CN115745784A - Method for purifying succinic acid and reducing sulfate radical content in succinic acid - Google Patents
Method for purifying succinic acid and reducing sulfate radical content in succinic acid Download PDFInfo
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- CN115745784A CN115745784A CN202211408642.6A CN202211408642A CN115745784A CN 115745784 A CN115745784 A CN 115745784A CN 202211408642 A CN202211408642 A CN 202211408642A CN 115745784 A CN115745784 A CN 115745784A
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Abstract
The invention discloses a method for purifying succinic acid and reducing sulfate radical content in succinic acid, which comprises the steps of dissolving, flocculating adsorption, salting out crystallization, re-dissolving, basic anion exchange resin adsorption, crystallization and the like. Compared with the prior art, the method has the advantages that the purity of the obtained product is more than 99.8 percent, the sulfate ion content is less than 0.005 percent, the total yield is high, the product purity is high, the technical scheme is simple, heavy metal barium ions are not needed, and the prepared product can be used in most application fields and has wide market application value.
Description
Technical Field
The invention relates to a method for purifying succinic acid, in particular to a method for purifying succinic acid and reducing sulfate radical content in succinic acid.
Background
Succinic acid, commonly known as succinic acid, is a dicarboxylic acid in the form of colorless crystals, a monosodium glutamate, which is soluble in water, ethanol and diethyl ether, and insoluble in chloroform and dichloromethane. The important application of the succinic acid is to prepare five-membered heterocyclic compounds; succinic acid (including salts) can be used in food industry such as bean paste, soy sauce, japanese wine, flavoring ham, sausage, aquatic product, etc.; succinic acid can be used as a preservative, an ionic chelating agent, a surfactant and in lubricants, additives, elastomers; meanwhile, the method can also be used in the pharmaceutical industry.
The industrial production methods are many, and mainly include oxidation, hydrogenation, acrylic acid oxo synthesis, electrolysis, acetylene, fermentation, and the like. The oxidation method is that paraffin is deeply oxidized to generate a mixture of various carboxylic acids, and the succinic acid is obtained after separation steps of steam distillation, crystallization and the like. The hydrogenation method is characterized in that maleic anhydride or fumaric acid is subjected to hydrogenation reaction under the action of a catalyst to generate succinic acid, and then the succinic acid is separated to obtain a finished product. The catalyst is nickel or noble metal, and the reaction temperature is about 130-140 ℃. The method for synthesizing the acrylic acid by carbonyl synthesis comprises the step of generating the succinic acid by acrylic acid and carbon monoxide under the action of a catalyst. Has not been industrialized. The succinic acid can be obtained by electrolyzing phthalic anhydride, sulfuric acid and water in a ratio of 1: 0.5: 4 in a ceramic electrolytic cell by an electrolytic method. The raw material synthesized by the electrolytic method is maleic acid or maleic anhydride, the cathode and the anolyte are separated by a cationic membrane by dilute sulfuric acid, and the cathode and the anode are both generally made of lead plates and are generally synthesized by a plate-frame type electrolytic cell. Acetylene method, acetylene reacts with carbon monoxide and water in acidic medium in the presence of catalyst to obtain succinic acid. A fermentation method. Compared with the traditional chemical method, the method for producing the succinic acid by the microbial fermentation method has the advantages that: the production cost is competitive; renewable agricultural resources including carbon dioxide are used as raw materials, so that the dependence on petrochemical raw materials is avoided; reduces the pollution of the chemical synthesis process to the environment. The main synthesis methods at present are electrolytic synthesis methods and fermentation methods.
The electrolysis method has obvious advantages in industrial application and better environment friendliness, but the product obtained by the electrolysis method has too high sulfate radical content and is difficult to remove, so that the application of succinic acid in high-end fields is influenced, and the multi-directional development of succinic acid is limited.
Disclosure of Invention
The invention aims to provide a method for purifying succinic acid and reducing sulfate radical content in the succinic acid, which improves the purity of succinic acid (succinic acid) products, reduces the sulfate radical content in the succinic acid, expands the application of the succinic acid, and particularly relates to the application in high-end fields.
In order to achieve the purpose, the method for purifying the succinic acid and reducing the sulfate radical content in the succinic acid comprises the following steps:
(1) Adding deionized water into a reaction kettle, introducing nitrogen, keeping the nitrogen atmosphere in the reaction kettle, heating to 50-60 ℃, adding crude succinic acid, stirring and dissolving to obtain a succinic acid aqueous solution;
(2) Adding the succinic acid aqueous solution obtained in the step (1) into 0.05 percent of cationic polyacrylamide solution, slowly stirring for 10-15 minutes, standing, and filtering to obtain filtrate;
(3) Slowly adding inorganic salt into the filtrate obtained in the step (2), simultaneously cooling to 20-25 ℃, salting out for crystallization, and separating out succinic acid solid;
(4) Washing the succinic acid solid obtained in the step (3), and dissolving again to obtain a succinic acid aqueous solution;
(5) Enabling the succinic acid aqueous solution obtained in the step (4) to flow through activated basic anion exchange resin to obtain resin purifying liquid;
(6) And (4) cooling the resin purified liquid obtained in the step (5) to 0-5 ℃, crystallizing, washing and drying to obtain a succinic acid product.
Preferably, the purity of the crude succinic acid in the step (1) is 85-98%, and the sulfate radical content is 0.5-2%.
Preferably, the inorganic salt in step (3) is at least one of sodium dihydrogen phosphate and sodium phosphate.
Preferably, the washing liquid adopted in the washing process in the step (4) and the step (6) is deionized water with the temperature of 2-8 ℃.
Preferably, the basic anion exchange resin in step (5) is a strongly basic anion exchange resin or a weakly basic anion exchange resin, preferably a strongly basic anion exchange resin.
Preferably, the content of sulfate ions in the resin purified liquid is detected in real time in the step (5), and the detection method is ion chromatography.
Preferably, the succinic acid product obtained in the step (6) has the purity of more than 99.8 percent and the sulfate ion content of less than 0.005 percent.
Preferably, the crystallization mother liquor in the step (6) can be used for dissolving the crude product in the step (1), so that the total yield is improved.
Preferably, the weight of the inorganic salt in the step (3) is 30-40% of the weight of the crude succinic acid.
According to the method, fine solid particles and partial sulfate radicals in the crude product can be removed through flocculation adsorption of 0.05% cationic polyacrylamide solution; through the salting-out crystallization step, the purity of the crude product can be obviously improved, the sulfate radical content is obviously reduced, through the addition of inorganic salt and the synergistic effect of ions, the yield of the succinic acid precipitation crystallization step is higher, the sulfate radical removal rate is higher, and the crystallization purity is ensured; a small amount of residual sulfate radicals in the crude product can be adsorbed by the basic anion exchange resin to obtain a high-quality succinic acid product; the crystallization mother liquor is reused, and the recrystallization yield is improved. Different crystallization processes and temperatures are adopted in the step (3) and the step (5), so that the sulfate radical content in the crude product is efficiently removed while the yield is considered.
The inorganic salt used in salting out crystallization can be reused after evaporation crystallization, and the alkaline anion exchange resin can be reused after regeneration.
Compared with the prior art, the method has the advantages that the purity of the obtained product is more than 99.8 percent, the sulfate ion content is less than 0.005 percent, the total yield is high, the product purity is high, the technical scheme is simple, heavy metal barium ions are not needed, and the prepared product can be used in most application fields and has wide market application value.
Detailed Description
The technical solutions in the embodiments of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
A method for purifying succinic acid and reducing the content of sulfate radicals in the succinic acid comprises the following steps:
(1) Adding 1 ton of deionized water into a reaction kettle, introducing nitrogen, keeping the nitrogen atmosphere in the reaction kettle, heating to 50-60 ℃, adding 235 kg of crude succinic acid, stirring and dissolving to obtain a succinic acid aqueous solution, wherein the purity of the crude succinic acid is 86%, and the sulfate radical content is 1.8%;
(2) Adding 20L of 0.05% cationic polyacrylamide solution into the succinic acid aqueous solution obtained in the step (1), slowly stirring for 10-15 minutes, standing, and filtering to obtain filtrate;
(3) Slowly adding 75 kg of sodium phosphate into the filtrate obtained in the step (2), simultaneously cooling to 20-22 ℃, salting out and crystallizing, and separating out succinic acid solid;
(4) Washing the succinic acid solid obtained in the step (3) with deionized water at 3 ℃, and dissolving again to obtain a succinic acid aqueous solution;
(5) Enabling the succinic acid aqueous solution obtained in the step (4) to flow through activated strong-base anion exchange resin to obtain resin purifying liquid, and detecting the sulfate radical content of the effluent liquid in real time by using ion chromatography;
(6) And (3) cooling the resin purified liquid obtained in the step (5) to 0-5 ℃ for crystallization, washing and drying to obtain a succinic acid product, wherein the crystallization mother liquor can be used for dissolving the crude product in the step (1).
Example 2
A method for purifying succinic acid and reducing sulfate radical content in succinic acid comprises the following steps:
(1) Adding 1 ton of deionized water into a reaction kettle, introducing nitrogen, keeping the nitrogen atmosphere in the reaction kettle, heating to 50-60 ℃, adding 200 kg of crude succinic acid, stirring and dissolving to obtain a succinic acid aqueous solution, wherein the purity of the crude succinic acid is 94%, and the sulfate radical content is 0.6%;
(2) Adding 20L of 0.05% cationic polyacrylamide solution into the succinic acid aqueous solution obtained in the step (1), slowly stirring for 10-15 minutes, standing, and filtering to obtain filtrate;
(3) Slowly adding 80 kg of sodium phosphate into the filtrate obtained in the step (2), simultaneously cooling to 23-25 ℃, and salting out crystals to separate out succinic acid solid;
(4) Washing the succinic acid solid obtained in the step (3) with deionized water at 7 ℃, and dissolving again to obtain a succinic acid aqueous solution;
(5) Enabling the succinic acid aqueous solution obtained in the step (4) to flow through activated weak-base anion exchange resin to obtain resin purifying liquid, and detecting the sulfate radical content of the effluent liquid in real time by using ion chromatography;
(6) And (3) cooling the resin purified liquid obtained in the step (5) to 0-5 ℃ for crystallization, washing and drying to obtain a succinic acid product, wherein the crystallization mother liquor can be used for dissolving the crude product in the step (1).
Example 3
A method for purifying succinic acid and reducing sulfate radical content in succinic acid comprises the following steps:
(1) Adding 1 ton of deionized water into a reaction kettle, introducing nitrogen, keeping the nitrogen atmosphere in the reaction kettle, heating to 50-60 ℃, adding 215 kg of crude succinic acid, stirring and dissolving to obtain a succinic acid aqueous solution, wherein the purity of the crude succinic acid is 93%, and the sulfate radical content is 1.0%;
(2) Adding 30L of 0.05% cationic polyacrylamide solution into the succinic acid aqueous solution obtained in the step (1), slowly stirring for 10-15 minutes, standing, and filtering to obtain filtrate;
(3) Slowly adding 74 kg of sodium dihydrogen phosphate into the filtrate obtained in the step (2), simultaneously cooling to 21-23 ℃, and salting out crystals to separate out succinic acid solid;
(4) Washing the succinic acid solid obtained in the step (3) with deionized water at 5 ℃, and dissolving again to obtain a succinic acid aqueous solution;
(5) Enabling the succinic acid aqueous solution obtained in the step (4) to flow through activated weak-base anion exchange resin to obtain resin purified liquid, and detecting the sulfate radical content of the effluent liquid in real time by using ion chromatography;
(6) And (3) cooling the resin purified liquid obtained in the step (5) to 0-5 ℃ for crystallization, washing and drying to obtain a succinic acid product, wherein the crystallization mother liquor can be used for dissolving the crude product in the step (1).
Example 4
A method for purifying succinic acid and reducing sulfate radical content in succinic acid comprises the following steps:
(1) Adding 1 ton of deionized water into a reaction kettle, introducing nitrogen, keeping the nitrogen atmosphere in the reaction kettle, heating to 50-60 ℃, adding 210 kg of crude succinic acid, stirring and dissolving to obtain a succinic acid aqueous solution, wherein the purity of the crude succinic acid is 93%, and the sulfate radical content is 0.6%;
(2) Adding 20L of 0.05% cationic polyacrylamide solution into the succinic acid aqueous solution obtained in the step (1), slowly stirring for 10-15 minutes, standing, and filtering to obtain filtrate;
(3) Slowly adding 80 kg of a mixture of sodium phosphate and sodium dihydrogen phosphate into the filtrate obtained in the step (2), simultaneously cooling to 20-22 ℃, salting out and crystallizing, and separating out succinic acid solid;
(4) Washing the succinic acid solid obtained in the step (3) with deionized water at 2 ℃, and dissolving again to obtain a succinic acid aqueous solution;
(5) Enabling the succinic acid aqueous solution obtained in the step (4) to flow through activated strong-base anion exchange resin to obtain resin purifying liquid, and detecting the sulfate radical content of the effluent liquid in real time by using ion chromatography;
(6) And (3) cooling the resin purified liquid obtained in the step (5) to 0-5 ℃ for crystallization, washing and drying to obtain a succinic acid product, wherein the crystallization mother liquor can be used for dissolving the crude product in the step (1).
Comparative example 1
This example differs from example 4 in that: in the step (3), 80 kg of a mixture of sodium phosphate and sodium dihydrogen phosphate was not added.
The rest is the same as embodiment 4, and will not be described again.
Comparative example 2
The present embodiment differs from embodiment 4 in that: and (5) reducing.
The rest is the same as embodiment 4, and will not be described again.
Performance testing
TABLE 1 comparison of Performance indices of products made according to the invention
Remarking: the data in the table are measured according to GB/T34686-2017, wherein the sulfate ion measurement is carried out by ion chromatography or the national standard method.
The data in the table show that the performance preparation of the succinic acid products prepared in the embodiments 1 to 4 of the invention is superior to that of the national standard superior products, and particularly, the content of sulfate ions is obviously lower than that of the national standard superior products; in the comparative example 1, because a salting-out crystallization method is not adopted, the product yield is obviously reduced, part of performance indexes are lower than those of national standard superior products, and the sulfate radical content is obviously increased compared with that in the example 4; comparative example 2, which did not use ion exchange resin adsorption, gave a comparable yield, but the sulfate content was significantly higher than that of example 4.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (9)
1. A method for purifying succinic acid and reducing sulfate radical content in succinic acid is characterized by comprising the following steps:
(1) Adding deionized water into a reaction kettle, introducing nitrogen, keeping the nitrogen atmosphere in the reaction kettle, heating to 50-60 ℃, adding crude succinic acid, stirring and dissolving to obtain a succinic acid aqueous solution;
(2) Adding the succinic acid aqueous solution obtained in the step (1) into 0.05 percent of cationic polyacrylamide solution, slowly stirring for 10-15 minutes, standing, and filtering to obtain filtrate;
(3) Slowly adding inorganic salt into the filtrate obtained in the step (2), simultaneously cooling to 20-25 ℃, salting out for crystallization, and separating out succinic acid solid;
(4) Washing the succinic acid solid obtained in the step (3), and dissolving again to obtain a succinic acid aqueous solution;
(5) Allowing the succinic acid aqueous solution obtained in the step (4) to flow through activated basic anion exchange resin to obtain resin purified liquid;
(6) And (4) cooling the resin purified liquid obtained in the step (5) to 0-5 ℃, crystallizing, washing and drying to obtain a succinic acid product.
2. The method for purifying succinic acid and reducing sulfate radical content in succinic acid according to claim 1, wherein the purity of the crude succinic acid in step (1) is 85-98%, and the sulfate radical content is 0.5-2%.
3. The method of claim 1, wherein the inorganic salt in step (3) is at least one of sodium dihydrogen phosphate and sodium phosphate.
4. The method for purifying succinic acid and reducing sulfate radical content in succinic acid according to claim 1, wherein the washing liquid used in the washing process in steps (4) and (6) is deionized water at 2-8 ℃.
5. The method for purifying succinic acid and reducing sulfate content in succinic acid according to claim 1, wherein in the step (5), the basic anion exchange resin is a strong basic anion exchange resin or a weak basic anion exchange resin, preferably a strong basic anion exchange resin.
6. The method for purifying succinic acid and reducing sulfate content in succinic acid according to claim 1, wherein the content of sulfate ions in the resin purified liquid is detected in real time in step (5), and the detection method is ion chromatography.
7. The method of claim 1, wherein the succinic acid product obtained in step (6) has a purity of > 99.8% and a sulfate ion content of < 0.005%.
8. The method for purifying succinic acid and reducing sulfate content in succinic acid according to claim 1, wherein the mother liquor from step (6) can be used for dissolving crude products in step (1), thereby increasing the total yield.
9. The method for purifying succinic acid and reducing sulfate radical content in succinic acid according to claim 1, wherein the weight of the inorganic salt in the step (3) is 30-40% of the weight of the crude product of succinic acid.
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