CN115677484A - Method for preparing succinic acid from tartaric acid - Google Patents
Method for preparing succinic acid from tartaric acid Download PDFInfo
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- CN115677484A CN115677484A CN202211134012.4A CN202211134012A CN115677484A CN 115677484 A CN115677484 A CN 115677484A CN 202211134012 A CN202211134012 A CN 202211134012A CN 115677484 A CN115677484 A CN 115677484A
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Abstract
The invention relates to a method for preparing succinic acid from tartaric acid. The invention develops an innovative transfer hydrogenation reaction system for selectively generating succinic acid by hydrodeoxygenation of tartaric acid, wherein iodine simple substance is used as a transfer hydrogenation catalyst, methyl isobutyl ketone is used as a hydrogen donor and a solvent, the reaction can be carried out under normal pressure and nitrogen by using a pressure resistant pipe, and the tartaric acid is selectively converted into the succinic acid through the transfer hydrogenation process. A succinic acid yield of 85% was obtained. In addition, the generated succinic acid product has low solubility in methyl isobutyl ketone, so that the succinic acid can be precipitated in a solid form when being cooled to normal temperature, and the product can be conveniently separated by filtration. The method has high selectivity, uses cheap catalyst iodine, has mild reaction conditions, is easy to separate products, is easy to apply to industrialization, and has huge research and application values.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for preparing succinic acid from tartaric acid.
Background
Tartaric acid is a polyhydroxy, four-carbon dicarboxylic acid, and is widely available from biomass plants, such as tamarind and grape. One of the organic acids produced in the brewing industry in brewing wine is tartaric acid. Tartaric acid is typically produced by chemical and biological fermentation processes.
The succinic acid is an important biomass-based platform compound molecule and has wide application prospect. The succinic acid can be used for synthesizing food additives, medical intermediates, polyesters and plasticizers. Succinic acid is currently produced on an industrial scale by catalytic hydrogenation of maleic anhydride or maleic acid of fossil-based origin, which is a non-renewable source of raw materials and is not a green process. The use of biomass-based feedstocks for succinic acid production is an emerging alternative. In recent years, the use of NH in the preparation of succinic acid from tartaric acid has been reported 4 ReO 4 The catalyst yielded and separated maleic acid from tartaric acid in 24 hours. Pt/C catalyst and H for maleic acid after separation 2 (7 bar) further hydrogenated to generate the succinic acid at room temperature, thereby realizing the high-selectivity two-step method for generating the succinic acid by the tartaric acid (Chemusshem, 2016,9 (19): 2774-2778); vlacho et al used acetic acid, moO x Preparation of succinic acid (Catalysis Science) by high performance liquid phase Catalysis of tartaric acid under hydrogen atmosphere at 170 ℃ under the conditions of/BC and HBr&Technology,2017,7 (21): 4944-4954); use of MoO as Pag n-Torres et al X -0.3wt％Pd/TiO 2 The catalyst catalyzes tartaric acid to prepare succinic acid by hydrodeoxygenation (Chemcathem, 2021, 13 (5): 1294-1298). The studies reported at present all require some metal catalysis and reaction under hydrogen atmosphere, and the reaction conditions are not very mild. We have created a reaction mild and innovative transfer hydrogenation reaction system, and at present, there is no report on the preparation of succinic acid by using tartaric acid through an iodine-mediated transfer hydrogenation process.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a method for preparing succinic acid from tartaric acid.
The invention is realized by the following technical scheme:
a method for preparing succinic acid from tartaric acid comprises the following steps:
adding tartaric acid into a Schlenk reaction tube, adding an iodine catalyst, and finally adding a solvent and a hydrogen source; performing nitrogen replacement three times by using double rows of pipes; heating under stirring by a heating module; after the reaction, cooling the reaction tube to normal temperature in water bath; the succinic acid precipitates out in solid form and is separated by filtration to obtain succinic acid.
Further, the iodine catalyst is iodine simple substance or hydroiodic acid.
Further, the solvent and the hydrogen source are methyl ketones, including methyl isobutyl ketone, 2-butanone, 2-pentanone, 2-heptanone.
Further, the iodine catalyst: the molar ratio of the tartaric acid is 0.01-0.5, the adding amount of the solvent and the hydrogen source is 1-20 mL, the temperature of the heating module is 120-200 ℃, and the reaction time is 1-15 h.
Further, the product isolation can be directly isolated by filtration at low temperature using methyl isobutyl ketone as solvent.
Compared with the prior art, the invention has the beneficial effects that:
the invention develops an innovative transfer hydrogenation reaction system for selectively generating succinic acid by hydrodeoxygenation of tartaric acid, uses an iodine catalyst as a transfer hydrogenation catalyst, uses methyl ketones as a hydrogen donor and a solvent, can react under normal pressure nitrogen by using a pressure-resistant pipe, and has the yield of over 85 percent. When methyl isobutyl ketone is used as a solvent, succinic acid is precipitated in a solid form when cooled to normal temperature, and can be conveniently separated by filtration. The method has high selectivity, uses cheap catalyst, has mild reaction condition and easy separation of products, and has potential industrial application value.
Drawings
FIG. 1 is a schematic diagram of tartaric acid to succinic acid according to the present invention.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The method for preparing succinic acid from tartaric acid (shown in figure 1) comprises the following steps:
adding tartaric acid to the reactor, and reacting according to the iodine catalyst: tartaric acid = 0.01-0.5 mol ratio, adding catalyst, and finally adding 1-20 mL hydrogen donor solvent. Stirring and heating to 60-200 ℃ in nitrogen atmosphere. After reacting for 1-15 h, cooling the reactor. And detecting after treatment.
The iodine catalyst can be iodine simple substance, hydroiodic acid, or other iodine chemical substances capable of generating the iodine simple substance or the hydroiodic acid.
The hydrogen donor solvent includes but is not limited to methyl ketones such as MIBK, 2-butanone, 2-pentanone, 2-heptanone, etc.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
To a 25mL pressure-resistant glass reaction tube were added 1mmol of tartaric acid, 0.25mmol of iodine, and 2mL of MIBK. N Using double rows of tubes 2 The substitution was carried out three times. Then heating reaction is carried out by using a heating module, and the reaction lasts for 2h at 160 ℃. And after the reaction is finished, cooling the reaction tube to normal temperature in water bath. Extracting the reaction liquid taken out by using deionized water for 3 times, dissolving the solid after the reaction by using the deionized water, combining water phases and fixing the volume to 25ml, wherein the conversion rate of tartaric acid reaches 100 percent and the yield of succinic acid reaches 83 percent. The conversion rate of tartaric acid and the yield of succinic acid were analyzed and quantified by high performance liquid chromatography, and the conversion rate of tartaric acid and the yield of succinic acid were detected and calculated according to the following methods.
The instrument for detecting the concentration of tartaric acid and succinic acid is a Watts H-Class high performance liquid chromatograph (PDA detector, 234.2nm wavelength, ICSep Coregel 107H,7.8mm ID multiplied by 300mm liquid chromatography column, mobile phase is 0.6g/L dilute sulfuric acid).
Calculation of tartaric acid conversion:
conversion of tartaric acid =1- (remaining molar amount of tartaric acid/molar amount of tartaric acid charged) × 100%
Calculating the yield of the succinic acid:
yield of succinic acid = (molar amount of succinic acid/molar amount of tartaric acid put) × 100%
Example 2
Withstand voltage to 25mLA glass reaction tube was charged with 1mmol of tartaric acid, 0.25mmol of iodonium hydride and 2mL of MIBK. N Using double rows of tubes 2 The substitution was carried out three times. Then heating reaction is carried out by using a heating module, and the reaction lasts for 3h at 160 ℃. And after the reaction is finished, cooling the reaction tube to normal temperature in water bath. And extracting the taken reaction liquid for 3 times by using deionized water, dissolving the reacted solid by using the deionized water, combining water phases, and fixing the volume to 25ml, wherein the conversion rate of tartaric acid reaches 100%, and the yield of succinic acid reaches 83%.
Example 3
To a 25mL pressure-resistant glass reaction tube were added 1mmol of tartaric acid, 0.1mmol of iodine, and 2mL of MIBK. N Using double rows of tubes 2 The substitution was carried out three times. Then heating reaction is carried out by using a heating module, and the reaction lasts for 4h at 160 ℃. And after the reaction is finished, cooling the reaction tube to normal temperature in water bath. And extracting the taken reaction liquid for 3 times by using deionized water, dissolving the reacted solid by using the deionized water, combining water phases, and fixing the volume to 25ml, wherein the conversion rate of tartaric acid reaches 100%, and the yield of succinic acid reaches 85%.
Example 4
To a 25mL pressure-resistant glass reaction tube were added 1mmol of tartaric acid, 0.25mmol of iodine and 2mL of 2-butanone. N Using double rows of tubes 2 The substitution was carried out three times. Then heating reaction is carried out by using a heating module, and the reaction lasts for 1h at 160 ℃. And after the reaction is finished, cooling the reaction tube to normal temperature in water bath. And extracting the taken reaction liquid for 3 times by using deionized water, dissolving the reacted solid by using the deionized water, combining water phases, and fixing the volume to 25ml, wherein the conversion rate of tartaric acid is 32% and the yield of succinic acid is 8%.
Example 5
To a 25mL pressure-resistant glass reaction tube were added 1mmol of tartaric acid, 0.25mmol of iodine, and 2mL of MIBK. N Using double rows of tubes 2 The substitution was carried out three times. Then heating reaction is carried out by using a heating module, and reaction is carried out for 1h at 180 ℃. And after the reaction is finished, cooling the reaction tube to normal temperature in water bath. And extracting the taken reaction liquid for 3 times by using deionized water, dissolving the reacted solid by using the deionized water, combining water phases, and fixing the volume to 25ml, wherein the conversion rate of tartaric acid reaches 100%, and the yield of succinic acid reaches 83%.
Example 6
The procedure was to 50mL stainless steel2mmol tartaric acid, 0.5mmol iodine and 5mL MIBK were added to the steel autoclave respectively. Is charged into 1Mpa N 2 . Reacting at 160 ℃ for 3h. Then the high-temperature high-pressure reaction kettle is cooled to normal temperature in water bath. Extracting the reaction liquid taken out by deionized water for 3 times, dissolving the solid after reaction by the deionized water, combining water phases and fixing the volume to 25ml, wherein the conversion rate of tartaric acid reaches 100 percent and the yield of succinic acid reaches 80 percent.
Example 7
The operation steps are that 10mmol of tartaric acid, 2.5mmol of iodine and 20mL of MIBK are respectively added into a 50mL stainless steel high-pressure reaction kettle body. Charging into 1Mpa N 2 And reacting at 160 ℃ for 4h. Then the high-temperature high-pressure reaction kettle is cooled to normal temperature in water bath. And extracting the taken reaction liquid for 3 times by using deionized water, dissolving the reacted solid by using the deionized water, combining water phases, and fixing the volume to 250ml, wherein the conversion rate of tartaric acid reaches 100%, and the yield of succinic acid reaches 84%.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (5)
1. The method for preparing succinic acid from tartaric acid is characterized by comprising the following steps of:
adding tartaric acid into a Schlenk reaction tube, adding an iodine catalyst, and finally adding a solvent and a hydrogen source; performing nitrogen replacement three times by using a double-row pipe; heating under stirring by a heating module; after the reaction, cooling the reaction tube to normal temperature in water bath; the succinic acid precipitates out in solid form and is separated by filtration to obtain succinic acid.
2. The method for preparing succinic acid from tartaric acid according to claim 1, wherein the iodine catalyst is elemental iodine or hydroiodic acid.
3. The method for preparing succinic acid from tartaric acid according to claim 1, wherein the solvent and the hydrogen source are methyl ketones, including methyl isobutyl ketone, 2-butanone, 2-pentanone, 2-heptanone.
4. The method for preparing succinic acid from tartaric acid according to claim 1, wherein the iodine catalyst: the molar ratio of the tartaric acid is 0.01-0.5, the adding amount of the solvent and the hydrogen source is 1-20 mL, the temperature of the heating module is 120-200 ℃, and the reaction time is 1-15 h.
5. The method for preparing succinic acid from tartaric acid according to claim 3, wherein the product separation is directly separated by filtration at low temperature using methyl isobutyl ketone as solvent.
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| CN116143574A (en) * | 2023-03-07 | 2023-05-23 | 南昌大学 | Method for preparing 1-isobutyl-3, 5-dimethylbenzene and 1,3, 5-triisobutylbenzene from methyl isobutyl ketone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143574A (en) * | 2023-03-07 | 2023-05-23 | 南昌大学 | Method for preparing 1-isobutyl-3, 5-dimethylbenzene and 1,3, 5-triisobutylbenzene from methyl isobutyl ketone |
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