CN112574024B - Method for preparing succinic acid - Google Patents
Method for preparing succinic acid Download PDFInfo
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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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, 2,3-dihydroxysuccinic acid or 2-hydroxysuccinic acid reacts with hydrogen to obtain the 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
Technical Field
The invention relates to a method for preparing succinic acid, in particular to a method for preparing succinic acid from 2,3-dihydroxysuccinic 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 plant and human and animal tissues. 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 material 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 is difficult to separate systems. The multiphase 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 wastewater and the like, and needs to be further researched when being applied to industrial production in a large scale (2017,37 (3): 38-40 in Shanxi chemical industry). 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-dihydroxysuccinic acid is used as antioxidant synergist, retarder, tanning agent, chelating agent and medicament. Is widely used in the industries of medicine, food, leather making, textile and the like (synthetic chemistry, 2016,24 (3): 266-276). 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 characterized in that 2,3-dihydroxy succinic acid or 2-hydroxysuccinic acid is efficiently converted into a target product succinic acid in a water solution in one step, and the method is simple in process, green, environment-friendly and high in efficiency.
The invention provides a method for preparing succinic acid, which comprises the following steps:
in an aqueous solution, in the presence of a hydrodeoxygenation catalyst, 2,3-dihydroxysuccinic acid or 2-hydroxysuccinic acid reacts with hydrogen 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 1.2 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 a metal oxide loaded on the carrier, wherein the loading amount of the metal oxide is 0.25-90% based on the total mass of the carrier, preferablyFrom 1 to 60%, more preferably from 5 to 30%; 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 One 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 heteropoly acid has metal atom selected from one or more of W, mo, re, V, nb and Ta and hetero atom selected from one or more of Si or P, preferably one or more of tungstenic heteropoly acid, molybdenic heteropoly acid or rhenium-containing heteropoly acid, more preferably phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphorhenic acid, etc.
According to one embodiment of the invention, the process conditions are as follows:
in the aqueous solution formed by 2,3-dihydroxysuccinic acid or 2-hydroxysuccinic acid and water, the weight percentage content of 2,3-dihydroxysuccinic acid or 2-hydroxysuccinic acid can be 0.1-40%, preferably 0.5-25%, more preferably 1-10%.
The molar ratio of the noble metal in the supported noble metal catalyst in the hydrodeoxygenation catalyst to the 2,3-dihydroxysuccinic acid or 2-hydroxysuccinic acid 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.
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 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 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 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.
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/SiO 2 The preparation of (1):
0.1mol/L of PdCl 2 Mixing 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%. Placing the precursor prepared in the above steps in a quartz tube, calcining at 500 deg.C in air for 4h, and further 20% 2 +N 2 Reduction at medium 200 ℃ for 3h to obtain a supported Pd/SiO 2% 2 A catalyst.
Preparation of the Supported noble Metal catalyst according to the above-described method, 4% preparation of each of Pt/TiO 2 And 1% Ru/C.
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 percentage). 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 /C and 20% WO 3 /ZrO 2 . Different supported metal oxide catalysts are selected to be supportedThe precursor corresponding to the load component is prepared according to the example, if the load 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 heteropoly acid containing molybdenum, corresponding heteropoly acid containing molybdenum, 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 /SiO 2 ，10％SiMoO x /ZrO 2 And 5% of PReO x /C。
Example 1
By 2% of Pd/SiO 2 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of 2-hydroxysuccinic acid and 0.2g of 2% in a 30mL autoclave 2 Catalyst, 0.2g10% 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 180 ℃, 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 2
By 4% of Pt/TiO 2 +20％WO 3 /ZrO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of 2-hydroxysuccinic acid and 0.2g of 4% in a 30mL autoclave 2 Catalyst, 0.2g20% WO 3 /ZrO 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% Ru/C +5% 3 The catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.
0.5g of 2-hydroxysuccinic acid, 0.2g of Ru/C catalyst, 0.2g of 5% by weight of ReO in a 30mL autoclave 3 and/C catalyst and 10mL of water, sealing the reaction kettle, filling 2MPa hydrogen to replace residual air in the reaction kettle, 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 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 liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 4
By 2% of Pd/SiO 2 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of 2-hydroxysuccinic acid and 0.2g of 2% in a 30mL autoclave 2 Catalyst, 0.2g10% MoO 3 /TiO 2 Catalyst and 10mL of water are added after the reaction kettle is closedAnd (3) replacing residual air in the reaction kettle with 2MPa hydrogen, 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
By 2% of Pd/SiO 2 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of 2-hydroxysuccinic acid and 0.2g of 2% in a 30mL autoclave 2 Catalyst, 0.2g10% 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 220 ℃, 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 6
By 2% of Pd/SiO 2 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of 2-hydroxysuccinic acid and 0.2g of 2% in a 30mL autoclave 2 Catalyst, 0.2g10% 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. After the reaction is finished, addingAnd taking out the reaction kettle from the hot 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 7
By 4% of Pt/TiO 2 +20％PWO x /SiO 2 As a hydrodeoxygenation catalyst.
Adding 0.5g of 2-hydroxysuccinic acid, 0.2g of 4% Pt/TiO in a 30mL high-pressure reaction kettle 2 Catalyst, 0.2g20% PWO 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.
Example 8
By 2% of Pd/SiO 2 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of 2, 3-dihydroxybutanedioic acid, 0.2g of 2% in a 30mL autoclave 2 Catalyst, 0.2g10% 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 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 1% Ru/C +10% SiMoO x /ZrO 2 The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
0.5g of 2, 3-dihydroxybutanoic acid, 0.2g of Ru/C catalyst, 0.2g of 10% SiMoO in a 30mL autoclave x /ZrO 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 a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 10
By 2% of Pd/SiO 2 +5％PReO x The catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.
0.5g of 2, 3-dihydroxybutanedioic acid, 0.2g of 2% in a 30mL autoclave 2 Catalyst, 0.2g5% 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. 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 procedures of example 4, except that only 2% Pd/SiO was added 2 Catalyst without addition of 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 4, except that only 10% of MoO was added 3 /TiO 2 Catalyst without addition of 2% of Pd/SiO 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 "0.2g 10% MoO was added 3 /TiO 2 Catalyst "replacement" to "0.2g MoO 3 Catalyst ". The reaction results are shown in Table 1.
Comparative example 4
MoO at 10% according to the method of preparation example 1 3 /TiO 2 Further loading on the catalyst a 2-percent Pd component, yielding 2-percent Pd/10-percent MoO 3 /TiO 2 Co-supported catalyst
The reaction was carried out according to the procedure of example 4, except that "0.2g 2% was added 2 Catalyst, 0.2g10% MoO 3 /TiO 2 Catalyst "replacement" 0.2g 2% Pd/10% 3 /TiO 2 Co-supported catalyst ". The reaction results are shown in Table 1.
The data in the table 1 show that the method for preparing succinic acid provided by the invention can well realize the conversion of 2,3-dihydroxy succinic acid or 2-hydroxy succinic acid to important chemical raw material succinic acid in aqueous solution. The succinic acid yield of 92 percent can be obtained from 2-malic acid, and the succinic acid yield of 85 percent can be obtained from 2,3-dihydroxy succinic 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 cannot be achieved by using a combination of a supported noble metal catalyst and a metal oxide or a noble metal and metal oxide co-supported 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
Claims (22)
1. A method of making succinic acid comprising:
in an aqueous solution, in the presence of a hydrodeoxygenation catalyst, 2,3-dihydroxy succinic acid or 2-hydroxysuccinic acid reacts 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 noble metal is selected from one or more of Ru, rh, pd, os, ir and Pt, and the metal oxide is selected from 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.
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 method of claim 1 wherein the noble metal is selected from the group consisting of Ru, pd and Pt.
5. A process according to claim 1, wherein the heteropolyacid is selected from one or more of a tungstenic heteropolyacid, a molybdenitic heteropolyacid or a rhenium-bearing heteropolyacid.
6. A process according to claim 1, wherein the heteropolyacid is selected from phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid and phosphorhenic acid.
7. The process according to claim 1, wherein the supported noble metal catalyst comprises a support and a noble metal supported on the support, the supported metal oxide catalyst comprises a support and a metal oxide supported on the support, and the supported heteropolyacid catalyst comprises a support and a heteropolyacid supported on the support.
8. The process according to claim 7, wherein the supported noble metal catalyst has a noble metal loading of 0.25 to 10% based on the total mass of the support.
9. The process according to claim 7, wherein the supported noble metal catalyst is supported at a noble metal loading of 0.5 to 5% by mass based on the total mass of the carrier.
10. The process according to claim 7, wherein the supported metal oxide catalyst has a metal oxide loading of 1 to 60% based on the total mass of the carrier.
11. The process according to claim 7, wherein the supported metal oxide catalyst has a metal oxide loading of 5 to 30% based on the total mass of the carrier.
12. A process according to claim 7, wherein the supported heteropolyacid catalyst is supported at a loading of 1 to 60% based on the total mass of the support.
13. A process according to claim 7, wherein the supported heteropolyacid catalyst is supported at a loading of 5 to 30% based on the total mass of the support.
14. The process of claim 7, wherein the support is one or more of activated carbon, silica, zirconia, or titania.
15. The method of claim 1, wherein the 2,3-dihydroxybutanedioic acid or 2-hydroxybutanedioic acid is present in an aqueous solution in an amount of 0.5 to 25% by weight.
16. The method of claim 1, wherein the 2,3-dihydroxybutanedioic acid or 2-hydroxybutanedioic acid is present in the aqueous solution in an amount of 1 to 10% by weight.
17. The process of claim 1, wherein the molar ratio of the noble metal of the supported noble metal catalyst of the hydrodeoxygenation catalyst to the noble metal of 2,3-dihydroxybutanedioic acid or 2-hydroxybutanedioic acid is 1:5 to 500.
18. The method of claim 1, wherein the molar ratio of the noble metal in the supported noble metal catalyst in the hydrodeoxygenation catalyst to the 2,3-dihydroxybutanedioic acid or 2-hydroxybutanedioic acid is 1 to 250.
19. The process according to claim 1, wherein the reaction is carried out at a pressure of 1 to 6 MPa.
20. The process according to claim 1, wherein the reaction is carried out at a pressure of 2 to 4 MPa.
21. The process according to claim 1, wherein the reaction temperature is 150 ℃ to 250 ℃.
22. The process of claim 1, wherein the reaction temperature is from 180 ℃ to 220 ℃.
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| CN102794181A (en) * | 2011-05-27 | 2012-11-28 | 中科合成油技术有限公司 | Hydrodeoxygenation catalyst for Fischer Tropsch synthesis oil and preparation method and application of hydrodeoxygenation catalyst |
| CN107011154A (en) * | 2016-01-28 | 2017-08-04 | 北京大学 | A kind of method that adipic acid is prepared by furans -2,5- dicarboxylic acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102794181A (en) * | 2011-05-27 | 2012-11-28 | 中科合成油技术有限公司 | Hydrodeoxygenation catalyst for Fischer Tropsch synthesis oil and preparation method and application of hydrodeoxygenation catalyst |
| CN107011154A (en) * | 2016-01-28 | 2017-08-04 | 北京大学 | A kind of method that adipic acid is prepared by furans -2,5- dicarboxylic acids |
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| "Selective hydrodeoxygenation of tartaric acid to succinic acid";Jiayi Fu等;《Catal. Sci. Technol.》;20170830;第7卷;4944–4954页 * |
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