CN110272339A - A kind of method of separation and Extraction high-purity malic acid - Google Patents
A kind of method of separation and Extraction high-purity malic acid Download PDFInfo
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- CN110272339A CN110272339A CN201910599570.XA CN201910599570A CN110272339A CN 110272339 A CN110272339 A CN 110272339A CN 201910599570 A CN201910599570 A CN 201910599570A CN 110272339 A CN110272339 A CN 110272339A
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- Prior art keywords
- malic acid
- calcium
- acid
- acidolysis
- solid
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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
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Abstract
The present invention relates to a kind of methods of separation and Extraction high-purity malic acid, comprising 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, is separated by solid-liquid separation, collects solid；(2) obtained solid is mixed with water, acidolysis makes calcium malate be converted into hydrogen malate calcium, and filtrate is collected in filtering；Hydrogen malate calcium contained in the filtrate is crystallized, crystal is collected；(3) gained crystal is mixed with water, acidolysis makes hydrogen malate calcium be completely converted into malic acid, is separated by solid-liquid separation, and collects malic acid acid hydrolysis solution, is further processed to obtain purity up to 99.0% or more malic acid.Method provided by the invention is due to first converting hydrogen malate calcium for the slurries containing calcium malate and crystallizing, it can be improved malic acid acid hydrolysis solution concentration, acid hydrolysis solution pigment is reduced, thus the concentrated cost of process and decoloration difficulty after reducing, and the malic acid product purity finally obtained is high, high-quality.
Description
Technical field
The present invention relates to field of food chemical industry, and in particular to a kind of method of separation and Extraction high-purity malic 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
For food and medicine 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.L- apple is extracted from malic acid fermentation liquid prepared by fermentation method and enzyme transforming process
Sour common method has acidolysis ion-exchange method and organic solvent extractionprocess.Existing acid dissociation is handed over skill, and processing step is complicated, product
Purity is low, yield is low.The problems such as there are it to be stripped difficulty for conventional organic solvent extraction, and product purity is low, dissolvent residual.
Summary of the invention
It is an object of the invention to solve the problems, such as existing apple acid production process, propose a kind of using malic acid
The method of hydrogen calcium crystallisation next life production of high purity malic acid.Method proposed by the present invention, which can be effectively removed in fermentation liquid, to be contained
Heteroacid (such as succinic acid, fumaric acid), to obtain the apple acid product of high-purity.
Specifically, including the following steps: the present invention provides a kind of method of separation and Extraction high-purity malic acid
(1) using fermentation method or the enzyme transforming process production resulting fermentation liquid containing calcium malate of malic acid as raw material, solid-liquid
Solid is collected in separation；
(2) step (1) obtained solid is mixed with water, acidolysis makes calcium malate be converted into hydrogen malate calcium, filters, and collects
Filtrate；Hydrogen malate calcium contained in the filtrate is crystallized, crystal is collected；
(3) crystal obtained by step (2) is mixed with water, acidolysis makes hydrogen malate calcium be completely converted into malic acid, solid-liquid point
From collection malic acid acid hydrolysis solution.
The extraction that method provided by the invention is directed to separates object are as follows: uses fermentation method known in the art or enzyme transforming process
Produce the resulting fermentation liquid of L MALIC ACID.Contain a large amount of calcium ion in the fermentation liquid, in addition to malic acid, also contains fourth two
The heteroacid radical ion such as acid, fumaric acid.Malic acid of the present invention refers to L MALIC ACID.
Step (1) of the present invention is separated by solid-liquid separation the fermentation liquid containing calcium malate and heteroacid, obtains containing apple
The solid and liquid two parts of sour calcium.In order to be enriched with calcium malate in solid portion, it is of the present invention be separated by solid-liquid separation 10~
It is advisable in the range of 100 DEG C, preferably 60~90 DEG C, more preferably 70~80 DEG C.Centrifugation can be used in the separation of solid and liquid
The conventional method of equal this fields.
In step (2) of the present invention, the solid containing calcium malate is mixed with water and is sized mixing, with water mixing rear slurry
Concentration is preferably 10~70%.The main purpose of step (2) described acidolysis is to convert calcium malate to hydrogen malate calcium and divide
From extraction.The acid that the acidolysis is added can be sulfuric acid or malic acid, and malic acid herein can be to apple of the present invention
Sour acid hydrolysis solution cycling and reutilization mother liquid obtained after being crystallized.The pH value of the acidolysis is preferably 1.5~4.5, more preferably
2.0~4.0, further preferably 2.5~3.0.The temperature of the acidolysis can within the scope of 10~100 DEG C, preferably 50~90
DEG C, more preferably 75~85 DEG C.Since the hydrogen malate calcium that step (2) obtains is core of the invention intermediate product, determine
The purity and yield of final product malic acid, the acidolysis of preferred steps (2) of the present invention are as follows: it is 2.9 that sulfuric acid to slurry pH value, which is added,
~3.0, acidolysis under conditions of 75~85 DEG C of temperature.
It is filtered after step (2) described acidolysis, as heated in acid hemolysis process, should filter while hot, it is solid that calcium sulfate can be obtained
Body and filtrate containing hydrogen malate calcium and other soluble impurities.It is separated by filtration after removing solid calcium sulphate, resulting filtrate
It is crystallized, crystallizes out hydrogen malate calcium from liquid, then through further isolated more pure hydrogen malate calcium
Solid and mother liquor；Mother liquor herein can return in step (1) and mix with fermentation liquid raw material, to make because containing heteroacid and impurity
Impurity, which passes through, to be segregated into the liquid after step (1) is separated by solid-liquid separation, and is then removed.Hydrogen malate calcium is crystallized
When, decrease temperature crystalline can be used, preferably crystallized at 10~15 DEG C, or use condensing crystallizing, solution is preferably concentrated into original
The 30~40% of quality, or above-mentioned decrease temperature crystalline and condensation crystallization method are used in combination.For the knot for improving the calcium containing hydrogen malate
Brilliant rate can be suitably added the substances such as calcium carbonate, calcium oxide, calcium hydroxide in crystallization process.
The purpose of acidolysis is that hydrogen malate calcium obtained by step (2) is made to be completely converted into apple in step (3) of the present invention
The dosage of acid, acid and acid that when acidolysis is added may insure to realize above-mentioned conversion purpose.Preferably as one kind of the invention
Scheme, step (3) described acidolysis are preferred are as follows: add sulfuric acid to slurries pH be 1.5~2.2, temperature be 20~100 DEG C under conditions of
Acidolysis, until reaction end.It after acidolysis, is separated by solid-liquid separation using the methods of filtering, removes solid calcium sulphate, can be obtained purer
Malic acid acid hydrolysis solution.
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 fermentation method or the enzyme transforming process production resulting fermentation liquid containing calcium malate of malic acid as raw material, heating
To 70~80 DEG C, solid (being rich in calcium malate) is collected in centrifuge separation；
(2) step (1) obtained solid is mixed with water and is sized mixing, it is 2.9~3.0 that sulfuric acid to slurry pH value, which is added, in temperature
Acidolysis under conditions of 75~85 DEG C, is filtered while hot, collects filtrate (being rich in hydrogen malate calcium)；To the filtrate carry out concentration and/
Or decrease temperature crystalline, filtering, collect crystal (being rich in hydrogen malate calcium)；
(3) crystal obtained by step (2) is mixed with water and is sized mixing, sulfuric acid is added and carries out acidolysis, turns hydrogen malate calcium all
Malic acid is turned to, is filtered, malic acid acid hydrolysis solution (being rich in malic acid) is collected.
In the malic acid acid hydrolysis solution that the method for the invention obtains be rich in malic acid, and contain in fermentation liquid succinic acid,
The heteroacid such as fumaric acid have been sufficiently removed.The malic acid acid hydrolysis solution can be further across decoloration, cation exchange, anion
The means such as exchange are to obtain purer malic acid solution, then are further passed through the means such as concentration, crystallization, separation, drying,
It can get high-purity apple acid crystal.
Compared with prior art, method provided by the invention is due to first converting malic acid for the slurries containing calcium malate
Hydrogen calcium simultaneously crystallizes, and the hydrogen malate calcium crystal purity of acquisition is high, so that the malic acid product purity finally obtained is high, high-quality.
The hydrogen malate calcium crystal obtained using the present invention can be improved malic acid acid hydrolysis solution concentration, reduce acid hydrolysis solution color by acidolysis
Element, thus the concentrated cost of process and decoloration difficulty after reducing.
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 present embodiments providing separation and Extraction high-purity malic acid, this method produce malic acid with fermentation method
Resulting fermentation liquid (being rich in calcium malate) is raw material, is proceeded as follows:
(1) 30.67kg fermentation liquid is heated to 70 DEG C, centrifuge separation obtains filtrate 21.96kg and calcium malate wet solid
7.98kg；
(2) step (1) calcium malate wet solid is mixed with 5.63kg water and is sized mixing, be added sulfuric acid to system pH be 3.0 into
Row acidolysis, then filtered at 75 DEG C, obtain filter cake 5.43kg and filtrate 10.21kg；The filtrate is cooled to 15 DEG C, filtering obtains
Obtain the wet crystal 4.73kg of hydrogen malate calcium；
(3) the wet crystal of hydrogen malate calcium obtained by step (2) is mixed with 3.35kg water and is sized mixing, sulfuric acid is added and carries out acidolysis extremely
Hydrogen malate calcium is completely converted into malic acid, be collected by filtration malic acid acid hydrolysis solution 6.32kg ((w/w) containing malic acid 48.3%,
Its heteroacid content < 0.1%)；
(4) acid hydrolysis solution obtained by step (3) is obtained into ion-exchange liquid by decoloration, ion-exchange (ion exchange resin) processing
7.4kg is concentrated into 3.38kg, and decrease temperature crystalline is collected by centrifugation crystal and washs, and obtains the wet crystal 1.82kg of malic acid and mother liquor
2.08kg；By the wet crystal drying of the malic acid, the apple acid crystal that purity is 99.2% is finally obtained.
Embodiment 2
A kind of method for present embodiments providing separation and Extraction high-purity malic acid, this method produce apple with enzyme transforming process
The resulting fermentation liquid of acid (being rich in calcium malate) is raw material, is proceeded as follows:
(1) 21.67kg fermentation liquid is heated to 80 DEG C, centrifuge separation obtains calcium malate wet solid 5.78kg；
(2) step (1) calcium malate wet solid 1.5kg is taken, mixes and sizes mixing with 3kg water, adds 1 step of embodiment (4)
Resulting mother liquor after crystallizing to malic acid until system pH is 2.9 progress acidolysis, then filters at 85 DEG C, obtains filtrate
6.75kg；The filtrate is concentrated into 2.435kg, is cooled to 10 DEG C, filtering obtains the wet crystal 1.983kg of hydrogen malate calcium；
(3) the wet crystal of hydrogen malate calcium obtained by step (2) is mixed with 1.7kg water and is sized mixing, sulfuric acid is added and carries out acidolysis extremely
Hydrogen malate calcium is completely converted into malic acid, and filtrate ((w/w) containing malic acid 41.93%, other heteroacid content < is collected by filtration
0.1%)；
(4) by filtrate obtained by step (3) after decoloration, ion-exchange (ion exchange resin) processing, concentration, decrease temperature crystalline,
Crystal is collected by centrifugation and washs, obtains malic acid wet crystal 838g and mother liquor 754g；By the wet crystal drying of the malic acid, finally
Obtain the apple acid crystal that purity is 99.5%.
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 of separation and Extraction high-purity malic acid, which comprises the steps of:
(1) it using fermentation method or the enzyme transforming process production resulting fermentation liquid containing calcium malate of malic acid as raw material, is separated by solid-liquid separation,
Collect solid；
(2) step (1) obtained solid is mixed with water, acidolysis makes calcium malate be converted into hydrogen malate calcium, and filter is collected in filtering
Liquid；Hydrogen malate calcium contained in the filtrate is crystallized, crystal is collected；
(3) crystal obtained by step (2) is mixed with water, acidolysis makes hydrogen malate calcium be completely converted into malic acid, is separated by solid-liquid separation, and receives
Collect malic acid acid hydrolysis solution.
2. the method according to claim 1, wherein also containing calcium succinate and fumaric acid in the fermentation liquid
Calcium.
3. method according to claim 1 or 2, which is characterized in that the temperature of step (1) described separation of solid and liquid be 10~
100 DEG C, preferably 60~90 DEG C, more preferably 70~80 DEG C.
4. method according to any one of claims 1 to 3, which is characterized in that the pH value of step (2) described acidolysis is
1.5~4.5, preferably 2.0~4.0, more preferably 2.5~3.0.
5. according to the method described in claim 4, it is characterized in that, the temperature of step (2) described acidolysis be 10~100 DEG C, it is excellent
It is selected as 50~90 DEG C, more preferably 75~85 DEG C.
6. method according to claim 4 or 5, which is characterized in that step (2) described acidolysis specifically: sulfuric acid is added extremely
Slurry pH value is 2.9~3.0, acidolysis under conditions of 75~85 DEG C of temperature.
7. method described in any one according to claim 1~6, which is characterized in that step (2) crystallization is decrease temperature crystalline
And/or condensing crystallizing；
The temperature of the decrease temperature crystalline is preferably 10~15 DEG C；The condensing crystallizing preferably by solution be concentrated into proper mass 30~
40%.
8. method described in any one according to claim 1~7, which is characterized in that step (3) described acidolysis are as follows: add sulfuric acid
It is 1.5~2.2 to slurries pH, acidolysis under conditions of temperature is 20~100 DEG C, until reaction end.
9. method according to claim 1 or 2, which comprises the steps of:
(1) using fermentation method or the enzyme transforming process production resulting fermentation liquid containing calcium malate of malic acid as raw material, 70 are heated to
~80 DEG C, solid is collected in centrifuge separation；
(2) step (1) obtained solid is mixed with water and is sized mixing, be added sulfuric acid to slurry pH value be 2.9~3.0, temperature 75~
Acidolysis under conditions of 85 DEG C, is filtered while hot, collects filtrate；Concentration and/or decrease temperature crystalline are carried out to the filtrate, filtered, is collected
Crystal；
(3) crystal obtained by step (2) is mixed with water and is sized mixing, sulfuric acid is added and carries out acidolysis, is completely converted into hydrogen malate calcium
Malic acid acid hydrolysis solution is collected in malic acid, filtering.
10. method described in any one according to claim 1~9, which is characterized in that taken off to the malic acid acid hydrolysis solution
Color, ion exchange resin treatment, then be concentrated, crystallize, separate, dry, obtain high-purity apple acid crystal.
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| CN201910599570.XA CN110272339A (en) | 2019-07-02 | 2019-07-02 | A kind of method of separation and Extraction high-purity malic acid |
| CN202010626545.9A CN111909025B (en) | 2019-07-02 | 2020-07-02 | Method for producing calcium hydrogen malate and application of method in production of malic acid |
| CN202010626544.4A CN111732506B (en) | 2019-07-02 | 2020-07-02 | Method for separating and extracting high-purity malic acid |
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| CN202010626544.4A Active CN111732506B (en) | 2019-07-02 | 2020-07-02 | Method for separating and extracting high-purity malic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112552164A (en) * | 2020-12-08 | 2021-03-26 | 日照金禾博源生化有限公司 | Process method for extracting malic acid from unqualified sodium citrate mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1081206A (en) * | 1992-07-14 | 1994-01-26 | 中国药科大学 | Method with preparing malic acid with enzyme engineering technology |
| CN1059700C (en) * | 1994-05-20 | 2000-12-20 | 广东省微生物研究所 | High-yield saltant aspergillus N1-14' for L-malic acid and method for producing L-malic acid |
| CN101117315B (en) * | 2007-07-10 | 2011-06-01 | 安徽丰原生物化学股份有限公司 | Production method of citric acid |
| CN104357340B (en) * | 2014-11-17 | 2017-08-01 | 中国食品发酵工业研究院 | A kind of method that bioconversion fumaric acid produces L malic acid |
| 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 |
| CN106957224A (en) * | 2016-01-12 | 2017-07-18 | 中粮生物化学（安徽）股份有限公司 | A kind of extracting method of citric acid |
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| CN112552164A (en) * | 2020-12-08 | 2021-03-26 | 日照金禾博源生化有限公司 | Process method for extracting malic acid from unqualified sodium citrate mother liquor |
| CN112552164B (en) * | 2020-12-08 | 2022-12-09 | 日照金禾博源生化有限公司 | Process method for extracting malic acid from unqualified sodium citrate mother liquor |
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