CN111732503A - Method for extracting malic acid from calcium malate solution - Google Patents
Method for extracting malic acid from calcium malate solution Download PDFInfo
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- CN111732503A CN111732503A CN202010626542.5A CN202010626542A CN111732503A CN 111732503 A CN111732503 A CN 111732503A CN 202010626542 A CN202010626542 A CN 202010626542A CN 111732503 A CN111732503 A CN 111732503A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention relates to a method for extracting malic acid from a calcium malate solution, which comprises the following steps: (1) adding sulfuric acid into fermentation liquor containing calcium malate obtained by producing malic acid by a fermentation method or an enzymatic conversion method as a raw material for acidolysis, removing insoluble substances, and collecting a solution containing malic acid; (2) introducing the solution containing malic acid obtained in the step (1) into cation exchange resin to obtain cation-removed solution; (3) and (3) introducing the cation-removed solution obtained in the step (2) into anion exchange resin, adsorbing malic acid on the resin, washing with a detergent, adding dilute sulfuric acid for resolution, and collecting malic acid resolution liquid. The method provided by the invention has the characteristics of simple process, convenience in operation, high yield, high product quality and the like.
Description
Technical Field
The invention belongs to the field of food chemical industry, and particularly relates to a method for extracting malic acid from a calcium malate solution to produce malic acid.
Background
Malic acid, also known as 2-hydroxysuccinic acid, has two stereoisomers due to an asymmetric carbon atom in the molecule. In nature, it exists in three forms, namely D-malic acid, L-malic acid and their mixture DL-malic acid. The malic acid is white crystal or crystalline powder, has strong hygroscopicity, and is easily soluble in water and ethanol. Has a particularly pleasant sour taste. Malic acid is mainly used in food industry, and is an excellent sour agent and preservative. And has important application in clinical medicine, daily chemical health care, chemical industry and building industry.
The production methods at present comprise a chemical synthesis method, a fermentation method and an enzymatic production process. The chemical synthesis method has large investment and high technical requirement, and the synthesized product is DL-malic acid. The dilute calcium malate solution prepared by a fermentation method and an enzyme conversion method cannot effectively separate impurities such as sugar, protein and the like in the dilute calcium malate solution at present. Common methods for extracting malic acid from fermentation liquor include acidolysis and organic solvent extraction. The existing acidolysis process has complex process steps, low product purity and low yield. The conventional organic solvent extraction method has the problems of difficult back extraction, low product purity, solvent residue and the like.
Disclosure of Invention
The invention aims to solve the problems of difficult separation and low yield of impurities such as sugar, protein and the like in the product obtained by the existing malic acid production, provides a method for extracting and producing malic acid from a calcium malate solution, and improves the product quality and the yield.
Specifically, the method provided by the invention comprises the following steps:
(1) adding sulfuric acid into fermentation liquor containing calcium malate obtained by producing malic acid by a fermentation method or an enzymatic conversion method as a raw material for acidolysis, removing insoluble substances, and collecting a solution containing malic acid;
(2) introducing the solution containing malic acid obtained in the step (1) into cation exchange resin to obtain cation-removed solution;
(3) and (3) introducing the cation-removed solution obtained in the step (2) into anion exchange resin, adsorbing malic acid on the resin, washing with a detergent, adding dilute sulfuric acid for resolution, and collecting malic acid resolution liquid.
The raw material to be extracted by the method provided by the invention is fermentation liquor obtained by producing L-malic acid by adopting a conventional fermentation method or an enzymatic conversion method in the field. Generally, the fermentation broth contains a large amount of calcium malate and a large amount of impurities such as sugar and protein. The malic acid is L-malic acid.
In the method provided by the invention, the step (1) aims to carry out acidolysis on the fermentation liquor prepared by a fermentation method or an enzymatic conversion method by adding sulfuric acid, and mainly removes calcium ions existing in the form of calcium malate in the fermentation liquor, thereby obtaining calcium sulfate solid and a solution containing malic acid. The pH value of the solution after the sulfuric acid is added for acidolysis is preferably 1.2-3.5, and more preferably 2.0-2.6; the acidolysis temperature is preferably 30-90 ℃, and more preferably 60-85 ℃. The solution obtained by acidolysis contains a large amount of solid calcium sulfate, and the solution containing malic acid can be obtained after the solid calcium sulfate is removed by a filtration method.
In order to enhance the final separation effect, the present invention further removes cations, especially calcium ions, from the mixed solution in step (2), and contacts the malic acid-containing solution with a cation exchange resin (optionally a styrenic or acrylic cation exchange resin) to obtain a dilute malic acid-containing solution.
After calcium ions are sufficiently removed, in the step (3), the solution containing malic acid is introduced into anion exchange resin (styrene-like or acrylic acid-based anion exchange resin can be selected), so that the malic acid and the anion exchange resin are sufficiently adsorbed, and the malic acid is separated from impurities such as sugar, protein and the like in the dilute solution according to the difference of affinity of the anion exchange resin to the impurities such as the malic acid, the sugar, the protein and the like. In order to ensure sufficient adsorption of the target substance and reduce adsorption of impurities, the present invention preferably uses parameters involved in the adsorption process. Wherein the adsorption flow rate is preferably 0.5-3.5 BV/h (column volume/hour), more preferably 1.5-2.0 BV/h; the adsorption temperature is preferably 10-70 ℃, and more preferably 20-50 ℃.
In the adsorption process, a small amount of impurities may remain on the ion exchange resin, and in order to fully remove the remaining impurities, the step (3) adopts a detergent to wash the adsorption saturated resin column. The detergent can be soft water or malic acid analysis liquid, preferably malic acid analysis liquid, and the malic acid analysis liquid can adopt the malic acid analysis liquid finally obtained in the step, so that the malic acid analysis liquid can be recycled. The washing temperature is preferably 20-70 ℃, and more preferably 30-60 ℃.
In order to ensure sufficient resolution of malic acid adsorbed on the resin and to sufficiently enrich malic acid in the resolving liquid, the present invention preferably selects parameters involved in the resolving process. Wherein the concentration of the dilute sulfuric acid in the analysis solution is 0.5-15%, preferably 2.0-8.0%, and more preferably 2.5-5.0%; the analysis flow rate is preferably 0.5-3.5 BV/h, more preferably 1.5-2.0 BV/h; the desorption temperature is preferably 20 to 70 ℃, and more preferably 30 to 50 ℃.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
As a preferable scheme of the invention, the method comprises the following specific steps:
(1) heating fermentation liquor containing calcium malate obtained by producing malic acid by a fermentation method or enzyme conversion to 60-85 ℃, adding sulfuric acid for acidolysis until the pH of the system is 2.0-2.6, filtering and separating, and collecting solution containing malic acid;
(2) introducing the solution containing malic acid obtained in the step (1) into cation exchange resin to remove cations;
(3) and (3) introducing the cation-removed solution obtained in the step (2) into an anion exchange resin column according to 1.5-2.0 BV/h to be fully adsorbed with resin, then washing the adsorption resin by using pure water or malic acid analysis solution, finally introducing dilute sulfuric acid with the concentration of 2.5-5.0% according to 1.5-2.0 BV/h to carry out analysis, and collecting the malic acid analysis solution.
According to the method provided by the invention, firstly, sulfuric acid is added into the fermentation liquor for acidolysis, dilute solution containing malic acid is obtained after cations are sufficiently removed, and then separation of malic acid and impurities is realized based on the affinity difference of anion exchange resin to the malic acid and impurities such as sugar, protein and the like, so that the malic acid analysis solution is finally obtained.
The obtained malic acid solution is refined by conventional refining methods in the industry such as decolorization, cation exchange, anion exchange and the like to obtain a pure malic acid solution, and further concentrated, crystallized, separated and dried to obtain a malic acid product.
Compared with the prior art, the method provided by the invention uses the anion exchange resin with strong selectivity on malic acid as an adsorption medium, so that the malic acid in a dilute solution is effectively separated from impurities such as sugar, protein and the like, and a pure malic acid analysis solution is obtained by dilute sulfuric acid analysis; the method provided by the invention has the advantages that the yield of the malic acid is high, and the malic acid in the malic acid dilute solution is adsorbed and purified by adopting a resin adsorption method, so that the production yield of the malic acid is improved; in addition, the invention preferably adopts malic acid analytic solution to wash the adsorption saturated resin, thereby improving the quality and the concentration of the analytic solution. The method provided by the invention has the advantages of short process flow, convenient operation, high purity of the obtained malic acid, improved yield of the malic acid and reduced production cost.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples.
Example 1
This example provides a method for extracting malic acid, which uses 37.86kg of fermentation broth containing calcium malate obtained by producing malic acid by fermentation method as raw material, where the fermentation broth contains 15.6% (w/w, calculated value) of malic acid, and the following specific operations are performed:
(1) heating the fermentation liquor to 70 ℃, adding sulfuric acid for acidolysis until the pH of the solution is 2.2, and filtering and separating to obtain 11.45kg of calcium sulfate filter cake and 31.41kg of filtrate (the malic acid content is 18.70% (w/w);
(2) introducing the filtrate obtained in step (1) into styrene strongly acidic cation exchange resin to remove cations to obtain malic acid cation-removed solution 33.5kg (malic acid content 17.45%, Ca)2+Content 15 ppm);
(3) and (3) introducing the cation removal solution obtained in the step (2) into an acrylic acid series weak-base anion exchange resin column according to the ratio of 1.5BV/h to be fully adsorbed with resin, then washing the adsorption resin by using 1.5BV pure water, and finally, analyzing by using 1.5BV dilute sulfuric acid with the concentration of 3.0% to obtain 35.2kg of malic acid analysis solution with the malic acid content of 16.36%.
And (3) carrying out conventional decoloration and ion exchange resin treatment on the malic acid analysis solution to obtain 36.5kg of malic acid solution, wherein the malic acid solution contains 15.54% (w/w) of malic acid, and the yield of the malic acid is 96.04%.
Example 2
This example provides a method for extracting malic acid, which uses 32.65kg of a fermentation broth containing calcium malate obtained by producing malic acid by fermentation method as a raw material, where the fermentation broth contains 15.2% (w/w, calculated value) of malic acid, and the following specific operations are performed:
(1) heating the fermentation liquor to 75 ℃, adding sulfuric acid for acidolysis until the pH of the solution is 2.0, and filtering and separating to obtain 10.76kg of calcium sulfate filter cake and 28.62kg of filtrate (the malic acid content is 17.25% (w/w));
(2) introducing the filtrate obtained in step (1) into styrene strongly acidic cation exchange resin, and removing cations to obtain 30.82kg of malic acid cation-removed solution (malic acid content 15.95%, Ca)2+Content 10 ppm);
(3) and (3) introducing the cation removal solution obtained in the step (2) into an acrylic acid series weak-base anion exchange resin column at the rate of 1.5BV/h for full adsorption with resin, washing the adsorption resin by using 1.0BV of malic acid solution obtained in the example 1, and finally, analyzing by using 2.0BV of dilute sulfuric acid with the concentration of 2.5% to obtain 35.5kg of malic acid solution with the malic acid content of 16.4%.
The malic acid analysis solution is treated by conventional decoloration and ion exchange resin to obtain 38.64kg of malic acid solution, wherein the malic acid solution contains 12.53% (w/w) of malic acid, and the yield of the malic acid is 97.56%.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for extracting malic acid from a calcium malate solution for producing malic acid is characterized by comprising the following steps:
(1) adding sulfuric acid into fermentation liquor containing calcium malate obtained by producing malic acid by a fermentation method or an enzymatic conversion method as a raw material for acidolysis, removing insoluble substances, and collecting a solution containing malic acid;
(2) introducing the solution containing malic acid obtained in the step (1) into cation exchange resin to obtain cation-removed solution;
(3) and (3) introducing the cation-removed solution obtained in the step (2) into anion exchange resin, adsorbing malic acid on the resin, washing with a detergent, adding dilute sulfuric acid for resolution, and collecting malic acid resolution liquid.
2. The method according to claim 1, wherein the pH value of the system after adding sulfuric acid in the step (1) is 1.2-3.5, preferably 2.0-2.6.
3. The method according to claim 1 or 2, wherein the temperature of the acid hydrolysis in step (1) is 30 to 90 ℃, preferably 60 to 85 ℃.
4. The method according to claim 1, wherein the flow rate of the adsorption in step (3) is 0.5-3.5 BV/h, preferably 1.5-2.0 BV/h.
5. The method according to claim 4, wherein the temperature of the adsorption in step (3) is 10-70 ℃, preferably 20-50 ℃.
6. The method of claim 1, wherein the detergent in step (3) is water or malic acid solution.
7. The method according to claim 1, wherein the concentration of the dilute sulfuric acid in the step (3) is 0.5-15%, preferably 2-8%.
8. The method according to claim 1 or 7, wherein the flow rate of the desorption in the step (3) is 0.5-3.5 BV/h, preferably 1.5-2.0 BV/h.
9. The method of claim 1, comprising the steps of:
(1) heating fermentation liquor containing calcium malate obtained by producing malic acid by a fermentation method or enzyme conversion to 60-85 ℃, adding sulfuric acid for acidolysis until the pH of the system is 2.0-2.6, filtering and separating, and collecting solution containing malic acid;
(2) introducing the solution containing malic acid obtained in the step (1) into cation exchange resin to remove cations;
(3) and (3) introducing the cation-removed solution obtained in the step (2) into an anion exchange resin column according to 1.5-2.0 BV/h to be fully adsorbed with resin, then washing the adsorption resin by using pure water or malic acid analysis solution, finally introducing dilute sulfuric acid with the concentration of 2-8% according to 1.5-2.0 BV/h to carry out analysis, and collecting the malic acid analysis solution.
10. The method according to any one of claims 1 to 9, characterized in that the malic acid solution obtained in step (3) is refined, and then concentrated, crystallized, separated and dried to obtain a malic acid product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910591006.3A CN110256227A (en) | 2019-07-02 | 2019-07-02 | A method of extracting production malic acid from calcium malate solution |
| CN2019105910063 | 2019-07-02 |
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| CN111732503A true CN111732503A (en) | 2020-10-02 |
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| CN201910591006.3A Pending CN110256227A (en) | 2019-07-02 | 2019-07-02 | A method of extracting production malic acid from calcium malate solution |
| CN202010626542.5A Withdrawn CN111732503A (en) | 2019-07-02 | 2020-07-02 | Method for extracting malic acid from calcium malate solution |
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| CN201910591006.3A Pending CN110256227A (en) | 2019-07-02 | 2019-07-02 | A method of extracting production malic acid from calcium malate solution |
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| CN111892498A (en) * | 2020-08-24 | 2020-11-06 | 新拓洋生物工程有限公司 | Method for extracting L-malic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068419A (en) * | 1986-12-18 | 1991-11-26 | Uop | Separation of an organic acid from a fermentation broth with an anionic polymeric adsorbent |
| CN1067451A (en) * | 1991-06-04 | 1992-12-30 | 中国科学院微生物研究所 | Production of l-malic acid by fixed cells |
| CN1081206A (en) * | 1992-07-14 | 1994-01-26 | 中国药科大学 | Method with preparing malic acid with enzyme engineering technology |
| CN106148209A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院天津工业生物技术研究所 | New binary organic acid produces bacterial strain and preparation thereof and application |
-
2019
- 2019-07-02 CN CN201910591006.3A patent/CN110256227A/en active Pending
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2020
- 2020-07-02 CN CN202010626542.5A patent/CN111732503A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068419A (en) * | 1986-12-18 | 1991-11-26 | Uop | Separation of an organic acid from a fermentation broth with an anionic polymeric adsorbent |
| CN1067451A (en) * | 1991-06-04 | 1992-12-30 | 中国科学院微生物研究所 | Production of l-malic acid by fixed cells |
| CN1081206A (en) * | 1992-07-14 | 1994-01-26 | 中国药科大学 | Method with preparing malic acid with enzyme engineering technology |
| CN106148209A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院天津工业生物技术研究所 | New binary organic acid produces bacterial strain and preparation thereof and application |
Non-Patent Citations (2)
| Title |
|---|
| 何姗: "大孔树脂分离发酵苹果酸的静态吸附工艺研究", 《化工时刊》 * |
| 叶青等: "碱性离子交换树脂分离 L-苹果酸的研究", 《精细化工》 * |
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