A process for the production of succinic acid from tartaric acid
By using an iodine catalyst and a methyl ketone solvent for transfer hydrogenation, the problems of harsh reaction conditions and difficult product separation in the preparation of succinic acid from tartaric acid in the prior art have been solved, achieving the preparation of succinic acid with high selectivity and high yield, which is suitable for industrial applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANCHANG UNIV
- Filing Date
- 2022-09-15
- Publication Date
- 2026-06-12
AI Technical Summary
The existing methods for preparing succinic acid from tartaric acid require metal catalysts and a hydrogen atmosphere, resulting in unmild reaction conditions and difficulties in product separation.
The transfer hydrogenation reaction was carried out using an iodine catalyst and a methyl ketone solvent. The reaction was carried out in a pressure-resistant tube under nitrogen atmosphere at atmospheric pressure. After the reaction, succinic acid precipitated in solid form and was separated by filtration.
The preparation of succinic acid with high selectivity and high yield (over 85%) was achieved. The reaction conditions were mild, and the product was easy to separate, showing potential for industrial application.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of chemical synthesis, specifically relating to a method for preparing succinic acid from tartaric acid. Background Technology
[0002] Tartaric acid is a polyhydroxy, four-carbon dicarboxylic acid that can be widely obtained from biomass plants, such as tamarind and grapes. It is one of the organic acids produced during winemaking in the wine industry. Tartaric acid is generally produced through chemical and biological fermentation methods.
[0003] Succinic acid is an important biomass-based platform compound with broad application prospects. Succinic acid can be used to synthesize food additives, pharmaceutical intermediates, polyesters, and plasticizers. Currently, succinic acid is produced on an industrial scale by catalytic hydrogenation of maleic anhydride or maleic acid from fossil-based sources. This method uses non-renewable raw materials and is not a green process. Therefore, using biomass-based raw materials to prepare succinic acid is an emerging alternative method. In recent years, there have been research reports on the preparation of succinic acid from tartaric acid. Zhang et al. used NH4ReO4 catalyst to obtain and separate maleic acid from tartaric acid within 24 hours. The separated maleic acid was further hydrogenated with Pt / C catalyst and H2 (7 bar) at room temperature to generate succinic acid, realizing a highly selective two-step method for the production of succinic acid from tartaric acid (Chemsuschem, 2016, 9(19): 2774-2778); Vlacho et al. used acetic acid and MoO2 to produce succinic acid. x High-efficiency liquid-phase catalysis of tartaric acid to succinic acid under the conditions of BC and HBr at 170 °C and hydrogen atmosphere (Catalysis Science & Technology, 2017, 7(21): 4944-4954); Pagán-Torres et al. used MoO X -0.3wt% Pd / TiO2 catalyst catalyzes the hydrodeoxygenation of tartaric acid to prepare succinic acid (Chemcatchem, 2021, 13(5): 1294-1298). Current reported studies all require some metal catalysis and need to be carried out in a hydrogen atmosphere, and the reaction conditions are not very mild. We have pioneered a mild and innovative transfer hydrogenation reaction system. Currently, there are no reports on the preparation of succinic acid from tartaric acid through iodine-mediated transfer hydrogenation. Summary of the Invention
[0004] In view of the shortcomings and difficulties in the existing technology, the present invention aims to provide a method for preparing succinic acid from tartaric acid.
[0005] This invention is achieved through the following technical solution:
[0006] A method for preparing succinic acid from tartaric acid includes the following steps:
[0007] Tartaric acid was added to a Schlenk reaction tube, followed by an iodine catalyst, and finally a solvent and a hydrogen source. Nitrogen was purged three times using a double-row tube. The reaction was heated with stirring on a heating module. After the reaction, the reaction tube was cooled to room temperature in a water bath. Succinic acid precipitated out as a solid and was separated by filtration to obtain succinic acid.
[0008] Furthermore, the iodine catalyst is elemental iodine or hydroiodic acid.
[0009] Furthermore, the solvent and hydrogen source are methyl ketones, including methyl isobutyl ketone, 2-butanone, 2-pentanone, and 2-heptanone.
[0010] Furthermore, the molar ratio of iodine catalyst to tartaric acid is 0.01–0.5, the amount of solvent and hydrogen source added is 1–20 mL, the temperature of the heating module is 120–200 °C, and the reaction time is 1–15 h.
[0011] Furthermore, when using methyl isobutyl ketone as a solvent, the product separation can be achieved by direct filtration at low temperatures.
[0012] Compared with the prior art, the beneficial effects of the present invention are:
[0013] This invention develops an innovative transfer hydrogenation reaction system to selectively generate succinic acid from tartaric acid through hydrodeoxygenation. It utilizes an iodine catalyst as the transfer hydrogenation catalyst, methyl ketones as the hydrogen donor and solvent, and the reaction can be carried out under atmospheric pressure and nitrogen atmosphere using a pressure-resistant tube, achieving a yield of over 85%. When using methyl isobutyl ketone as the solvent, succinic acid precipitates as a solid upon cooling to room temperature, which can be easily separated by filtration. This method offers high selectivity, uses inexpensive catalysts, has mild reaction conditions, and the products are easily separated, demonstrating potential industrial application value. Attached Figure Description
[0014] Figure 1 This is a schematic diagram of the preparation of succinic acid from tartaric acid according to the present invention. Detailed Implementation
[0015] The present invention will be described below through specific embodiments, but the present invention is not limited thereto.
[0016] A method for preparing succinic acid from tartaric acid according to the present invention (e.g.) Figure 1 (As shown), follow these steps:
[0017] Tartaric acid was added to the reactor, followed by catalyst at a molar ratio of iodine catalyst to tartaric acid of 0.01–0.5. Finally, 1–20 mL of hydrogen-donating solvent was added. The reactor was stirred and heated to 60–200 °C under a nitrogen atmosphere. After reacting for 1–15 hours, the reactor was cooled. The resulting product was then analyzed.
[0018] The iodine catalyst described herein may be elemental iodine, hydroiodic acid, or other iodine chemicals that can generate elemental iodine or hydroiodic acid.
[0019] The hydrogen-donating solvents mentioned therein include, but are not limited to, methyl ketones such as MIBK, 2-butanone, 2-pentanone, and 2-heptanone.
[0020] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.
[0021] Example 1
[0022] Add 1 mmol tartaric acid, 0.25 mmol iodine, and 2 mL MIBK to a 25 mL pressure-resistant glass reaction tube. Perform N2 replacement three times using a double-row tube. Then, heat the reaction at 160 °C for 2 hours using a heating module. After the reaction, cool the reaction tube to room temperature in a water bath. Extract the reaction solution three times with deionized water. Dissolve the solids in deionized water, combine the aqueous phases, and dilute to 25 mL. The conversion rate of tartaric acid reached 100%, and the yield of succinic acid was 83%. The conversion rate of tartaric acid and the yield of succinic acid were analyzed and quantified by high-performance liquid chromatography (HPLC). The detection and calculation of the conversion rate of tartaric acid and the yield of succinic acid were performed according to the following methods.
[0023] The concentrations of tartaric acid and succinic acid were detected using a Waters H-Class series high-performance liquid chromatograph (PDA detector, wavelength 234.2 nm, ICSep Coregel 107H, 7.8 mm ID × 300 mm liquid chromatographic column, mobile phase 0.6 g / L dilute sulfuric acid).
[0024] Calculation of tartaric acid conversion rate:
[0025] Tartaric acid conversion rate = 1 - (remaining molar amount of tartaric acid / added molar amount of tartaric acid) × 100%
[0026] Calculation of succinic acid yield:
[0027] succinic acid yield = (molar amount of succinic acid / molar amount of tartaric acid added) × 100%
[0028] Example 2
[0029] Add 1 mmol tartaric acid, 0.25 mmol hydroiodine, and 2 mL MIBK to a 25 mL pressure-resistant glass reaction tube. Perform N2 replacement three times using a double-row tube. Then, heat the reaction at 160 °C for 3 hours using a heating module. After the reaction, cool the reaction tube to room temperature in a water bath. Extract the collected reaction solution three times with deionized water. Dissolve the solids after the reaction in deionized water, combine the aqueous phases, and bring the volume to 25 mL. The conversion rate of tartaric acid reached 100%, and the yield of succinic acid was 83%.
[0030] Example 3
[0031] Add 1 mmol tartaric acid, 0.1 mmol iodine, and 2 mL MIBK to a 25 mL pressure-resistant glass reaction tube. Perform N2 replacement three times using a double-row tube. Then, heat the reaction at 160 °C for 4 hours using a heating module. After the reaction, cool the reaction tube to room temperature in a water bath. Extract the collected reaction solution three times with deionized water. Dissolve the solids in deionized water, combine the aqueous phases, and bring the volume to 25 mL. The conversion rate of tartaric acid reached 100%, and the yield of succinic acid was 85%.
[0032] Example 4
[0033] Add 1 mmol tartaric acid, 0.25 mmol iodine, and 2 mL 2-butanone to a 25 mL pressure-resistant glass reaction tube. Perform N2 purging three times using a double-row tube. Then, heat the reaction at 160 °C for 1 h using a heating module. After the reaction, cool the reaction tube to room temperature in a water bath. Extract the collected reaction solution three times with deionized water. Dissolve the solids in deionized water, combine the aqueous phases, and bring the volume to 25 mL. The conversion rate of tartaric acid was 32%, and the yield of succinic acid was 8%.
[0034] Example 5
[0035] Add 1 mmol tartaric acid, 0.25 mmol iodine, and 2 mL MIBK to a 25 mL pressure-resistant glass reaction tube. Perform N2 replacement three times using a double-row tube. Then, heat the reaction at 180 °C for 1 h using a heating module. After the reaction, cool the reaction tube to room temperature in a water bath. Extract the collected reaction solution three times with deionized water. Dissolve the solids after the reaction in deionized water, combine the aqueous phases, and bring the volume to 25 mL. The conversion rate of tartaric acid reached 100%, and the yield of succinic acid was 83%.
[0036] Example 6
[0037] The procedure involved adding 2 mmol of tartaric acid, 0.5 mmol of iodine, and 5 mL of MIBK to a 50 mL stainless steel high-pressure reactor. 1 MPa of N2 was then introduced. The reaction was carried out at 160 °C for 3 hours. The high-temperature, high-pressure reactor was then cooled to room temperature in a water bath. The extracted reaction solution was extracted three times with deionized water. The resulting solid was dissolved in deionized water, and the aqueous phases were combined and brought to a final volume of 25 mL. The conversion rate of tartaric acid reached 100%, and the yield of succinic acid was 80%.
[0038] Example 7
[0039] The procedure involved adding 10 mmol of tartaric acid, 2.5 mmol of iodine, and 20 mL of MIBK to a 50 mL stainless steel high-pressure reactor. The reactor was then charged with 1 MPa of N2 and reacted at 160 °C for 4 hours. The high-temperature, high-pressure reactor was then cooled to room temperature in a water bath. The resulting reaction solution was extracted three times with deionized water. The solid phases were dissolved in deionized water, and the aqueous phases were combined and brought to a final volume of 250 mL. The conversion rate of tartaric acid reached 100%, and the yield of succinic acid was 84%.
[0040] The above description merely illustrates preferred embodiments of the present invention, and while the description is relatively specific and detailed, it should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications, improvements, and substitutions without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this patent should be determined by the appended claims.
Claims
1. A method for preparing succinic acid from tartaric acid, characterized in that, Includes the following steps: Tartaric acid, followed by an iodine catalyst, and finally a solvent and hydrogen source were added to a Schlenk reaction tube. Nitrogen purging was performed three times using a double-row tube. The reaction was heated with stirring on a heating module. After the reaction, the reaction tube was cooled to room temperature in a water bath. Succinic acid precipitated as a solid, and the product was separated by filtration. The iodine catalyst was elemental iodine or hydroiodic acid. The solvent and hydrogen source were methyl ketones, including methyl isobutyl ketone, 2-butanone, 2-pentanone, and 2-heptanone. The molar ratio of iodine catalyst to tartaric acid was 0.01–0.
5. The amount of solvent and hydrogen source added was 1–20 mL. The temperature of the heating module was 120–200 °C, and the reaction time was 1–15 h.
2. The method for preparing succinic acid from tartaric acid according to claim 1, characterized in that, The product separation is performed by direct filtration at low temperature when methyl isobutyl ketone is used as the solvent.