A process for the preparation of methane tricarboxylic acid from ketoglutaric acid and glyoxylic acid
Patent Information
- Application Number
- CN202311854022.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-29
- Publication Date
- 2026-09-08
- Estimated Expiration
- 2043-12-29
AI Technical Summary
但是该反应中需要使用有毒的氰乙酸和大量的有机溶剂，且该反应过程较为低效
[0022] The raw materials used in the method of this invention are derived from biomass, and the solvent used is H2O. H2 is used as a reducing agent, and the reaction process is green and does not produce byproducts that are harmful to the environment.
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Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing methanetriacetic acid from ketoglutaric acid and glyoxylic acid, belonging to the field of organic synthesis technology. Background Technology
[0002] Methanetriacetic acid (MTA) is used as a precursor in the synthesis of metal-organic frameworks, organometallic complex catalysts, and pharmaceuticals. Currently, the main production process for MTA involves the sequential dehydration, condensation, hydrogenation, and hydrolysis of citric acid and cyanoacetic acid. However, this reaction requires toxic cyanoacetic acid and large amounts of organic solvents, and the process is relatively inefficient. Therefore, the synthesis of MTA from abundant renewable biomass through catalytic conversion has attracted considerable attention. Summary of the Invention
[0003] The purpose of this invention is to provide a method for preparing methanetriacetic acid from ketoglutaric acid and glyoxylic acid. The ketoglutaric acid and glyoxylic acid raw materials used in this invention are derived from renewable biomass, and the preparation process is environmentally friendly, green and pollution-free.
[0004] The method for preparing methanetriacetic acid provided by the present invention includes the following steps:
[0005] S1. Ketoglutaric acid and glyoxylic acid undergo aldol condensation to yield 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid;
[0006] S2, the 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid is hydrogenated and deoxygenated to obtain methanetriacetic acid.
[0007] In the preparation method of the present invention, in step S1, the aldol condensation is carried out in the presence of an alkaline catalyst;
[0008] The amount of the alkaline catalyst used is 5-120% of the mass of the ketoglutaric acid;
[0009] The alkaline catalyst may be NaOH, KOH, ammonia, MgO, CaO, or magnesium-zirconium composite oxide;
[0010] In step S1, the solvent used for the aldol condensation is preferably water, and the reaction conditions are as follows:
[0011] The temperature is 30–70℃, and the time is 1–24 hours.
[0012] In the preparation method of the present invention, in step S2, the hydrodeoxygenation is carried out in the presence of hydrogen and a catalyst;
[0013] The catalyst is a supported catalyst, with TiO2, SiO2, ZrO2, CeO2, Al2O3 and activated carbon as the support, and metals and oxides as the active components;
[0014] The metal is at least one of Pd, Pt, Rh, Ru, and Ni;
[0015] The oxide is ReO. x and / or MoO x x = 1 to 3;
[0016] The loading of the metal is 0.5% to 5%, and the loading of the oxide is 1% to 15%.
[0017] In the preparation method of the present invention, in step S2, the amount of catalyst used is 10 to 200% of the mass of 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid.
[0018] In the preparation method of this invention, the reaction conditions for hydrogenation deoxygenation in step S2 are as follows:
[0019] The temperature is 180–220℃, the time is 4–24h, and the H2 pressure is 1–4MPa.
[0020] In the preparation method of the present invention, in step S2, the solvent used for hydrogenation deoxygenation is water.
[0021] Compared with the prior art, the present invention has the following advantages:
[0022] The raw materials used in the method of this invention are derived from biomass, and the solvent used is H2O. H2 is used as a reducing agent, and the reaction process is green and does not produce byproducts that are harmful to the environment. Detailed Implementation
[0023] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.
[0024] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.
[0025] In the following examples, the catalyst was prepared as follows:
[0026] 1. Preparation of supported Pd / TiO2 catalysts
[0027] The preparation of a Pd / TiO2 catalyst with a loading of 2% is used as an example for non-limiting explanation.
[0028] 2 mL of [Pd(NH3)4](NO3)2 aqueous solution (Pd concentration 10 mg / mL) and 10 mL of deionized water were added to a 100 mL round-bottom flask equipped with a stirrer and stirred until homogeneous. Then, 1 g of TiO2 was added to the solution, and the mixture was stirred at 600 rpm at room temperature for 6 h. After evaporating the water, the solid sample was dried in an oven at 110 °C for 12 h to obtain the catalyst precursor. The catalyst precursor was transferred to a quartz tube and calcined in flowing air for 3 h, followed by calcination in 20% H2 / N2 at 500 °C for 2 h to obtain the supported 2% Pd / TiO2 catalyst.
[0029] 2. Loaded MoO x Preparation of TiO2 catalyst
[0030] Take MoO x MoO2 with a loading of 10% x The preparation of the / TiO2 catalyst is used as an example for non-limiting explanation.
[0031] Add 5 mL of (NH4)6Mo7O to a 100 mL round-bottom flask equipped with a stir bar. 24 An aqueous solution (Mo concentration of 20 mg / mL) and 10 mL of deionized water were mixed thoroughly. Then, 1 g of TiO₂ was added to the solution, and the mixture was stirred at 600 rpm at room temperature for 6 h. After evaporating the water, the solid sample was dried in an oven at 110 °C for 12 h to obtain the catalyst precursor. The catalyst precursor was transferred to a quartz tube and calcined in flowing air for 3 h to obtain supported 10% MoO₂. x / TiO2 catalyst.
[0032] 3. Loaded Pd-MoO x Preparation of TiO2 catalyst
[0033] With Pd and MoO x Pd-MoO2 loadings of 2% and 10% respectively x The preparation of the / TiO2 catalyst is used as an example for non-limiting explanation.
[0034] Add 5 mL of (NH4)6Mo7O to a 100 mL round-bottom flask equipped with a stir bar. 24 A mixture of 2 mL of [Pd(NH3)4](NO3)2 aqueous solution (Pd concentration 10 mg / mL) and 10 mL of deionized water was prepared and stirred until homogeneous. Then, 1 g of TiO2 was added to the solution, and the mixture was stirred at 600 rpm at room temperature for 6 h. After evaporating the water, the solid sample was dried in an oven at 110 °C for 12 h to obtain the catalyst precursor. The catalyst precursor was transferred to a quartz tube and calcined in flowing air for 3 h to obtain supported Pd-MoO2.x / TiO2 catalyst, in which Pd and MoO x The loads were 2% and 10%, respectively.
[0035] 4. Load-based ReO x / / Preparation of TiO2 catalyst
[0036] Take ReO x ReO with 10% load x The preparation of the / TiO2 catalyst is used as an example for non-limiting explanation.
[0037] Add 5 mL of HReO4 aqueous solution (Re concentration 20 mg / mL) and 10 mL of deionized water to a 100 mL round-bottom flask equipped with a stirrer, and stir until homogeneous. Then add 1 g of TiO2 to the solution and stir at 600 rpm at room temperature for 6 h. After evaporating the water, dry the solid sample in an oven at 110 °C for 12 h to obtain the catalyst precursor. Transfer the catalyst precursor to a quartz tube and calcine it in flowing air for 3 h to obtain supported 10% ReO2. x / TiO2 catalyst.
[0038] Example 1
[0039] The reaction equation for the preparation of methanetriacetic acid according to this invention is as follows:
[0040]
[0041] 1. Ketoglutaric acid and glyoxylic acid are converted into 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid.
[0042] The following is a non-limiting explanation using NaOH catalyst as an example.
[0043] In a 50 mL autoclave, 6.72 g of KOH (115% of the mass of ketoglutaric acid), 5.84 g of ketoglutaric acid, 2.96 g of glyoxylic acid, and 20 mL of deionized water were added. The autoclave was sealed and placed in a heater to 50 °C, with the stirring speed controlled at 600 rpm. After 5 hours, heating was stopped, and the mixture was cooled to room temperature. The reaction solution was brought to a final volume of 100 mL, and the reaction products were analyzed using high-performance liquid chromatography (HPLC) (Shodex SUGAR SH1011 column). The substrates ketoglutaric acid and glyoxylic acid were completely converted, with a yield of 97% for 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid. The resulting 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid solution was used directly in the next reaction without separation.
[0044] 2,3-Carboxymethyl-2-hydroxy-4-oxoglutaric acid is converted to methanetriacetic acid.
[0045] With Pd and MoO x The loadings of Pd / TiO2 and MoO were 2% and 10%, respectively. x The following is a non-limiting explanation using TiO2 catalyst as an example.
[0046] In a 50 mL autoclave, 1 mL of 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid solution, 13 mL of deionized water, 6 mL of hydrochloric acid solution (1.0 mol / L), 50 mg of Pd / TiO2 catalyst, and 0.1 g of MoO2 were added sequentially. x / TiO2 catalyst (the amount of catalyst used was 23% of the mass of 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid). After sealing the reactor, 1 MPa of H2 was introduced to displace the air in the reactor. This process of purging and venting was repeated three times. Then, 2 MPa of H2 was introduced, and the reactor was placed in a heating furnace and heated to 200°C. The stirring rate of the reactor was controlled at 600 rpm. After 24 hours, heating was stopped, and the reactor was cooled to room temperature, and the H2 in the reactor was released. The reaction solution and catalyst were separated by vacuum filtration. The filtrate was brought to a final volume of 100 mL, and the reaction products were analyzed by high performance liquid chromatography (using a Shodex SUGARSH 1011 column). The conversion rate of the substrate 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid was 100%, and the yield of methanetriacetic acid was 89%.
[0047] Based on the above results, using ketoglutaric acid and glyoxylic acid as raw materials, the total yield of methanetriacetic acid was 86% after a two-step reaction. The method of this invention is an effective method for synthesizing methanetriacetic acid.
[0048] Example 2
[0049] 1. Ketoglutaric acid and glyoxylic acid are converted into 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid.
[0050] The following is a non-limiting explanation using MgO catalyst as an example.
[0051] In a 50 mL autoclave, add 0.3 g MgO (5% of the mass of ketoglutaric acid), 5.84 g ketoglutaric acid, 2.96 g g glyoxylic acid, 4.80 g NaOH, and 20 mL deionized water. Seal the autoclave and place it in a heater to 50 °C, maintaining a stirring speed of 600 rpm. After 3 hours, stop heating and allow to cool to room temperature. Make up to 100 mL of the reaction mixture and analyze the reaction products using high-performance liquid chromatography (HPLC) (Shodex SUGARSH 1011 column). The substrates ketoglutaric acid and glyoxylic acid were completely converted, with a yield of 97% for 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid. The resulting 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid solution was used directly in the next reaction without separation.
[0052] 2,3-Carboxymethyl-2-hydroxy-4-oxoglutaric acid is converted to methanetriacetic acid.
[0053] With Pd and ReO x The loadings of Pd / TiO2 and ReO were 2% and 10%, respectively. x The following is a non-limiting explanation using TiO2 catalyst as an example.
[0054] In a 50 mL autoclave, 1 mL of 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid solution, 13 mL of deionized water, 6 mL of hydrochloric acid solution (1.0 mol / L), 50 mg of Pd / TiO2 catalyst, and 0.8 g of ReO2 were added sequentially. x / TiO2 catalyst (catalyst dosage was 182% of the mass of 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid). After sealing the reactor, 1 MPa of H2 was introduced to displace the air in the reactor. This process of purging and venting was repeated three times. Then, 2 MPa of H2 was introduced, and the reactor was placed in a heating furnace and heated to 200°C. The stirring rate of the reactor was controlled at 600 rpm. After 12 hours, heating was stopped, and the reactor was cooled to room temperature, releasing the H2. The reaction solution and catalyst were separated by vacuum filtration. The filtrate was brought to a final volume of 100 mL, and the reaction products were analyzed using high-performance liquid chromatography (HPLC) (Shodex SUGARSH 1011 column). The conversion rate of the substrate 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid was 100%, and the yield of methanetriacetic acid was 80%.
Claims
1. A method for preparing methanetriacetic acid, comprising the following steps: S1. Ketoglutaric acid and glyoxylic acid undergo aldol condensation to yield 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid; S2, the 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid is hydrogenated and deoxygenated to obtain methanetriacetic acid; The hydrodeoxygenation is carried out in the presence of hydrogen and a catalyst. The catalyst is a supported catalyst, with TiO2, SiO2, ZrO2, CeO2, Al2O3 and activated carbon as the support, and metals and oxides as the active components; The metal is at least one of Pd, Pt, Rh, Ru and Ni; The oxide is ReO. x and / or MoO X x = 1~3; The loading of the metal is 0.5-5%, and the loading of the oxide is 1-15%.
2. The preparation method according to claim 1, characterized in that: In step S1, the aldol condensation is carried out in the presence of an alkaline catalyst; The amount of the alkaline catalyst used is 5-120% of the mass of the ketoglutaric acid.
3. The preparation method according to claim 2, characterized in that: The alkaline catalyst is NaOH, KOH, ammonia, MgO, CaO, or magnesium-zirconium composite oxide.
4. The preparation method according to any one of claims 1-3, characterized in that: In step S1, the solvent used for the aldol condensation is water, and the reaction conditions are as follows: The temperature is 30~70℃, and the time is 1~24 h.
5. The preparation method according to any one of claims 1-3, characterized in that: In step S2, the amount of catalyst used is 10 to 200% of the mass of 3-carboxymethyl-2-hydroxy-4-oxoglutaric acid.
6. The preparation method according to any one of claims 1-3, characterized in that: In step S2, the reaction conditions for the hydrodeoxygenation are as follows: The temperature is 180~220℃, the time is 4~24 h, and the H2 pressure is 1~4MPa.
7. The preparation method according to any one of claims 1-3, characterized in that: In step S2, the solvent used for hydrodeoxygenation is water.