CN102432479A - Method for extracting L-valine from L-valine fermentation liquid - Google Patents

Method for extracting L-valine from L-valine fermentation liquid Download PDF

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CN102432479A
CN102432479A CN2011104567262A CN201110456726A CN102432479A CN 102432479 A CN102432479 A CN 102432479A CN 2011104567262 A CN2011104567262 A CN 2011104567262A CN 201110456726 A CN201110456726 A CN 201110456726A CN 102432479 A CN102432479 A CN 102432479A
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xie ansuan
liquid
nanofiltration
valine
filtration
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CN102432479B (en
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王海雷
彭芳菊
钟秀如
孟祥杰
刘康乐
龚华
梁是森
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Tongliao Meihua Biotechnology Co., Ltd.
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MEIHUA BIOTECH GROUP CO Ltd
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Abstract

The invention relates to the field of amino acid extraction techniques, and discloses a method for extracting L-valine from an L-valine fermentation liquid. The method comprises the following steps: micro-filtering an L-valine fermentation liquid, regulating the pH value of the micro-filtrate to neutrality, sequentially adsorbing with cation resin and anion resin, carrying out primary concentration and crystallization, carrying out nano-filtration, decolorizing the nano-filtrate, and carrying out secondary concentration and crystallization to obtain the L-valine. In the invention, the nano-filtration trapped fluid and the secondary mother solution are respectively sent back to the ion-exchange adsorption step and nano-filtration step for circulation. The invention changes the traditional ion-exchange adsorption technique of directly adsorbing L-valine into the technique of adsorbing impurities and secondary concentration and crystallization, thereby greatly enhancing the purity and yield of the product L-valine, reducing the waste water amount and avoiding environmental pollution by preparing generated waste into feeds.

Description

A kind of method of from the L-valine fermentation liquid, extracting the L-Xie Ansuan
Technical field
The present invention relates to amino acid extraction process field, a kind of method of from the L-valine fermentation liquid, extracting the L-Xie Ansuan specifically is provided.
Background technology
The L-Xie Ansuan, formal name used at school 2-amino-3 Methylbutanoic acid is one of eight kinds of indispensable amino acids of human body, is referred to as branched-chain amino acid with L-leucine, L-Isoleucine.The L-Xie Ansuan can be used for preparing aminoacids complex transfusion, and amino acid transfusion is nutrition agent and matabolizing improvement agent, can be used for treating muscular dystrophy, and to wound, iron wound, the recovery of operation patients has unusual effect.In addition, L-Xie Ansuan and L-Isoleucine all are limiting amino acids in feed, and when L-Xie Ansuan consumption level is higher, the L-Xie Ansuan will become first limiting amino acid.
At present, the basic process for extracting of L-Xie Ansuan has the precipitator method, ion exchange method and full embrane method.The precipitator method are to combine to form deposition with the specificity of L-Xie Ansuan according to precipitation agent, and separation and Extraction then, this method have yield height, advantage such as easy and simple to handle, still, have the heavy technical problem of environmental pollution; Though full embrane method wastewater flow rate is few, film can only be removed a large amount of inorganic ions and macromolecular foreign protein, and a large amount of amino acid close with the L-Xie Ansuan that exist in the fermented liquid can't be removed, and prepared finished product heteroacid is higher.
Take all factors into consideration various factors, ion exchange method slightly is superior to the precipitator method and full embrane method, also is amino acid extraction process method commonly used.Ion exchange method be with adjust pH under the fermented liquid of removing behind the thalline for acid, separate L-Xie Ansuan and impurity amino acid with strongly acidic cationic exchange resin, isolate the L-Xie Ansuan through the ammoniacal liquor wash-out at last.But still some negatively charged ion and cation impurity exist wherein, and are that main impurity amino acid (mainly being L-Ala) is close with L-Xie Ansuan character with the L-Ala, can't effectively separate, and cause L-Xie Ansuan purity lower.If want to improve the purity of L-Xie Ansuan, will adopt multistage ion exchange column string post to extract, this has just caused production process to produce great amount of wastewater, and consumes too much ion exchange resin, increases cost.In addition, it is also lower to utilize ion exchange method to extract the extraction yield of L-Xie Ansuan, and depleted trapped fluid and mother liquor are prone to cause environmental pollution.More than all factors, make the preparation technology of L-Xie Ansuan further to improve.
Summary of the invention
In view of this, the present invention provides a kind of method of from the L-valine fermentation liquid, extracting the L-Xie Ansuan, makes this method can improve the extraction yield and the purity of L-Xie Ansuan.
For realizing the foregoing invention purpose, the present invention provides following technical scheme:
A kind of method of from the L-valine fermentation liquid, extracting the L-Xie Ansuan comprises:
Step 1, L-valine fermentation liquid micro-filtration is obtained micro-filtration cleaner liquid and micro-filtration trapped fluid, regulating micro-filtration cleaner liquid pH value be 6-8, then with strongly acidic cationic exchange resin absorption, follows to adsorb with weakly basic anion exchange resin again and obtains ion exchange liquid;
Step 2, with ion exchange liquid in 50-70 ℃ of following condensing crystal to concentrating the back volume for concentrating the 1/8-1/6 of front volume, the centrifugal acquisition L-Xie Ansuan coarse crystallization and first mother liquor;
Step 3, L-Xie Ansuan coarse crystallization is used dissolved in distilled water, use the nf membrane nanofiltration of molecular weight, obtain nanofiltration cleaner liquid and nanofiltration trapped fluid as 800-1000D;
Step 4, adjusting nanofiltration trapped fluid pH value are 6-8, then with strongly acidic cationic exchange resin absorption, then obtain ion exchange liquid, ion exchange liquid repeating step 2 with weakly basic anion exchange resin absorption again;
Nanofiltration cleaner liquid decolouring back extremely concentrates the back volume for concentrating the 1/8-1/6 of front volume, the centrifugal acquisition L-Xie Ansuan finished product and second mother liquor in 50-70 ℃ of following condensing crystal;
Step 5, second mother liquor use the nf membrane nanofiltration of molecular weight as 800-1000Da, obtain nanofiltration cleaner liquid and nanofiltration trapped fluid, repeating step 4.
Particular flow sheet is referring to Fig. 1.
Wherein, The L-valine fermentation liquid is after L-Xie Ansuan commonly used is produced bacterial strain and fermenting raw materials in the industry, to obtain; The said concentrated back of step 2 and step 4 volume all is preferably and concentrates 1/7 of front volume, and said decolouring is stirred 40min for adding the medicinal powdery activated carbon that accounts for nanofiltration cleaner liquid volume 0.5-0.8% down in 50-70 ℃.
The L-valine fermentation liquid generally contains more metallic cation, negatively charged ion, L-Ala and a spot of other impurity amino acid after the production strain fermentation is intact.Traditional ion exchange method is adjusted downward to fermented liquid pH value and is lower than L-Xie Ansuan iso-electric point; Make fermented liquid be sour environment; Make the L-Xie Ansuan positively charged; Utilize strongly acidic cationic exchange resin absorption L-Xie Ansuan, reach and other amino acid and the isolating purpose of impurity, then through the elutriant wash-out.Though Most amino-acids and L-Xie Ansuan nature difference are bigger, can separate, L-Ala is close with L-Xie Ansuan character, and is similar with the L-Xie Ansuan with the resin absorption ability, can't delamination, and some cation impurities also are prone to sneak into wherein.
The present invention is 5.96 according to L-Xie Ansuan iso-electric point; Preparation is carried out the fermented liquid pH value of IX absorption and adjusted to 6-8; Be preferably 7, make fermented liquid be the partial neutral environment, strong acidic ion resin and weak anion resin under this environment to L-Xie Ansuan adsorptive power a little less than; But inorganic salt and the amino acid whose absorption of small amount of impurities to other are more obvious, can be except that the most impurity removing L-Ala.Because the solubleness of L-Ala is 2 times of the L-Xie Ansuan, and L-Xie Ansuan solubility with temperature changes not obviously, so under comparatively high temps, make L-Ala through condensing crystal and other amino acid of not eliminating are dissolved in the solution, reaches isolating purpose.In order to guarantee higher purity, the present invention after utilizing nanofiltration once more condensing crystal further remove impurity.Wherein, the temperature of the said condensing crystal of step 2 and step 4 all is preferably 65 ℃, and the said pH value of step 1 and step 4 all preferably is adjusted to 7.
Condensing crystal as well known to those skilled in the art generally all carries out under vacuum; In addition; The present invention earlier through resin cation(R.C.) absorption, then again through resin anion(R.A) absorption, is to be acid because fermented liquid descends through resin cation(R.C.) absorption back pH value with fermented liquid; Help anionic adsorption effect, better remove anionic impurity.When adsorbing, last flow velocity is 0.8-1.0 times of resin cation(R.C.) volume per hour, and the volume ratio of resin cation(R.C.) and resin anion(R.A) is 5: 8-10.
Wherein, As preferably; Said strongly acidic cationic exchange resin is for having sulfonic Zeo-karb on vinylbenzene-divinylbenzene interpolymer; Like C100 type strongly acidic cationic exchange resin or 732 type strongly acidic cationic exchange resins, other also can be used for absorption like WA-2 type strong acidic ion resin; Said weakly basic anion exchange resin is the polyacrylic weakly base resin, like the A830 weakly basic anion exchange resin.
To the lower problem of traditional technology L-Xie Ansuan extraction yield; The present invention continues to be recycled to the circulation of IX absorption operation with the nanofiltration trapped fluid; Second mother liquor is continued to be recycled to the circulation of nanofiltration operation, greatly reduced the loss of fermented liquid raw material, help improving the extraction yield of L-Xie Ansuan.
Can know through contrast technical scheme of the present invention and conventional solution; Conventional solution is to utilize resin absorption L-Xie Ansuan, and the present invention utilizes resin absorption impurity, and the L-Xie Ansuan accounts for the overwhelming majority in the fermented liquid; So can know by inference under the L-Xie Ansuan crystalline situation that obtains as much; Traditional technology must need to use more resin, and the method for the invention is the impurity that occupies the minority owing to what adsorb, and the resin usage quantity is less.The resin usage quantity is many more, and the clear water that need go back unmodified resin is just many, and the waste water of generation is just many more, therefore, compares the method for the invention with traditional technology and can reduce wastewater discharge.
In addition, the ion exchange method environmental pollution is bigger also has trapped fluid and the mother liquor behind the micro-filtration, and its COD (chemical oxygen demand) is higher.Traditional technology does not often add processing promptly discharges, and also can't receive effect preferably even handle.And the present invention as optimal technical scheme, also comprises that the micro-filtration trapped fluid that step 1 is obtained mixes with first mother liquor that step 2 obtains, drying for effective head it off, processes L-Xie Ansuan feed.Contain abundant tropina, inorganic salt and multiple amino acids in the micro-filtration trapped fluid and first mother liquor, good growth promoting function is arranged, solved the pollution problem of micro-filtration trapped fluid and mother liquor simultaneously, realize the purpose of zero release for animal.
In the simultaneous test of the method for the invention and conventional ion exchange process; Adopt the L-valine fermentation liquid of identical source, volume to extract; The result shows that the extraction yield of the method for the invention L-Xie Ansuan is about 65%; Purity detects through HPLC and is higher than 98%, and the L-Xie Ansuan extraction yield of conventional ion exchange process is about 60%, and it is about 95% that purity detects through HPLC.
Can know by above technical scheme; The present invention changes the mode that conventional ion exchange absorbing process directly adsorbs the L-Xie Ansuan; Change absorption impurity into, extract the L-Xie Ansuan through secondary concentration crystalline method then, can greatly improve L-Xie Ansuan product gas purity and yield; Reduce wastewater flow rate and can the waste that produced be used to prepare feed, avoid environmental pollution.
Description of drawings
Shown in Figure 1 is the method flow diagram that from the L-valine fermentation liquid, extracts the L-Xie Ansuan according to the invention.
Embodiment
The invention discloses a kind of method of from the L-valine fermentation liquid, extracting the L-Xie Ansuan, those skilled in the art can use for reference this paper content, suitably improve processing parameter and realize.Special needs to be pointed out is that all similarly replace and change apparent to those skilled in the art, they all are regarded as and are included in the present invention.Method of the present invention is described through preferred embodiment, and the related personnel obviously can change or suitably change and combination methods and applications as herein described in not breaking away from content of the present invention, spirit and scope, realizes and use technology of the present invention.
Below in conjunction with embodiment, further set forth the present invention.
Embodiment 1: the method for the invention is extracted the L-Xie Ansuan
1, process for extracting
Fermented liquid after the L-Xie Ansuan fermentation strain of the learning from else's experience fermentation obtains 8L micro-filtration cleaner liquid and micro-filtration trapped fluid (the micro-filtration trapped fluid is subsequent use) after 0.05-0.1 μ m aperture ceramic membrane is handled; It is 6-7 that the micro-filtration cleaner liquid is regulated the pH value; Cross 1L C100 strong acidic ion resin earlier with the flow velocity of 13.3ml/min then, after 1.6L A830 weak anion resin.Will be through the ion exchange liquid after the yin, yang ion exchange resin is handled in 65 ℃ of following Concentrated and crystallized in vacuum; To concentrating the back volume for concentrating 1/7 of front volume; Reduce to spinning behind the normal temperature; Obtain the L-Xie Ansuan coarse crystallization and first mother liquor (first mother liquor is subsequent use), it is that 100% Xie Ansuan is 420g that L-Xie Ansuan coarse crystallization is amounted to into purity.
Getting 8.4L zero(ppm) water dissolves above-mentioned coarse crystallization in the time of 65 ℃; Crossing molecular weight after the dissolving fully is the nf membrane of 1000Da; Obtain nanofiltration cleaner liquid and nanofiltration trapped fluid, the nanofiltration trapped fluid is regulated pH value for being recycled to the circulation of IX absorption operation behind the 6-7, and the nanofiltration cleaner liquid is got 0.8% the pharmaceutical acceptable powder shaped activated carbon that accounts for its volume and in the time of 65 ℃, stirred 40min and decolour; Suction filtration obtains printing opacity and is 99% destainer.
With above-mentioned destainer Concentrated and crystallized in vacuum in 65 ℃ the time, to concentrating the back volume for concentrating 1/7 of front volume, the liquid concentrator of gained in 40-50 ℃ of following spinning, is obtained the L-Xie Ansuan finished product and second mother liquor, second mother liquor is recycled to the circulation of nanofiltration operation.
In 60 ℃ of time oven dry, the gained final product quality is 350g with L-Xie Ansuan finished product, and detected result meets the USP24 standard, and product yield is 65%, and it is 99% that purity detects through HPLC.
2, the simultaneous test of product yield and purity
Utilize traditional technology to extract: get with 1 in the L-valine fermentation liquid of identical source and volume; Downward modulation fermented liquid pH value is acid; After the absorption of C100 strong acidic ion resin, use the ammoniacal liquor wash-out, twice condensing crystal in elutriant decolouring back; The final product yield is 59%, and it is 95% that purity detects through HPLC.
Compare with purity with product yield of the present invention, the L-Xie Ansuan that traditional technology is extracted is all not high, and color and luster is pure white bright not as the method for the invention extraction L-Xie Ansuan, and this is to cause owing to wherein containing assorted amino acid.
3, the preparation of L-Xie Ansuan feed
The micro-filtration trapped fluid subsequent use in 1 and first mother liquor are mixed, spraying drying, L-Xie Ansuan feeds product, the L-valine content is about 40%.
Embodiment 2: the method for the invention is extracted the L-Xie Ansuan
1, process for extracting
Fermented liquid after the L-Xie Ansuan fermentation strain of the learning from else's experience fermentation obtains 60m after 0.05-0.1 μ m aperture ceramic membrane is handled 3Micro-filtration cleaner liquid and micro-filtration trapped fluid (the micro-filtration trapped fluid is subsequent use), it is 7-8 that the micro-filtration cleaner liquid is regulated the pH value, crosses 7.5m earlier with the flow velocity of 6ml/min then 3732 type strong acidic ion resins are after 13.5m 3The A830 weak anion resin.Will be through the ion exchange liquid after the yin, yang ion exchange resin is handled in 50 ℃ of following Concentrated and crystallized in vacuum; To concentrating the back volume for concentrating 1/6 of front volume; Reduce to spinning behind the normal temperature; Obtain the L-Xie Ansuan coarse crystallization and first mother liquor (first mother liquor is subsequent use), it is that 100% Xie Ansuan is 3182kg that L-Xie Ansuan coarse crystallization is amounted to into purity.
Get 64m 3Zero(ppm) water dissolves above-mentioned coarse crystallization in the time of 50 ℃; Crossing molecular weight after the dissolving fully is the nf membrane of 800Da; Obtain nanofiltration cleaner liquid and nanofiltration trapped fluid, the nanofiltration trapped fluid is regulated pH value for being recycled to the circulation of IX absorption operation behind the 6-7, and the nanofiltration cleaner liquid is got 0.5% the pharmaceutical acceptable powder shaped activated carbon that accounts for its volume and in the time of 65 ℃, stirred 40min and decolour; Suction filtration obtains printing opacity and is 99% destainer.
With above-mentioned destainer Concentrated and crystallized in vacuum in 50 ℃ the time, to concentrating the back volume for concentrating 1/6 of front volume, the liquid concentrator of gained in 40-50 ℃ of following spinning, is obtained the L-Xie Ansuan finished product and second mother liquor, second mother liquor is recycled to the circulation of nanofiltration operation.
In 60 ℃ of time oven dry, the gained final product quality is 2651kg with L-Xie Ansuan finished product, and detected result meets the USP24 standard, and product yield is 64%, and it is 98% that purity detects through HPLC.
2, the simultaneous test of product yield and purity
Utilize traditional technology to extract: get with 1 in the L-valine fermentation liquid of identical source and volume; Downward modulation fermented liquid pH value is acid; After the absorption of 732 type strong acidic ion resins, use the ammoniacal liquor wash-out, twice condensing crystal in elutriant decolouring back; The final product yield is 60%, and it is 96% that purity detects through HPLC.
Compare with purity with product yield of the present invention, the L-Xie Ansuan that traditional technology is extracted is all not high, and color and luster is pure white bright not as the method for the invention extraction L-Xie Ansuan, and this is to cause owing to wherein containing assorted amino acid.
3, the preparation of L-Xie Ansuan feed
The micro-filtration trapped fluid subsequent use in 1 and first mother liquor are mixed, spraying drying, L-Xie Ansuan feeds product, the L-valine content is about 40%.
Embodiment 3: the method for the invention is extracted the L-Xie Ansuan
1, process for extracting
Fermented liquid after the L-Xie Ansuan fermentation strain of the learning from else's experience fermentation obtains 8L micro-filtration cleaner liquid and micro-filtration trapped fluid (the micro-filtration trapped fluid is subsequent use) after 0.05-0.1 μ m aperture ceramic membrane is handled; It is 6-7 that the micro-filtration cleaner liquid is regulated the pH value; Cross 1L WA-2 type strong acidic ion resin earlier with the flow velocity of 13.3ml/min then, after 1.6L A830 weak anion resin.Will be through the ion exchange liquid after the yin, yang ion exchange resin is handled in 70 ℃ of following Concentrated and crystallized in vacuum; To concentrating the back volume for concentrating 1/8 of front volume; Reduce to spinning behind the normal temperature; Obtain the L-Xie Ansuan coarse crystallization and first mother liquor (first mother liquor is subsequent use), it is that 100% Xie Ansuan is 413g that L-Xie Ansuan coarse crystallization is amounted to into purity.
Getting 8.4L zero(ppm) water dissolves above-mentioned coarse crystallization in the time of 65 ℃; Crossing molecular weight after the dissolving fully is the nf membrane of 1000Da; Obtain nanofiltration cleaner liquid and nanofiltration trapped fluid, the nanofiltration trapped fluid is regulated pH value for being recycled to the circulation of IX absorption operation behind the 6-7, and the nanofiltration cleaner liquid is got 0.6% the pharmaceutical acceptable powder shaped activated carbon that accounts for its volume and in the time of 65 ℃, stirred 40min and decolour; Suction filtration obtains printing opacity and is 99% destainer.
With above-mentioned destainer Concentrated and crystallized in vacuum in 70 ℃ the time, to concentrating the back volume for concentrating 1/8 of front volume, the liquid concentrator of gained in 40-50 ℃ of following spinning, is obtained the L-Xie Ansuan finished product and second mother liquor, second mother liquor is recycled to the circulation of nanofiltration operation.
In 60 ℃ of time oven dry, the gained final product quality is 342g with L-Xie Ansuan finished product, and detected result meets the USP24 standard, and product yield is 66%, and it is 99% that purity detects through HPLC.
2, the simultaneous test of product yield and purity
Utilize traditional technology to extract: get with 1 in the L-valine fermentation liquid of identical source and volume; Downward modulation fermented liquid pH value is acid; After the absorption of WA-2 type strong acidic ion resin, use the ammoniacal liquor wash-out, twice condensing crystal in elutriant decolouring back; The final product yield is 58%, and it is 94% that purity detects through HPLC.
Compare with purity with product yield of the present invention, the L-Xie Ansuan that traditional technology is extracted is all not high, and color and luster is pure white bright not as the method for the invention extraction L-Xie Ansuan, and this is to cause owing to wherein containing assorted amino acid.
3, the preparation of L-Xie Ansuan feed
The micro-filtration trapped fluid subsequent use in 1 and first mother liquor are mixed, spraying drying, L-Xie Ansuan feeds product, the L-valine content is about 40%.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.

Claims (10)

1. a method of from the L-valine fermentation liquid, extracting the L-Xie Ansuan is characterized in that, comprising:
Step 1, L-valine fermentation liquid micro-filtration is obtained micro-filtration cleaner liquid and micro-filtration trapped fluid, regulating micro-filtration cleaner liquid pH value be 6-8, then with strongly acidic cationic exchange resin absorption, follows to adsorb with weakly basic anion exchange resin again and obtains ion exchange liquid;
Step 2, with ion exchange liquid in 50-70 ℃ of following condensing crystal to concentrating the back volume for concentrating the 1/8-1/6 of front volume, the centrifugal acquisition L-Xie Ansuan coarse crystallization and first mother liquor;
Step 3, L-Xie Ansuan coarse crystallization is used dissolved in distilled water, use the nf membrane nanofiltration of molecular weight, obtain nanofiltration cleaner liquid and nanofiltration trapped fluid as 800-1000D;
Step 4, adjusting nanofiltration trapped fluid pH value are 6-8, then with strongly acidic cationic exchange resin absorption, then obtain ion exchange liquid, ion exchange liquid repeating step 2 with weakly basic anion exchange resin absorption again;
Nanofiltration cleaner liquid decolouring back extremely concentrates the back volume for concentrating the 1/8-1/6 of front volume, the centrifugal acquisition L-Xie Ansuan finished product and second mother liquor in 50-70 ℃ of following condensing crystal;
Step 5, second mother liquor use the nf membrane nanofiltration of molecular weight as 800-1000Da, obtain nanofiltration cleaner liquid and nanofiltration trapped fluid, repeating step 4.
2. according to the said method of claim 1, it is characterized in that said strongly acidic cationic exchange resin is for to have sulfonic Zeo-karb on vinylbenzene-divinylbenzene interpolymer.
3. according to the said method of claim 2, it is characterized in that said on vinylbenzene-divinylbenzene interpolymer, to have sulfonic Zeo-karb be C100 type strongly acidic cationic exchange resin or 732 type strongly acidic cationic exchange resins.
4. according to the said method of claim 1, it is characterized in that said weakly basic anion exchange resin is the polyacrylic weakly base resin.
5. according to the said method of claim 4, it is characterized in that said polyacrylic weakly base resin is the A830 weakly basic anion exchange resin.
6. according to the said method of claim 1, it is characterized in that the temperature of the said condensing crystal of step 2 and step 4 is 65 ℃.
7. according to the said method of claim 1, it is characterized in that the said pH value of step 1 and step 4 all is adjusted to 7.
8. according to the said method of claim 1, it is characterized in that the said concentrated back of step 2 and step 4 volume is and concentrates 1/7 of front volume.
9. according to the said method of claim 1, it is characterized in that said decolouring is stirred 40min for adding the medicinal powdery activated carbon that accounts for nanofiltration cleaner liquid volume 0.5-0.8% down in 50-70 ℃.
10. according to any said method of claim 1-9, it is characterized in that, also comprise:
The micro-filtration trapped fluid that step 1 is obtained mixes with first mother liquor that step 2 obtains, drying, processes L-Xie Ansuan feed.
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CN103232353A (en) * 2013-04-12 2013-08-07 北京轻发生物技术中心 Method for separating and extracting L-valine from broth with high efficiency
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CN105348122A (en) * 2015-10-30 2016-02-24 安徽丰原发酵技术工程研究有限公司 Method for purifying L-alanine final mother liquor
CN106748871A (en) * 2016-11-29 2017-05-31 岳阳科罗德联合化学工业有限公司 A kind of green circulatory industrial production process of amino acid surfactant
CN112979482A (en) * 2020-12-25 2021-06-18 安徽华恒生物科技股份有限公司 High-purity L-valine and preparation method and application thereof
CN115745827A (en) * 2022-09-22 2023-03-07 山东佰萃生特殊医学用途配方食品有限公司 Extraction process for producing calcium pantothenate by fermentation method

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CN103232353A (en) * 2013-04-12 2013-08-07 北京轻发生物技术中心 Method for separating and extracting L-valine from broth with high efficiency
CN104557578A (en) * 2015-02-09 2015-04-29 河北天宁生物科技有限公司 Improved valine extraction process through microbial fermentation and method for preparing foliar fertilizer
CN105348122A (en) * 2015-10-30 2016-02-24 安徽丰原发酵技术工程研究有限公司 Method for purifying L-alanine final mother liquor
CN105294467A (en) * 2015-11-20 2016-02-03 山东恩贝生物工程有限公司 Novel process for extracting feed-grade valine from fermentation liquid
CN105294467B (en) * 2015-11-20 2017-12-19 山东恩贝生物工程有限公司 A kind of technique that feed grade valine is extracted from zymotic fluid
CN106748871A (en) * 2016-11-29 2017-05-31 岳阳科罗德联合化学工业有限公司 A kind of green circulatory industrial production process of amino acid surfactant
CN106748871B (en) * 2016-11-29 2019-03-05 岳阳科罗德联合化学工业有限公司 A kind of green circulatory industrial production process of amino acid surfactant
CN112979482A (en) * 2020-12-25 2021-06-18 安徽华恒生物科技股份有限公司 High-purity L-valine and preparation method and application thereof
CN112979482B (en) * 2020-12-25 2024-02-02 安徽华恒生物科技股份有限公司 High-purity L-valine as well as preparation method and application thereof
CN115745827A (en) * 2022-09-22 2023-03-07 山东佰萃生特殊医学用途配方食品有限公司 Extraction process for producing calcium pantothenate by fermentation method

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