid.
Wherein the hydrodeoxygenation catalyst is a mixture of a supported noble metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst.
Specifically, the catalyst may be a mixture of a supported noble metal catalyst and at least one supported metal oxide catalyst, a mixture of a supported noble metal catalyst and at least one supported heteropolyacid catalyst, or a mixture of a supported noble metal catalyst and at least one supported metal oxide catalyst and at least one supported heteropolyacid catalyst.
Wherein (mass of supported noble metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) =1:0.1 to 100, preferably 1.2 to 10, more preferably 1.
The supported noble metal catalyst comprises a carrier and noble metal supported on the carrier, wherein the supported amount of the noble metal is 0.25-10%, preferably 0.5-5%, and more preferably 1-3% based on the total mass of the carrier; the carrier is selected from one or more of activated carbon, silica, zirconia and titania; the noble metal is selected from one or more of Ru, rh, pd, os, ir and Pt, preferably Ru, pd and Pt.
The supported metal oxide catalyst comprises a carrier and metal oxide loaded on the carrier, wherein the loading amount of the metal oxide is 0.25-90%, preferably 1-60%, and more preferably 5-30% based on the total mass of the carrier; the carrier is selected from one or more of activated carbon, silica, zirconia or titania; the metal oxide is MoO 3 、WO 3 Or ReO 3 Preferably MoO 3 。
The supported heteropolyacid catalyst comprises a carrier and heteropolyacid loaded on the carrier, wherein the loading amount of the heteropolyacid is 0.25-90%, preferably 1-60%, and more preferably 5-30% based on the total mass of the carrier; the carrier is one or more of activated carbon, silicon dioxide, zirconia or titanium dioxide; the metal atom in the heteropoly acid is selected from one or more of W, mo, re, V, nb and Ta, the hetero atom is selected from one or more of Si or P, preferably one or more of tungstenic heteropoly acid, molybdenic heteropoly acid or rhenium heteropoly acid, and more preferably phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphothrenic acid and the like.
The mixture of the supported noble metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst according to the process of the present invention can be formulated by simple mechanical mixing.
The supported noble metal catalyst can be prepared according to the existing method, such as an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method and a deposition-precipitation methodOr vacuum infusion methods. During the specific preparation, after the metal deposition, the solid powder is dried in an oven at 100-140 ℃ for about 6-24 hours, the obtained supported catalyst precursor is calcined in the air at 300-800 ℃ for a period of time, and then in a reducing atmosphere (such as H) 2 Or H 2 And N 2 Mixed atmosphere of (b) at a temperature of 200 to 500 c for about 6 to 24 hours to obtain a supported noble metal catalyst.
The supported metal oxide catalyst or supported heteropolyacid catalyst can be prepared according to the existing method, such as adopting an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method or a vacuum impregnation method; during the specific preparation, after the deposition of the metal oxide precursor or the heteropoly acid precursor, the solid powder is placed in an oven at 100-140 ℃ and dried for about 6-24 hours, and the obtained supported catalyst precursor is calcined in the air at 300-800 ℃ for about 6-24 hours to obtain the supported metal oxide catalyst or the supported heteropoly acid catalyst.
The supported metal oxide catalyst or the supported heteropolyacid catalyst and the supported noble metal catalyst can be uniformly ground according to a certain proportion before reaction and then added into a reaction system, and can also be respectively added into the reaction system according to a certain proportion.
According to one embodiment of the invention, the process conditions are as follows:
in the aqueous solution formed by the furoic acid and water, the mass percentage of the furoic acid can be 0.1-40%, preferably 0.5-25%, and more preferably 1-10%.
The molar ratio of the noble metal in the supported noble metal catalyst to the furoic acid in the hydrodeoxygenation catalyst can be 1:1 to 1000, preferably 1:5 to 500, more preferably 1 to 250.
The reaction can be carried out at a pressure of from 1MPa to 6MPa, preferably from 2MPa to 4 MPa.
The temperature of the reaction may be 150 ℃ to 250 ℃, preferably 160 ℃ to 240 ℃, more preferably 180 ℃ to 220 ℃.
The reaction time may be 1 to 40 hours, preferably 5 to 30 hours, and more preferably 10 to 20 hours.
When the method is used for preparing the 5-hydroxyvaleric acid, the reaction can be carried out in a reaction kettle, after the reaction is finished, the reaction kettle is cooled to room temperature, the pressure of the reaction kettle is relieved, after a kettle cover is opened, a liquid-solid mixture is taken out for suction filtration and separation, the obtained liquid is analyzed by liquid chromatography, and the conversion rate and the product yield are calculated. The method of the invention can also adopt other conventional reactors, such as fixed bed reactors and the like.
The catalyst component used in the invention can resist acid corrosion, and therefore can be directly used for the water phase reaction of the furoic acid. The catalyst has better selective cleavage activity for C-O bonds adjacent to carboxyl groups, and can obtain 5-hydroxyvaleric acid with high yield.
According to the method for preparing 5-hydroxyvaleric acid, furoic acid is used as a raw material, water is used as a solvent, a methanol solvent is not used, other miscellaneous elements are not introduced except a used heterogeneous catalyst, and the yield of the 5-hydroxyvaleric acid is high, so that the method not only further reduces the production cost, but also is more environment-friendly.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Preparation example 1
Preparation of Supported noble Metal catalyst 2%:
adding 0.1mol/L RuCl 2 Mixing 2.1mL of the solution with 3.0mL of deionized water, stirring uniformly, then adding 1.00g of the activated carbon carrier into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and then drying for 12 hours in an oven at 110 ℃ to obtain a catalyst precursor. The loading of Ru is 2% (mass percentage). Placing the precursor prepared in the above steps in a quartz tube, calcining at 500 deg.C in air for 4h, and then 20% 2 +N 2 Reducing at 200 deg.C for 3h to obtain a supported 2% Ru/C catalyst.
The supported noble gold is prepared according to the methodRespectively preparing 4% of Pt/ZrO from the catalyst 2 And 1% of Pd/SiO 2 。
Preparation example 2
MoO content of the supported metal oxide catalyst 10% 3 /TiO 2 The preparation of (1):
0.2g of ammonium molybdate is mixed with 5.0mL of water, the mixture is stirred evenly, and then TiO is added 2 Adding 1.00g of carrier into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and drying in an oven at 110 ℃ for 12 hours to obtain a catalyst precursor. MoO 3 The supporting amount of (B) is 10 mass%. Placing the precursor prepared in the above step in a quartz tube, calcining at 500 deg.C in air for 3 hours to obtain a content of 10% MoO 3 /TiO 2 。
The supported metal oxide catalysts were prepared according to the above method, each supported 5% ReO 3 /SiO 2 And 20% of WO 3 /ZrO 2 . Different supported metal oxide catalysts are prepared by selecting precursors corresponding to the supported components, for example, the supported component is ReO 3 When the precursor is ammonium perrhenate, the precursor can be selected; the load component is WO 3 When the precursor is ammonium metatungstate, ammonium metatungstate can be selected as the precursor.
Preparation example 3
Preparation of the supported heteropolyacid catalyst:
the preparation method of different supported heteropolyacid catalysts is similar to that of supported metal oxides, and the precursors corresponding to the supported components are selected to prepare the supported heteropolyacid catalysts according to the examples, if the supported components are tungstic heteropolyacids such as phosphotungstic acid, silicotungstic acid and the like, the corresponding tungstic heteropolyacids such as phosphotungstic acid, silicotungstic acid and the like can be selected as the precursors; when the load component is a molybdenum-containing heteropoly acid, the corresponding molybdenum-containing heteropoly acid, such as phosphomolybdic acid, silicomolybdic acid and the like, can be selected as a precursor.
The supported heteropolyacid catalyst was prepared as described above, and was loaded with 20% of PWO each x /C，10％SiMoO x /TiO 2 And 5% of PReO x /SiO 2 。
Example 1
By 2% Ru/C +10% MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g 2% Ru/C catalyst (wherein the molar ratio of Ru to furoic acid is about 1: 113), 0.2g 10% MoO 3 /TiO 2 And (3) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 2
By 4% of Pt/ZrO 2 +20％WO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g of 4% Pt/ZrO in a 30mL autoclave 2 Catalyst (wherein the molar ratio of Pt to furoic acid is about 1, 109), 0.2g 20% wo 3 /TiO 2 And (3) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 3
By 1% Pd/SiO 2 +5％ReO 3 /SiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g of 1% of Pd/SiO in a 30mL autoclave 2 Catalyst (wherein the molar ratio of Pd to furoic acid is about 1, 238), 0.2g 5% reo 3 /SiO 2 And (3) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 4
By 2% Ru/C +10% MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g 2% Ru/C catalyst (wherein the molar ratio of Ru to furoic acid is about 1: 113), 0.2g 10% MoO 3 /TiO 2 And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting at the rotating speed of 700rpm for 20 hours. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 5
By 2% Ru/C +10% MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL high pressure autoclave, 0.5g furoic acid, 0.2g 2% Ru/C catalyst (wherein the molar ratio of Ru to furoic acid is about 1: 113), 0.2g 10% MoO 3 /TiO 2 Catalyst and 10mL of water, filling 2MPa of hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times,2MPa of hydrogen is filled into the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 220 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 6
By 2% Ru/C +10% MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g 2% Ru/C catalyst (wherein the molar ratio of Ru to furoic acid is about 1: 113), 0.2g 10% MoO 3 /TiO 2 And (3) filling 4MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 4MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 7
By 4% of Pt/ZrO 2 +20％PWO x and/C as hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g of 4% Pt/ZrO in a 30mL autoclave 2 Catalyst (wherein the molar ratio of Pt to furoic acid is about 1, 109), 0.2g 20% pwo x And C, catalyst and 10mL of water, sealing the reaction kettle, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. After the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, and opening the kettleAnd (4) taking out the liquid-solid mixture, performing suction filtration separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 8
By 1% Pd/SiO 2 +10％SiMoO x /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g of 1% of Pd/SiO in a 30mL autoclave 2 Catalyst (where the molar ratio of Pd to furoic acid is 1, 238), 0.2g 10% simoo x /TiO 2 And (3) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 9
By 2% Ru/C +5% x /SiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of furoic acid, 0.2g 2% Ru/C catalyst (wherein the molar ratio of Ru to furoic acid is about 1: 113), 0.2g 5% PReO in a 30mL autoclave x /SiO 2 And (3) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Comparative example 1
The reaction was carried out according to the procedure of example 4, except that only 2% Ru/C catalyst was added, not 10% MoO 3 /TiO 2 A catalyst. The reaction results are shown in Table 1.
Comparative example 2
The reaction was carried out according to the procedure of example 8, except that only 1% of Pd/SiO was added 2 Catalyst without addition of 10% SiMoO x /TiO 2 A catalyst. The reaction results are shown in Table 1.
Comparative example 3
The reaction was carried out according to the procedure of example 4, except that only 10% of MoO was added 3 /TiO 2 Catalyst, without addition of 2% Ru/C catalyst. The reaction results are shown in Table 1.
Comparative example 4
The reaction was carried out according to the procedures of example 8, except that only 10% SiMoO was added x /TiO 2 Catalyst without addition of 1% of Pd/SiO 2 A catalyst. The reaction results are shown in Table 1.
As can be seen from the data in Table 1, the method for preparing 5-hydroxypentanoic acid provided by the invention can well realize the conversion of furoic acid into 5-hydroxypentanoic acid in an aqueous solution, and the yield of 5-hydroxypentanoic acid can be up to 97%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
TABLE 1 reaction conditions, conversion and yield of 5-hydroxyvaleric acid for examples and comparative examples
Figure BDA0002182739680000091

Claims (27)

1. A process for preparing 5-hydroxyvaleric acid comprising: reacting furoic acid with hydrogen in the presence of a hydrodeoxygenation catalyst in an aqueous solution to obtain the 5-hydroxyvaleric acid, wherein the hydrodeoxygenation catalyst is a mixture of a supported precious metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst, the precious metal is selected from one or more of Ru, rh, pd, os, ir and Pt, and the metal oxide is MoO 3 、WO 3 Or ReO 3 The metal atom in the heteropoly acid is selected from one or more of W, mo, re, V, nb and Ta, and the heteroatom is selected from one or more of Si or P.
2. The process according to claim 1, wherein in the hydrodeoxygenation catalyst, (mass of supported noble metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) =1:0.1 to 100.
3. The process according to claim 1, wherein in the hydrodeoxygenation catalyst, (mass of supported noble metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) = 1.
4. The process according to claim 1, wherein in the hydrodeoxygenation catalyst, (mass of supported noble metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) = 1.
5. The process according to claim 1, wherein the supported noble metal catalyst comprises a carrier and a noble metal supported on the carrier, and the supported amount of the noble metal is 0.25 to 10% based on the total mass of the carrier.
6. The process according to claim 5, wherein the supported amount of the noble metal is 0.5 to 5% by mass based on the total mass of the support.
7. The process according to claim 5, wherein the noble metal is supported at a level of 1 to 3% by mass based on the total mass of the carrier.
8. The process according to claim 1, wherein the supported metal oxide catalyst comprises a carrier and a metal oxide supported on the carrier, and the metal oxide is supported at a content of 0.25 to 90% by mass based on the total mass of the carrier.
9. The process according to claim 8, wherein the metal oxide is supported in an amount of 1 to 60% by mass based on the total mass of the support.
10. The process according to claim 8, wherein the metal oxide is supported at a content of 5 to 30% by mass based on the total mass of the support.
11. A process according to claim 1, wherein the supported heteropolyacid catalyst comprises a support and a heteropolyacid supported on the support, the heteropolyacid being selected from one or more of a tungstenic heteropolyacid, a molybdenic heteropolyacid or a rhenium-containing heteropolyacid.
12. A process according to claim 11, wherein the heteropolyacid is selected from phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphorhenic acid.
13. A process according to claim 11, wherein the heteropolyacid is loaded at a level of from 0.25% to 90% based on the total mass of the support.
14. A process according to claim 11, wherein the heteropolyacid is supported at a loading of 1 to 60% based on the total mass of the support.
15. A process according to claim 11, wherein the heteropolyacid is supported at a loading of 5 to 30% based on the total mass of the support.
16. A process according to claim 5, 8 or 11 wherein the support is one or more of activated carbon, silica, zirconia or titania.
17. The method according to claim 1, wherein the furoic acid is present in an aqueous solution of 0.1-40% by weight.
18. The method according to claim 1, wherein the furoic acid is present in an aqueous solution of 0.5 to 25% by weight of furoic acid and water.
19. The method according to claim 1, wherein the furoic acid is present in an aqueous solution of 1 to 10% by weight of furoic acid and water.
20. The process according to claim 1, wherein the molar ratio of said noble metal to said furoic acid in said hydrodeoxygenation catalyst is from 1:1 to 1000.
21. The process of claim 1 wherein the molar ratio of said noble metal to said furoic acid in said hydrodeoxygenation catalyst is 1:5 to 500.
22. The process according to claim 1, wherein the molar ratio of the noble metal to the furoic acid in the hydrodeoxygenation catalyst is from 1 to 50.
23. The process according to claim 1, wherein the reaction is carried out at a pressure of 1MPa to 6 MPa.
24. The process according to claim 1, wherein the reaction is carried out at a pressure of 2MPa to 4 MPa.
25. The process according to claim 1, wherein the reaction temperature is 150 ℃ to 250 ℃.
26. The process of claim 1, wherein the reaction temperature is 160 ℃ to 240 ℃.
27. The process of claim 1, wherein the reaction temperature is from 180 ℃ to 220 ℃.
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