CN112574024A - Method for preparing succinic acid - Google Patents

Method for preparing succinic acid Download PDF

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CN112574024A
CN112574024A CN201910926605.6A CN201910926605A CN112574024A CN 112574024 A CN112574024 A CN 112574024A CN 201910926605 A CN201910926605 A CN 201910926605A CN 112574024 A CN112574024 A CN 112574024A
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catalyst
supported
acid
noble metal
heteropolyacid
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CN112574024B (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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    • 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
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    • 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
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    • 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
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    • 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
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—Rhenium
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/10—Succinic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a method for preparing succinic acid, which comprises the following steps: in an aqueous solution, in the presence of a hydrodeoxygenation catalyst, reacting 2, 3-dihydroxysuccinic acid or 2-hydroxysuccinic acid with hydrogen to obtain succinic 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 succinic acid yield is high.

Description

Method for preparing succinic acid
Technical Field
The invention relates to a method for preparing succinic acid, in particular to a method for preparing succinic acid from 2, 3-dihydroxy succinic acid or 2-hydroxysuccinic acid in aqueous solution.
Background
Succinic Acid (i.e., Succinic Acid, CAS: 110-15-6) is a common natural organic Acid found in a wide variety of plants and tissues of humans and animals. As a C4 platform compound, succinic acid is an important organic chemical raw material and intermediate, is mainly used for preparing pentaheterocyclic compounds such as succinic anhydride and the like, and is also used for preparing alkyd resin, paint, dye, food flavoring agent, photographic materials and the like. It can be used in the pharmaceutical industry for the production of a variety of drugs. Thus, succinic acid is considered by the U.S. department of energy to be one of the 12 most valuable future refined products.
At present, methods for producing succinic acid include electrolytic synthesis, catalytic hydrogenation, and biological fermentation. The electrolytic synthesis method is to take maleic acid (anhydride) as a raw material to electrolyze to obtain succinic acid. In the actual production, the electrolytic synthesis method still has the problems of high power consumption, electrode corrosion and the like. The catalytic hydrogenation method generally uses maleic anhydride as a raw material, and performs hydrogenation in a certain catalytic system to prepare succinic anhydride, and then performs hydrolysis to obtain high-purity succinic acid. However, homogeneous catalysis is limited in industrial application because it uses expensive noble metal catalysts and separation of the systems is difficult. The heterogeneous catalytic process is still in the pilot plant stage at present. In addition, the electrolysis method and the catalytic hydrogenation method both use non-renewable petroleum-based maleic anhydride as a raw material, and are not beneficial to the sustainable development of the chemical industry of China. The biological fermentation method is to produce the succinic acid and the derivatives thereof by using starch, cellulose, glucose or other wastes which can be utilized by microorganisms as raw materials and utilizing bacteria or other microorganisms for fermentation. However, the biological method has the problems of low production efficiency, complex separation and purification process, large amount of waste water and the like, and the large-scale application of the biological method to industrial production needs further research (Shanxi chemical industry, 2017,37(3): 38-40). Therefore, the method for synthesizing the succinic acid in an environment-friendly and efficient manner by using the heterogeneous catalysis method from renewable biomass-based raw materials has very important scientific research and application values.
On the other hand, 2, 3-dihydroxysuccinic acid (i.e., tartaric acid, CAS: 87-69-4) and 2-hydroxysuccinic acid (i.e., malic acid, CAS: 617-48-1) are common important chemicals based on green mature biofermentation. 2, 3-dihydroxy succinic acid is used as antioxidant synergist, retarder, tanning agent, chelating agent and medicine. Widely used in the industries of medicine, food, leather, textile and the like (synthetic chemistry, 2016,24(3): 266-. The 2-hydroxysuccinic acid is widely applied to the food and medicine industries (technical report of food science, 2019,37(2): 1-9). Therefore, the synthesis of succinic acid from 2, 3-dihydroxysuccinic acid or 2-hydroxysuccinic acid has important contribution to reducing the dependence on petroleum-based products and further improving the application value of succinic acid, and has very important economic significance for the development and utilization of the whole biomass.
Disclosure of Invention
The invention provides a method for preparing succinic acid, which is used for efficiently converting 2, 3-dihydroxy succinic acid or 2-hydroxysuccinic acid into a target product succinic acid in one step in an aqueous solution, and has the characteristics of simple process, environmental friendliness and high efficiency.
The invention provides a method for preparing succinic acid, which comprises the following steps:
in an aqueous solution, 2, 3-dihydroxysuccinic acid or 2-hydroxysuccinic acid reacts with hydrogen in the presence of a hydrodeoxygenation catalyst to obtain the succinic acid.
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 hydrodeoxygenation catalyst can be a mixture of a supported noble metal catalyst and at least one supported metal oxide catalyst, can also be a mixture of a supported noble metal catalyst and at least one supported heteropolyacid catalyst, and can also be a mixture of a supported noble metal catalyst, 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 1:0.2 to 10, more preferably 1:0.5 to 5.
The supported noble metal catalyst comprises a carrier and noble metals supported on the carrier, wherein the supported amount of the noble metals 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 MoO3、WO3Or ReO3One or more of (a).
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.
According to one embodiment of the invention, the process conditions are as follows:
in the aqueous solution formed by the 2, 3-dihydroxysuccinic acid or the 2-hydroxysuccinic acid and water, the mass percentage of the 2, 3-dihydroxysuccinic acid or the 2-hydroxysuccinic acid is 0.1-40%, preferably 0.5-25%, and more preferably 1-10%.
In the hydrodeoxygenation catalyst, the molar ratio of the noble metal in the supported noble metal catalyst to the 2, 3-dihydroxybutanedioic acid or the 2-hydroxybutanedioic acid can be 1: 1 to 1000, preferably 1:5 to 500, more preferably 1:50 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.
The hydrodeoxygenation catalyst used in the method of the invention is a mixture of a supported noble metal catalyst and at least one supported metal oxide catalyst or at least one supported heteropolyacid catalyst, and can be prepared by a simple mechanical mixing manner.
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, a deposition-precipitation method or a vacuum impregnation method. During the specific preparation, after metal deposition, the solid powder is placed in an oven at 100-140 ℃ for drying 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 the calcination is carried out in a reducing atmosphere (such as H)2Or H2And N2Mixed atmosphere) at a temperature of 200 to 500 ℃ for about 6 to 24 hours to obtain a supported noble metal catalyst.
The supported metal oxide catalyst or the supported heteropolyacid catalyst can be prepared according to the existing method, such as an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method or a vacuum impregnation method; during the 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 ℃ for drying 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.
When the method is used for preparing the succinic acid, the succinic acid can be prepared in a reaction kettle, after the reaction is finished, the reaction kettle is taken out, cooled to room temperature, the pressure of the reaction kettle is relieved, 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.
According to the method for preparing the succinic acid, water is used as a solvent, other miscellaneous elements are not introduced except for a used heterogeneous catalyst, and the succinic acid yield 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
Supported noble metal catalyst 2% Pd/SiO2The preparation of (1):
0.1mol/L of PdCl2Mixing 2.1mL of the solution with 3.0mL of deionized water, stirring uniformly, then adding 1.00g of 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 amount of Pd was 2 mass%. Putting the precursor prepared in the step into a quartz tube, firstly calcining for 4H at 500 ℃ in the air, and then calcining for 20% H2+N2Reducing for 3h at the temperature of 200 ℃ to obtain the load type 2 percent Pd/SiO2A catalyst.
The supported noble metal catalyst is prepared according to the method, and 4 percent of Pt/TiO is respectively prepared2And 1% Ru/C.
Preparation example 2
Supported metal oxide catalyst 10% MoO3/TiO2The preparation of (1):
0.2g of ammonium molybdate is mixed with 5.0mL of water, the mixture is stirred evenly, and then TiO is added2Adding 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. MoO3The supporting amount of (B) is 10 mass%. Putting the precursor prepared in the step into a quartz tube, and calcining the precursor in the air at 500 ℃ for 3 hours to obtain 10% MoO3/TiO2。
The supported metal oxide catalyst is prepared according to the method, and 5 percent of ReO is loaded respectively3C and 20% WO3/ZrO2. Different supported metal oxide catalysts are prepared by selecting precursors corresponding to supported components, for example, the supported component is ReO3When the precursor is ammonium perrhenate, the precursor can be selected; the load component is WO3When 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 is prepared according to the method, and 20 percent of PWO is loaded respectivelyx/SiO2，10％SiMoOx/ZrO2And 5% PReOx/C。
Example 1
With 2% Pd/SiO2+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 2% Pd/SiO2Catalyst, 0.2g 10% MoO3/TiO2And (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
With 4% Pt/TiO2+20％WO3/ZrO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 4% Pt/TiO was added2Catalyst, 0.2g 20% WO3/ZrO2And (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
With 1% Ru/C + 5% ReO3The catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 1% Ru/C catalyst, 0.2g of 5% ReO3The reaction kettle is sealed and filled with 2MPa hydrogen to replace the residual air in the reaction kettle, the reaction kettle is filled with water of 10mL and the reaction kettle is filled with hydrogen after the reaction kettle is sealed for three times2MPa hydrogen, 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
With 2% Pd/SiO2+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 2% Pd/SiO2Catalyst, 0.2g 10% MoO3/TiO2And (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 5
With 2% Pd/SiO2+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 2% Pd/SiO2Catalyst, 0.2g 10% MoO3/TiO2And (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 220 ℃, 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) covering, 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 6
With 2% Pd/SiO2+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 2% Pd/SiO2Catalyst, 0.2g 10% MoO3/TiO2And (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
With 4% Pt/TiO2+20％PWOx/SiO2As a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 4% Pt/TiO was added2Catalyst, 0.2g 20% PWOx/SiO2And (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 8
With 2% Pd/SiO2+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2, 3-dihydroxybutanedioic acid, 0.2g of 2% Pd/SiO2Catalyst, 0.2g 10% MoO3/TiO2And (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
With 1% Ru/C + 10% SiMoOx/ZrO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2, 3-dihydroxybutanoic acid, 0.2g of 1% Ru/C catalyst, 0.2g of 10% SiMoOx/ZrO2And (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 10
With 2% Pd/SiO2+5％PReOxThe catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g of 2, 3-dihydroxybutanedioic acid, 0.2g of 2% Pd/SiO2Catalyst, 0.2g 5%PReOxAnd 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. 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% Pd/SiO was added2Catalyst without addition of 10% MoO3/TiO2A catalyst. The reaction results are shown in Table 1.
Comparative example 2
The reaction was carried out according to the procedure of example 4, except that only 10% MoO was added3/TiO2Catalyst without addition of 2% Pd/SiO2A 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 "0.2 g of 10% MoO" was added3/TiO2Catalyst "replacement by" 0.2g MoO3Catalyst ". The reaction results are shown in Table 1.
Comparative example 4
The procedure of preparation 1 was followed at 10% MoO3/TiO2Further loading 2% Pd component on the catalyst to obtain 2% Pd/10% MoO3/TiO2Co-supported catalyst
The reaction was carried out according to the procedure of example 4, except that "0.2 g of 2% Pd/SiO 2" was added2Catalyst, 0.2g 10% MoO3/TiO2Catalyst "replacement" 0.2g 2% Pd/10% MoO3/TiO2Co-supported catalyst ". The reaction results are shown in Table 1.
As can be seen from the data in Table 1, the method for preparing succinic acid provided by the invention can well realize the conversion of 2, 3-dihydroxysuccinic acid or 2-hydroxysuccinic acid to important chemical raw material succinic acid in aqueous solution. The succinic acid yield of up to 92 percent can be obtained from 2-hydroxysuccinic acid, and the succinic acid yield of up to 85 percent can be obtained from 2, 3-dihydroxysuccinic acid.
As can be seen from comparative examples 1 and 2, neither the supported noble metal catalyst nor the supported metal oxide catalyst alone can yield a succinic acid product. As can be seen from comparative examples 3 and 4, the succinic acid yield level of the catalyst system of the present invention could not be achieved using the combination of the supported noble metal catalyst and the metal oxide or the co-supported noble metal and metal oxide catalyst.
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 the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
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 succinic acid yield of examples and comparative examples
Figure BDA0002219126710000091

Claims (13)

1. A method of preparing succinic acid, comprising:
in an aqueous solution, in the presence of a hydrodeoxygenation catalyst, reacting 2, 3-dihydroxysuccinic acid or 2-hydroxysuccinic acid with hydrogen to obtain succinic 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.
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, preferably 1:0.2 to 10, more preferably 1:0.5 to 5.
3. The process according to claim 1, wherein the supported noble metal catalyst comprises a support and a noble metal supported on the support, the noble metal being selected from one or more of Ru, Rh, Pd, Os, Ir and Pt, preferably Ru, Pd and Pt.
4. The process according to claim 3, wherein the supported noble metal catalyst is supported at a noble metal loading of 0.25 to 10%, preferably 0.5 to 5%, more preferably 1 to 3%, based on the total mass of the carrier.
5. The process according to claim 1, wherein the supported metal oxide catalyst comprises a carrier and a metal oxide selected from MoO supported on the carrier3、WO3Or ReO3One or more of (a).
6. The process according to claim 5, wherein the supported metal oxide catalyst is supported in an amount of 0.25 to 90%, preferably 1 to 60%, more preferably 5 to 30%, based on the total mass of the carrier.
7. A process according to claim 1, wherein the supported heteropolyacid catalyst comprises a support and a heteropolyacid supported on the support, the heteropolyacid having metal atoms selected from one or more of W, Mo, Re, V, Nb and Ta and heteroatoms selected from one or more of Si or P, preferably one or more of a tungstenic heteropolyacid, a molybdenyl heteropolyacid or a rhenium-containing heteropolyacid, more preferably such as phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid and phosphotrhenic acid.
8. A process according to claim 7, wherein the supported heteropolyacid catalyst is supported at a level of from 0.25% to 90%, preferably from 1% to 60%, more preferably from 5% to 30%, based on the total mass of the support.
9. The process of any one of claims 3, 5, 7, wherein the support is one or more of activated carbon, silica, zirconia or titania.
10. The method according to claim 1, wherein the mass percentage of the 2, 3-dihydroxybutanedioic acid or 2-hydroxybutanedioic acid in the aqueous solution is 0.1-40%, preferably 0.5-25%, and more preferably 1-10%.
11. The process of claim 1, wherein the molar ratio of noble metal in the supported noble metal catalyst of the hydrodeoxygenation catalyst to the 2, 3-dihydroxybutanedioic acid or 2-hydroxybutanedioic acid is 1: 1 to 1000, preferably 1:5 to 500, more preferably 1:50 to 250.
12. The process according to claim 1, wherein the reaction is carried out at a pressure of 1 to 6MPa, preferably 2 to 4 MPa.
13. The process according to claim 1, wherein the reaction temperature is 150 ℃ to 250 ℃, preferably 160 ℃ to 240 ℃, more preferably 180 ℃ to 220 ℃.
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