CN110194714A - A method of separation malic acid and succinic acid - Google Patents
A method of separation malic acid and succinic acid Download PDFInfo
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- CN110194714A CN110194714A CN201910591503.3A CN201910591503A CN110194714A CN 110194714 A CN110194714 A CN 110194714A CN 201910591503 A CN201910591503 A CN 201910591503A CN 110194714 A CN110194714 A CN 110194714A
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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
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of methods for separating malic acid and succinic acid, and described method includes following steps: (1) using the fermentation method production resulting fermentation liquid of malic acid as raw material, sulfuric acid are added and carries out acidolysis, removes insoluble matter, collects solution；(2) step (1) acquired solution 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 and succinic acid are adsorbed on resin, are added dilute sulfuric acid and are parsed, and collect succinic acid desorbed solution and malic acid desorbed solution respectively.Method provided by the invention has the characteristics that simple process, easy to operate, product purity is high using suction-joint method separation malic acid and succinic acid.
Description
Technical field
The invention belongs to field of food chemical industry, and in particular to a method of separation malic acid and succinic acid.
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.
Succinic acid also known as succinic acid, succinic acid have sour colourless crystallization to be colourless or white, odorless；It is relatively close
1.572 (25/4 DEG C) are spent, 188 DEG C of fusing point, are decomposed at 235 DEG C；25 DEG C of solubility in water is 6.8g/100ml, is being depressurized
Lower distillation can distil；It can be dissolved in water, be slightly soluble in ethyl alcohol, ether and acetone.
The production method of malic acid has the production technologies such as chemical synthesis, fermentation method and enzyme process at present.Chemical synthesis is thrown
Money is big, and technical requirements are high, and the product of synthesis is DL-malic acid.In fermentation liquid extract the common method of malic acid have acid hydrolyzation and
Organic solvent extractionprocess, products obtained therefrom purity are low.For fermentation method obtain calcium malate and calcium succinate solution, at present still without
The separation of better method realization malic acid and succinic acid.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, the resulting fermentation liquid of malic acid is produced for fermentation method,
The method of a kind of effective separation malic acid and succinic acid is proposed, is produced to produce qualified malic acid and succinic acid
Product.
Specifically, method provided by the invention includes the following steps:
(1) using the fermentation method production resulting fermentation liquid of malic acid as raw material, sulfuric acid is added and carries out acidolysis, removes insoluble matter,
Collect solution；
(2) step (1) acquired solution 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 and succinic acid are inhaled
It invests on resin, adds dilute sulfuric acid and parsed, collect succinic acid desorbed solution and malic acid desorbed solution respectively.
The targeted raw material to be separated of method provided by the invention, to produce L MALIC ACID using this field normal fermentation method
Resulting fermentation liquid.In general, contain a large amount of calcium malate and calcium succinate in the fermentation liquid, and a large amount of sugar,
The impurity such as protein.Malic acid of the present invention refers to L MALIC ACID.
In separation method provided by the invention, the purpose of step (1) is the fermentation for being prepared fermentation method by the way that sulfuric acid is added
Liquid acidolysis, mainly removal fermentation liquid in the form of calcium malate and calcium succinate existing for calcium ion, to obtain calcium sulfate
Solid, and the mixed solution containing malic acid and succinic acid.The pH value of solution is preferably 1.2 after present invention addition sulfuric acid solution
~3.5, more preferably 1.5~2.5；The acidolysis temperature is preferably 30~90 DEG C, and more preferably 60~85 DEG C.Acidolysis is resulting
Solution contains a large amount of solid calcium sulphates, after removing by filter method, can be obtained the mixed solution containing malic acid and succinic 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 mixed solution containing malic acid and succinic acid is contacted with storng-acid cation exchange resin, to obtains containing apple
The weak solution of tartaric acid and succinic acid.
Sufficiently after removal calcium ion, step (3) of the present invention will contain malic acid and succinic acid be passed through alkalescent yin from
(polystyrene or acrylic acid type anion exchange resin can be selected) in sub-exchange resin, according to anion exchange resin to malic acid
With the difference of the impurity affinity such as succinic acid and sugar, albumen so that malic acid and the impurity such as succinic acid and sugar, albumen in weak solution
Reach separation, then parsed through dilute sulfuric acid, purer succinic acid solution and malic acid are respectively obtained using the method for Fractional Collections
Solution.
In order to ensure reducing the absorption of impurity while the abundant absorption of target substance, the present invention in adsorption process to relating to
And parameter carry out it is 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.
In order to ensure the malic acid being adsorbed on resin and succinic acid to be sufficiently separated, keep succinic acid abundant in fast component
It is enriched with malic acid sufficiently in slow component while enrichment, the present invention carries out parameter involved in resolving preferred.Its
In, the concentration of desorbed solution dilute sulfuric acid is preferably 0.5~15%, more preferably 2.0-8.0%；Parsing flow velocity is preferably 0.5~
3.5BV/h, more preferably 1.5~2.0BV/h；Resolution temperature is preferably 20~70 DEG C, and more preferably 30~50 DEG C.
As the committed step for ensuring that malic acid and succinic acid are sufficiently separated, the present invention is further preferably described for the parsing
Parsing specifically: with 1.5~2.0BV/h of flow velocity be passed through the dilute sulfuric acid of concentration 3.0~4.0% totally 5.0~5.5BV (column volume) into
Row parsing.Under the above conditions, it can be ensured that be sufficiently enriched in the desorbed solution of preceding 2.0BV in succinic acid, malic acid is later 3.0
It is sufficiently enriched in the desorbed solution of~3.5BV, two parts desorbed solution volume is suitable, and it is very convenient when operation to be actually collected.
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) using the fermentation method production resulting fermentation liquid of malic acid as raw material, 65~75 DEG C are heated to, addition sulfuric acid solution is extremely
System pH is 1.65~1.80, is separated by filtration, and solution is collected；
(2) step (1) acquired solution is passed through storng-acid cation exchange resin, removal cation；
(3) decationizing solution obtained by step (2) polystyrene weakly-basic anion is passed through by 1.5~2.0BV/h to hand over
It changes resin column and is sufficiently adsorbed with resin, then absorption resin is washed with pure water, is finally passed through by 1.5~2.0BV/h dense
5.0~5.5BV of dilute sulfuric acid of degree 3.0~4.0% is parsed, and the desorbed solution and enrichment malic acid of enrichment succinic acid are successively collected
Desorbed solution.
Method provided by the invention is first added sulfuric acid in fermentation liquid and carries out acidolysis, obtains dilute containing malic acid and succinic acid
Solution, then apple is realized to the affinity difference of the impurity such as malic acid, succinic acid and sugar, albumen based on anion exchange resin
Sour and succinic acid is separated with impurity, is further eluted by dilute sulfuric acid, is collected fast component and is obtained succinic acid desorbed solution, collects slowly
Component obtains malic acid desorbed solution.
The refining methd of gained malic acid desorbed solution and succinic acid desorbed solution through industry routine such as decoloration, cation are handed over
Change, the means such as anion exchange obtain pure malic acid solution and succinic acid solution, further by concentration, crystallization, separation,
Drying obtains apple acid product and succinic acid product respectively.
Compared with prior art, method provided by the invention produces the resulting fermentation liquid of malic acid for fermentation method, utilizes
Anion exchange resin realizes efficiently separating for malic acid and the impurity such as succinic acid and sugar, albumen, and process flow is short, operation side
Just, the malic acid of acquisition and succinic acid product purity are high, and improve the yield of malic acid and succinic acid, reduce and are produced into
This.
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 separating malic acid and succinic acid is present embodiments provided, malic acid is produced with 35.46kg fermentation method
Resulting fermentation liquid is raw material, is equivalent in the fermentation liquid containing malic acid 13.6% (w/w, calculated value) and succinic acid
3.42% (w/w, calculated value), carries out following concrete operations:
(1) fermentation liquid is heated to 70 DEG C, addition sulfuric acid solution to pH value of solution is 1.65, is separated by filtration, obtains sulphur
Sour calcium filter cake 9.45kg collects solution；
(2) step (1) acquired solution is passed through storng-acid cation exchange resin, removal cation, obtain malic acid with
Succinic acid decationizing solution 43.45kg (malic acid content 10.98%, succinic acid content 2.78%, Ca2+Content 52ppm)；
(3) decationizing solution obtained by step (2) is passed through polystyrene 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 5.0BV concentration 3.5%
Acid is parsed, and fast component succinic acid desorbed solution 2.0BV, quality 25.6kg are collected, through testing and analyzing succinic acid content
4.65% (w/w)；Slow component malic acid desorbed solution 3BV, quality 39.66kg are collected, through testing and analyzing malic acid content
11.85% (w/w).
By above-mentioned succinic acid desorbed solution and malic acid desorbed solution respectively through further decoloration, ion-exchange, concentration, crystallization, separation,
Drying and processing obtains apple acid product and succinic acid product, through detecting malic acid purity 99.25%, succinic acid purity
95.20%.
Embodiment 2
A kind of method for separating malic acid and succinic acid is present embodiments provided, malic acid institute is produced with 28.5kg fermentation method
The fermentation liquid obtained is raw material, is equivalent in the fermentation liquid containing malic acid 13.56% (w/w, calculated value) and succinic acid
3.55% (w/w, calculated value), carries out following concrete operations:
(1) fermentation liquid is heated to 70 DEG C, addition sulfuric acid solution to pH value of solution is 1.80, is separated by filtration, obtains sulphur
Sour calcium filter cake 8.35kg collects solution；Malic acid and succinic acid mixed filtrate 32.66kg are obtained, wherein malic acid content
11.78% (w/w), succinic acid content 3.08% (w/w)；
(2) step (1) acquired solution is passed through storng-acid cation exchange resin, removal cation, obtain malic acid with
Succinic acid decationizing solution 40.28kg (malic acid content 9.50% (w/w), succinic acid content 2.49% (w/w), Ca2+
100ppm)；
(3) decationizing solution obtained by step (2) is passed through polystyrene weak-base anion-exchange resin by 1.5BV/h
Column is sufficiently adsorbed with resin, is then washed with 2.0BV pure water to absorption resin, is finally used dilute sulphur of 5.5BV concentration 3.5%
Acid is parsed, and fast component succinic acid desorbed solution 2.0BV, quality 25.5kg are collected, through testing and analyzing succinic acid content
3.85% (w/w)；Slow component malic acid desorbed solution 3.5BV, quality 42.16kg are collected, through testing and analyzing malic acid content
8.95% (w/w).
By above-mentioned succinic acid desorbed solution and malic acid desorbed solution respectively through further decoloration, ion-exchange, concentration, crystallization, separation,
Drying and processing obtains apple acid product and succinic acid product, through detecting malic acid purity 99.85%, succinic acid product purity
96.75%.
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 separating malic acid and succinic acid, which comprises the steps of:
(1) using the fermentation method production resulting fermentation liquid of malic acid as raw material, sulfuric acid is added and carries out acidolysis, removes insoluble matter, collects
Solution；
(2) step (1) acquired solution 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 and succinic acid are adsorbed in
It on resin, adds dilute sulfuric acid and is parsed, collect succinic acid desorbed solution and malic acid desorbed solution respectively.
2. the method according to claim 1, wherein containing calcium malate and calcium succinate in the fermentation liquid.
3. the method according to claim 1, wherein step (1) be added sulfuric acid after system pH value be 1.2~
3.5, preferably 1.5~2.5.
4. method according to claim 1 or 3, which is characterized in that the temperature of step (1) described acidolysis is 30~90 DEG C,
Preferably 60~85 DEG C.
5. 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.
6. according to the method described in claim 5, it is characterized in that, the temperature of step (3) described absorption is 10~70 DEG C, preferably
It is 20~50 DEG C.
7. the method according to claim 1, wherein the concentration of step (3) described dilute sulfuric acid be 0.5~15%,
Preferably 2.0~8.0%.
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. according to claim 1, method described in 7 or 8, which is characterized in that step (3) described parsing specifically: with flow velocity 1.5
~2.0BV/h is passed through the dilute sulfuric acid of concentration 3.0~4.0%, and totally 5.0~5.5BV is parsed.
10. method according to claim 1 or 2, which comprises the steps of:
(1) using the fermentation method production resulting fermentation liquid of malic acid as raw material, 65~75 DEG C are heated to, addition sulfuric acid solution to system
PH is 1.65~1.80, is separated by filtration, and solution is collected；
(2) step (1) acquired solution is passed through storng-acid cation exchange resin, removal cation；
(3) decationizing solution obtained by step (2) is passed through polystyrene weakly-basic anion exchange tree by 1.5~2.0BV/h
Rouge column is sufficiently adsorbed with resin, is then washed with pure water to absorption resin, is finally passed through concentration 3.0 by 1.5~2.0BV/h
~4.0% 5.0~5.5BV of dilute sulfuric acid is parsed, and the desorbed solution of enrichment succinic acid and the solution of enrichment malic acid are successively collected
Analyse liquid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910591503.3A CN110194714A (en) | 2019-07-02 | 2019-07-02 | A method of separation malic acid and succinic acid |
| CN202010625145.6A CN111732502A (en) | 2019-07-02 | 2020-07-02 | Method for separating malic acid from succinic acid |
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| CN201910591503.3A CN110194714A (en) | 2019-07-02 | 2019-07-02 | A method of separation malic acid and succinic acid |
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| CN201910591503.3A Pending CN110194714A (en) | 2019-07-02 | 2019-07-02 | A method of separation malic acid and succinic acid |
| CN202010625145.6A Withdrawn CN111732502A (en) | 2019-07-02 | 2020-07-02 | Method for separating malic acid from succinic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114014751A (en) * | 2021-12-10 | 2022-02-08 | 新疆至臻化工工程研究中心有限公司 | Method for separating and extracting malic acid from succinic acid crystallization filtrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5068419A (en) * | 1986-12-18 | 1991-11-26 | Uop | Separation of an organic acid from a fermentation broth with an anionic polymeric adsorbent |
| US7241918B1 (en) * | 2003-03-18 | 2007-07-10 | Uop Llc | Separation of citric acid from gluconic acid in fermentation broth using a weakly or strongly basic anionic exchange resin adsorbent |
| CN101348428B (en) * | 2008-09-05 | 2011-01-05 | 江南大学 | Method for extracting amber acid in fermentation liquor by anion resin adsorption |
| US9233906B2 (en) * | 2009-12-31 | 2016-01-12 | Group Novasep SAS | Purification of succinic acid from the fermentation broth containing ammonium succinate |
| 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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| CN114014751A (en) * | 2021-12-10 | 2022-02-08 | 新疆至臻化工工程研究中心有限公司 | Method for separating and extracting malic acid from succinic acid crystallization filtrate |
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Application publication date: 20190903 |