CN110256227A - A method of extracting production malic acid from calcium malate solution - Google Patents
A method of extracting production malic acid from calcium malate solution Download PDFInfo
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- CN110256227A CN110256227A CN201910591006.3A CN201910591006A CN110256227A CN 110256227 A CN110256227 A CN 110256227A CN 201910591006 A CN201910591006 A CN 201910591006A CN 110256227 A CN110256227 A CN 110256227A
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- malic acid
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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
- C07C51/02—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
Abstract
The method that the present invention relates to a kind of to extract production malic acid from calcium malate solution, method includes the following steps: (1) is using fermentation method or the enzyme transforming process production resulting fermentation liquid containing calcium malate of malic acid as raw material, sulfuric acid is added and carries out acidolysis, insoluble matter is removed, the solution containing malic acid is collected；(2) solution containing malic acid obtained by step (1) is passed through storng-acid cation exchange resin, obtains decationizing solution；(3) decationizing solution obtained by step (2) is passed through weak-base anion-exchange resin, malic acid is adsorbed on resin, is washed with detergent, is added dilute sulfuric acid and is parsed, and malic acid desorbed solution is collected.Method provided by the invention has the characteristics that simple process, easy to operate, high income, product quality are high.
Description
Technical field
The invention belongs to field of food chemical industry, and in particular to a kind of side that production malic acid is extracted from calcium malate solution
Method.
Background technique
Malic acid also known as 2- hydroxysuccinic acid, due to there is an asymmetric carbon atom in molecule, there are two types of alloisomerisms
Body.In the Nature, exist in the form of three kinds, i.e. D-malic acid, L MALIC ACID and its mixture D L MALIC ACID.Malic acid is white
Color crystalline solid or crystalline powder have stronger hygroscopicity, soluble easily in water, ethyl alcohol.There is special pleasant tart flavour.Malic acid is main
It is a kind of excellent acid and antistaling agent for food industry.While it in clinical medicine, daily use chemicals health care, chemical industry and building
Building also has important application in industry.
Its production method has chemical synthesis, fermentation method and enzymatic production process at present.Chemical synthesis investment is big, technology
It is required that high, the product of synthesis is DL-malic acid.The calcium malate weak solution of fermentation method and enzyme transforming process preparation, still can not currently
The realization of the wherein impurity such as sugar, albumen is efficiently separated.The common method of malic acid is extracted in fermentation liquid acid hydrolyzation and organic molten
Agent extraction.Existing acidolysis process, processing step is complicated, and product purity is low, yield is low.Conventional organic solvent extraction exists
The problems such as it is stripped difficulty, and product purity is low, dissolvent residual.
Summary of the invention
Present invention aim to address the impurity separation difficulties, yield such as sugar, albumen in existing malic acid production products therefrom
Low problem proposes a kind of method for extracting production malic acid from calcium malate solution, improves product quality and yield.
Specifically, method provided by the invention includes the following steps:
(1) using fermentation method or the enzyme transforming process production resulting fermentation liquid containing calcium malate of malic acid as raw material, sulphur is added
Acid carries out acidolysis, removes insoluble matter, collects the solution containing malic acid；
(2) solution containing malic acid obtained by step (1) is passed through storng-acid cation exchange resin, it is molten obtains decationizing
Liquid；
(3) decationizing solution obtained by step (2) is passed through weak-base anion-exchange resin, malic acid is adsorbed in resin
On, it is washed with detergent, adds dilute sulfuric acid and parsed, collect malic acid desorbed solution.
The targeted raw material to be extracted of method provided by the invention, to be produced using this field normal fermentation method or enzymatic conversion
The resulting fermentation liquid of L MALIC ACID.In general, containing a large amount of calcium malate in the fermentation liquid, and a large amount of sugar, egg
The impurity such as white matter.Malic acid of the present invention refers to L MALIC ACID.
In method provided by the invention, the purpose of step (1) is to be prepared fermentation method or enzyme transforming process by the way that sulfuric acid is added
Fermentation liquid acidolysis, mainly in removal fermentation liquid in the form of calcium malate existing for calcium ion, to obtain calcium sulphate solid,
And the solution containing malic acid.The pH value of solution is preferably 1.2~3.5 after present invention addition sulfuric acid solution, and more preferably 2.0
~2.2；The acidolysis temperature is preferably 30~90 DEG C, and more preferably 60~85 DEG C.The resulting solution of acidolysis contains a large amount of solids
Calcium sulfate after removing by filter method, can be obtained the solution containing malic acid.
In order to improve final separating effect, the present invention further removes cation in mixed solution, especially in step (2)
It is calcium ion, the solution containing malic acid is contacted with storng-acid cation exchange resin, to obtains the weak solution containing malic acid.
Sufficiently after removal calcium ion, the solution containing malic acid is passed through weakly-basic anion exchange tree by step (3) of the present invention
(quasi-styrene system or acrylic acid type anion exchange resin can be selected) in rouge, inhales malic acid sufficiently with anion exchange resin
It is attached, according to anion exchange resin to the difference of the impurity affinity such as malic acid and sugar, albumen so that in weak solution malic acid and
The impurity such as sugar, albumen reach separation.In order to ensure reducing the absorption of impurity, the present invention while the abundant absorption of target substance
Parameter involved in adsorption process is carried out preferred.Wherein, adsorption flow rate is preferably 0.5~3.5BV/h (column volume/hour),
More preferably 1.5~2.0BV/h；Adsorption temp is preferably 10~70 DEG C, more preferably 20-50 DEG C.
Since a small amount of impurity may be remained on ion exchange resin in adsorption process, in order to which residual impurity is abundant
Removal, step (3) wash adsorption saturation resin column using detergent.Soft water or apple acidolysis can be selected in the detergent
Liquid, preferably malic acid desorbed solution are analysed, malic acid desorbed solution can be real using the final gained malic acid desorbed solution of this step herein
Its existing cycling and reutilization.The temperature of the washing is preferably 20~70 DEG C, and more preferably 30~60 DEG C.
In order to ensure sufficiently parsing the malic acid being adsorbed on resin, it is enriched with malic acid sufficiently in desorbed solution, originally
Invention carries out parameter involved in resolving preferred.Wherein, the concentration of desorbed solution dilute sulfuric acid is preferably 0.5~20%, more
Preferably 0.5~15%, further preferably 2.5-3.0%；Parsing flow velocity is preferably 0.5~3.5BV/h, and more preferably 1.5
~2.0BV/h；Resolution temperature is preferably 20~70 DEG C, and more preferably 30~50 DEG C.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can be combined with each other, obtain specific embodiment party
Formula.
As a preferred solution of the present invention, the method includes following specific steps:
(1) it using fermentation method or the enzymatic conversion production resulting fermentation liquid containing calcium malate of malic acid as raw material, is heated to
70~75 DEG C, addition sulfuric acid solution to system pH is 2.0~2.2, is separated by filtration, and collects the solution containing malic acid；
(2) solution containing malic acid obtained by step (1) is passed through storng-acid cation exchange resin, removal cation；
(3) decationizing solution obtained by step (2) acrylic acid series weakly-basic anion is passed through by 1.5~2.0BV/h to hand over
Change resin column and sufficiently adsorbed with resin, then absorption resin is washed with pure water or malic acid desorbed solution, finally by 1.5~
1.5~2.0BV of dilute sulfuric acid that 2.0BV/h is passed through concentration 2.5~3.0% is parsed, and malic acid desorbed solution is collected.
Sulfuric acid is first added in fermentation liquid and carries out acidolysis for method provided by the invention, sufficiently obtains after removal cation containing apple
The weak solution of tartaric acid, then apple is realized to the affinity difference of the impurity such as malic acid and sugar, albumen based on anion exchange resin
The separation of acid and impurity, it is final to obtain malic acid desorbed solution.
Refining methd of the gained malic acid desorbed solution through industry routine is such as decolourized, cation exchanges, anion exchange
Means obtain pure malic acid solution, further obtain apple acid product by concentration, crystallization, separation, drying.
Compared with prior art, method provided by the invention used to malic acid have the strong alkalescent yin of selectivity from
Sub-exchange resin is adsorbing medium, reaches the impurity such as malic acid and sugar, albumen and efficiently separates, passes through dilute sulfuric acid solution
Analysis obtains pure malic acid desorbed solution；Malic acid high income obtained by method provided by the invention, the present invention use resin adsorption
Method absorption purification is carried out to the malic acid in malic acid weak solution, improve malic acid yield；And the present invention is preferred
Adsorption saturation resin is washed using malic acid desorbed solution, improves desorbed solution quality and concentration.Side provided by the invention
Method process flow is short, easy to operate, the malic acid purity is high of acquisition, and improves malic acid yield, reduces production cost.
Specific embodiment
The preferred embodiment of the present invention is described in detail below in conjunction with embodiment.
Embodiment 1
A kind of method for extracting production malic acid is present embodiments provided, malic acid is resulting contains apple with fermentation method production
The fermentation liquid 37.86kg of calcium citrate malate is raw material, is equivalent in the fermentation liquid containing malic acid 15.6% (w/w, calculated value), into
The following concrete operations of row:
(1) fermentation liquid is heated to 70 DEG C, addition sulfuric acid solution to pH value of solution is 2.2, is separated by filtration, obtains sulfuric acid
Calcium filter cake 11.45kg and filtrate 31.41kg (malic acid content 18.70% (w/w)；
(2) filtrate obtained by step (1) is passed through storng-acid cation exchange resin, removal cation obtains malic acid and goes
Cationic solution 33.5kg (malic acid content 17.45%, Ca2+Content 15ppm)；
(3) decationizing solution obtained by step (2) is passed through acrylic acid series weak-base anion-exchange resin by 1.5BV/h
Column is sufficiently adsorbed with resin, is then washed with 1.5BV pure water to absorption resin, is finally used dilute sulphur of 1.5BV concentration 3.0%
Acid is parsed, and the malic acid desorbed solution 35.2kg of malic acid content 16.36% is obtained.
Above-mentioned malic acid desorbed solution is passed through into conventional decoloration, ion exchange resin treatment, malic acid solution 36.5kg is obtained,
Wherein (w/w) containing malic acid 15.54%, malic acid yield 96.04%.
Embodiment 2
A kind of method for extracting production malic acid is present embodiments provided, malic acid is resulting contains apple with fermentation method production
The fermentation liquid 32.65kg of calcium citrate malate is raw material, is equivalent in the fermentation liquid containing malic acid 15.2% (w/w, calculated value), into
The following concrete operations of row:
(1) fermentation liquid is heated to 75 DEG C, addition sulfuric acid solution to pH value of solution is 2.0, is separated by filtration, obtains sulfuric acid
Calcium filter cake 10.76kg and filtrate 28.62kg (malic acid content 17.25% (w/w)；
(2) filtrate obtained by step (1) is passed through storng-acid cation exchange resin, removal cation obtains malic acid and goes
Cationic solution 30.82kg (malic acid content 15.95%, Ca2+Content 10ppm)；
(3) decationizing solution obtained by step (2) is passed through acrylic acid series weak-base anion-exchange resin by 1.5BV/h
Column is sufficiently adsorbed with resin, is then washed with the resulting malic acid desorbed solution of 1.0BV embodiment 1 to absorption resin, finally
It is parsed with the dilute sulfuric acid of 2.0BV concentration 2.5%, obtains the malic acid desorbed solution 35.5kg of malic acid content 16.4%.
Above-mentioned malic acid desorbed solution is passed through into conventional decoloration, ion exchange resin treatment, malic acid solution is obtained
38.64kg, wherein (w/w) containing malic acid 12.53%, malic acid yield 97.56%.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of method for extracting production malic acid from calcium malate solution, which comprises the steps of:
(1) using fermentation method or enzyme transforming process production the resulting fermentation liquid containing calcium malate of malic acid as raw material, be added sulfuric acid into
Row acidolysis removes insoluble matter, collects the solution containing malic acid；
(2) solution containing malic acid obtained by step (1) is passed through storng-acid cation exchange resin, obtains decationizing solution；
(3) decationizing solution obtained by step (2) being passed through weak-base anion-exchange resin, malic acid is adsorbed on resin,
It is washed with detergent, adds dilute sulfuric acid and parsed, collect malic acid desorbed solution.
2. the method according to claim 1, wherein step (1) be added sulfuric acid after system pH value be 1.2~
3.5, preferably 2.0~2.2.
3. method according to claim 1 or 2, which is characterized in that the temperature of step (1) described acidolysis is 30~90 DEG C,
Preferably 60~85 DEG C.
4. the method according to claim 1, wherein the flow velocity of step (3) described absorption be 0.5~3.5BV/h,
Preferably 1.5~2.0BV/h.
5. according to the method described in claim 4, it is characterized in that, the temperature of step (3) described absorption is 10~70 DEG C, preferably
It is 20~50 DEG C.
6. the method according to claim 1, wherein step (3) detergent is water or malic acid desorbed solution.
7. the method according to claim 1, wherein the concentration of step (3) described dilute sulfuric acid be 0.5~15%,
Preferably 2.5~3.0%.
8. method according to claim 1 or claim 7, which is characterized in that the flow velocity of step (3) described parsing be 0.5~
3.5BV/h, preferably 1.5~2.0BV/h.
9. the method according to claim 1, wherein including the following steps:
(1) using fermentation method or the enzymatic conversion production resulting fermentation liquid containing calcium malate of malic acid as raw material, it is heated to 70~
75 DEG C, addition sulfuric acid solution to system pH is 2.0~2.2, is separated by filtration, and collects the solution containing malic acid；
(2) solution containing malic acid obtained by step (1) is passed through storng-acid cation exchange resin, removal cation；
(3) decationizing solution obtained by step (2) is passed through acrylic acid series weakly-basic anion exchange tree by 1.5~2.0BV/h
Rouge column is sufficiently adsorbed with resin, is then washed with pure water or malic acid desorbed solution to absorption resin, finally by 1.5~
1.5~2.0BV of dilute sulfuric acid that 2.0BV/h is passed through concentration 2.5~3.0% is parsed, and malic acid desorbed solution is collected.
10. method described in any one according to claim 1~9, which is characterized in that parse malic acid obtained by step (3)
Liquid is refined, then is concentrated, crystallized, separated, dried, and apple acid product is obtained.
Priority Applications (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 |
| CN202010626542.5A CN111732503A (en) | 2019-07-02 | 2020-07-02 | Method for extracting malic acid from calcium malate solution |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910591006.3A CN110256227A (en) | 2019-07-02 | 2019-07-02 | A method of extracting production malic acid from calcium malate solution |
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| CN110256227A true CN110256227A (en) | 2019-09-20 |
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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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| CN202010626542.5A Withdrawn CN111732503A (en) | 2019-07-02 | 2020-07-02 | Method for extracting malic acid from calcium malate solution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (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 |
| CN106148209B (en) * | 2015-03-23 | 2020-11-20 | 中国科学院天津工业生物技术研究所 | Novel binary organic acid producing strain and preparation and application thereof |
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- 2019-07-02 CN CN201910591006.3A patent/CN110256227A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Application publication date: 20190920 |