CN103804173B - A kind of process for purification of fermentation organic acid - Google Patents

A kind of process for purification of fermentation organic acid Download PDF

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CN103804173B
CN103804173B CN201210442787.8A CN201210442787A CN103804173B CN 103804173 B CN103804173 B CN 103804173B CN 201210442787 A CN201210442787 A CN 201210442787A CN 103804173 B CN103804173 B CN 103804173B
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organic acid
organic
accordance
liquid
ether
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CN103804173A (en
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高大成
李晓姝
吴丹
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/48Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/43Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/47Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption

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Abstract

The invention discloses a kind of process for purification of fermentation organic acid.The method comprises: I, will stop fermented liquid heat inactivation; II, acidifying make organic acid crystallization separate out, and obtain organic acid crystallization liquid; III, moisture organic acid filter cake organic acid crystallization liquid or filtration obtained mixes with ether organic solvent that organic acid is dissolved, and wherein adds appropriate basic solution, then carries out organic phase and aqueous phase separation; Organic phase after IV, separation, after washing, adds sorbent material, filtering and removing solid substance; The organic phase that V, step IV obtain is cooled to organic acid crystallization and separates out, and after filtration, drying obtains the organic acid production refined.The inventive method uses ether organic solvent and basic solution to refine organic acid, not only shortens technical process, saves the inputs such as equipment, time and energy consumption, and can obtain the polymerization-grade product that purity is high, total nitrogen content is low, be more suitable for suitability for industrialized production.

Description

A kind of process for purification of fermentation organic acid
Technical field
The present invention relates to a kind of organic acid process for purification, from fermented liquid, particularly obtain high purity organic acid method.
Background technology
The organic acid molecule general formula of indication of the present invention is C nh 2n-2o 4, wherein n is 10-18, is that microorganism utilizes the fermentation such as liquid wax and the meta-bolites that obtains.Its fermented liquid is complicated heterogeneous system, secretory product etc. wherein containing unreacted carbon source, microorganism cells and fragment, the substratum do not utilized and meta-bolites and microorganism, especially wherein to grade impurity containing a large amount of protein, pigment and ash, have a strong impact on purity and the application of product, and bring difficulty to this kind organic acid Extractive technology.
At present, very high to this kind organic acid purity requirement on market, particularly the purity requirement of polymerization-grade is higher, general requirement organic acid list acid purity is at more than 98.5wt%, total nitrogen < 30 μ g/g, only has at present and could obtain with organic solvent method purification the polymerization-grade product meeting this and require, and generally, even if purity reaches requirement, its total nitrogen content is still more difficult reaches requirement.
In long-chain biatomic acid process for purification disclosed in CN01142806.6, with long-chain biatomic acid dry powder for raw material, alcohols is used to make solvent treatment long-chain biatomic acid.The diprotic acid of this method first in fermented liquid is first after charcoal absorption, then acidizing crystal, filtration, washing and dry diprotic acid crystalli-zation cake obtain long-chain biatomic acid dry powder, then adopts organic solvent to refine.In the method, the solvent that refining diprotic acid adopts is alcohols, and when heating for dissolving, alcohol easily and diprotic acid generation esterification, causes the reduction of the finished product purity, limits the application in polymerization.The raw material that the method is refined is that moisture filter cake obtains diprotic acid dry powder after drying, raw aqueous quantitative limitation is reduced to the turndown ratio of the method, adds the equipment that thick acid is dry, causes this technical process longer, add production cost.When organic solvent refines diprotic acid, adopt sorbent material generally can reach the requirement of decolouring, but still the more difficult small molecular protein removed wherein, make total nitrogen content undesirable.
In long-chain biatomic acid process for purification disclosed in CN200410018255.7, first pre-treatment is carried out to fermentation method reaction solution, to remove thalline wherein and residual alkane or lipid acid, obtain organic acid clear liquid, then carry out acidizing crystal, acidizing crystal liquid obtains organic acid crude product through filter press again; Finally the crude product obtained refined in high vacuum conditions by wiped film vaporization, short course distillation device or adopt organic solvent to refine.After the diprotic acid crude product that the method obtains and solvent are dissolved, filtration etc. is not taked to remove the operation steps of insoluble impurities, in decrease temperature crystalline process, insoluble impurities must adsorb crystal surface like this, have impact on product purity, brings bad impact to the application of product.And the solvent treatment diprotic acid process in the method, include the solvent recrystallization operation of twice, solvent consumption is larger, add the burden that solvent recuperation is refining, cause operating process comparatively complicated, and the diprotic acid purity adopting solvent method to refine to obtain is the highest only 98.75wt%, produce slightly fluctuate time, just may can not get qualified product.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of organic acid process for purification.Compared with prior art, the inventive method technique is simple, and energy consumption is low, and supplies consumption is few, and the organic acid purity obtained is high, and the foreign matter content such as small protein and pigment is low, is suitable for suitability for industrialized production.
Organic acid process for purification of the present invention, comprising:
I, fermented liquid heat inactivation will be stopped;
II, acidifying make organic acid crystallization separate out, and obtain organic acid crystallization liquid;
III, organic acid filter cake organic acid crystallization liquid or filtration obtained mixes with organic solvent that organic acid is dissolved, described organic solvent to be carbon number be 2 ~ 8 ethers, wherein in above-mentioned system, add the basic solution that mass concentration is 0.5% ~ 30.0%, be preferably 1.0 wt% ~ 15.0 wt%, the add-on of basic solution is 20wt% ~ 500 wt% of organic acid butt weight, be preferably 50 wt% ~ 200 wt%, after mixing, carry out organic phase and aqueous phase separation;
After organic phase washed with water after IV, separation, add sorbent material, filtering and removing solid substance;
The organic phase that V, step IV obtain is cooled to organic acid crystallization and separates out, and after filtration, drying obtains the organic acid production refined.
In the inventive method, stopping fermented liquid described in step I is that microorganism utilizes liquid wax to ferment the meta-bolites obtained, and the organic acid molecule general formula wherein contained is C nh 2n-2o 4, wherein n is 10-18, and organic acid can be single a kind of organic acid, also can be mixed organic acid.After stopping fermented liquid heat inactivation, can carry out the impurity such as filtering and removing thalline, filtration can adopt the ordinary methods such as membrane filtration and equipment.Also can in Step II I the impurity such as filtering and removing thalline.Heat inactivation temperature is generally 75 DEG C ~ 100 DEG C.
In the inventive method, the acidifying described in Step II can adopt ordinary method to carry out.The pH value of described acidifying is 2.0 ~ 4.0, and Heating temperature is 80 ~ 100 DEG C.The above-mentioned acidifying of the present invention acid used can be the H of any concentration 2sO 4, HNO 3, HCl or H 3pO 4.
Step II I organic solvent used is ethers, the carbon number of described ethers is 2 ~ 8, be preferably one or more of ether, propyl ether, isopropyl ether, butyl ether, ethyl isobutyl ether, amyl ether, isoamyl oxide, hexyl ether etc., one or more of more preferably positive propyl ether, isopropyl ether, n-butyl ether, ethyl isobutyl ether, isoamyl oxide etc.
In the inventive method, the weight ratio of organic solvent and organic acid butt is 1:1 ~ 15:1, is preferably 2:1 ~ 7:1.Organic acid crystallization liquid or organic acid filter cake and organic solvent preferably dissolve in a heated condition, and Heating temperature is generally 80 DEG C ~ 150 DEG C, preferably 90 ~ 120 DEG C, concrete according to selecting the boiling point of solvent to determine, generally lower than the boiling temperature of used solvent.
Described basic solution is selected from one or more the solution in sodium bicarbonate, sodium carbonate, sodium hydroxide, saleratus, salt of wormwood, potassium hydroxide.
In the inventive method, can add in step IV deionized water wash organic phase once or once more than, and isolate aqueous phase.
In the inventive method, sorbent material in step IV is one or more in gac, atlapulgite etc., and be preferably gac, add-on is the 0.01wt% ~ 2.0wt% of organic acid butt weight, be preferably 0.01wt% ~ 1.0wt%, adsorption time is 30min ~ 60min.
In the inventive method, till in step V, crystallisation by cooling temperature is generally and makes organic acid sufficient crystallising, temperature is generally 10 DEG C ~ 30 DEG C.
In the inventive method, the organic solvent filtrate obtained in step V, can recycle.
The inventive method can obtain the organic acid production of highly purified single kind, also can obtain mixed organic acid product.
Although it is this area ordinary method that organic solvent method refines this kind organic acid, but the optimum solvent used in existing method and best operational path, also purity requires (98.5%) purity a little more than product quality indicator can only be obtained, this is disadvantageous to the stably manufactured of full scale plant, when production is slightly fluctuated, just qualified product may be can not get.The ether solvent that the inventive method adopts belongs to dipole moment compound, polarity is weak, high molecular weight protein does not dissolve wherein, the insoluble solid formed was easy to filter, then appropriate basic solution is added to containing in organic acid ethers organic phase, wherein part organic acid is made to change into organic acid salt and in being soluble in the aqueous phase, under the effect of salt effect, make the small molecules organonitrogen in solvent phase and pigment be transferred in the aqueous solution, and only use the sorbent material of minute quantity just can obtain purity be greater than 99.8% and total nitrogen be less than the organic acid production of 30 μ g/g.In the art, it has been very difficult that object quality product reaches polymerization-grade index request, purity often improves 0.1 percentage point and total nitrogen to reduce by 1 μ g/g is all very difficult on this basis, and be also all significant and value, this is to the steady running of guarantee full scale plant, improve the aspects such as conforming product rate, having important effect, is also obviously to the quality influence of the polymerization products such as follow-up synthesizing engineering plastic.
The inventive method, while acquisition high purity organic acid production, the advantages such as also have technological process simple, energy consumption is low, and supplies consumption is few.
Embodiment
Process for purification of the present invention is further illustrated below by embodiment.In the present invention, wt% is massfraction.
In the inventive method, containing liquid wax, thalline, the substratum do not utilized, meta-bolites and microorganism secretion thing etc. in fermented liquid, especially wherein containing impurity such as a large amount of protein, pigments.Organic acid crystallization liquid can adopt this area usual method to obtain, as adopted following at least one scheme:
(1) will stop fermented liquid heat and leave standstill, and divide the liquid wax going to upper strata, then cooling also filtration sterilization, obtains filtrate and is acidified with acid to pH2.0 ~ 4.0, and heat simultaneously, obtain organic acid crystallization liquid, or organic acid solution filtration is obtained filter cake;
Actual conditions is: termination fermented liquid is heated 75 DEG C ~ 100 DEG C, leave standstill, then the liquid wax that upper strata is residual is divided, be cooled to 60 DEG C ~ 90 DEG C again, through micro-filtration and/or ultrafiltration apparatus, filtering the impurity such as thalline obtains clear liquid excessively, the clear liquid obtained is added acid for adjusting pH value to 2.0 ~ 4.0, and be heated to 80 DEG C ~ 100 DEG C, obtain organic acid crystallization liquid, or organic acid solution filtration is obtained filter cake.
(2) fermented liquid is heated to 75 DEG C ~ 100 DEG C, and is acidified to pH value 2.0 ~ 4.0, leave standstill, Separation and Recovery liquid wax, obtains organic acid crystallization liquid.
(3) fermented liquid is heated to 75 DEG C ~ 90 DEG C, enters micro-filtration or ultra-filtration equipment, remove thalline and liquid wax etc., the acidification of filtrate obtained to pH value 2.0 ~ 4.0, and is heated to 80 DEG C ~ 100 DEG C, obtains organic acid crystallization liquid, or aqueous solutions of organic acids filtration is obtained filter cake.
Embodiment 1
Get 200ml and obtain C by Candida tropicalis fermentation 12h 22o 4organic acid fermentation liquid, concentration is the fermented liquid of 160g/l.Be heated to 80 DEG C, use H 2sO 4pH value is adjusted to 3.0, leaves standstill 2h, point liquid wax going solution residual, obtains the C of mycetome 12h 22o 4organic acid crystallization liquid.
The C obtaining mycetome 12h 22o 4organic acid crystallization liquid and positive propyl ether (positive propyl ether and C 12h 22o 4weight ratio is 7:1) after mixing, add 1wt%NaOH aqueous solution 32g, and be heated to 85 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 30ml deionized water wash organic phase again, again divide phase of anhydrating; Subsequently to adding 0.3g gac insulation decolouring 30min in organic phase, then cross and filter gac, the organic phase after decolouring is cooled to 30 DEG C of crystallizations and obtains C 12h 22o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 2
Get 200ml and obtain C by Candida tropicalis fermentation 12h 22o 4organic acid fermentation liquid, concentration is the fermented liquid of 160g/l.Be heated to 80 DEG C, use H 2sO 4pH value is adjusted to 3.0, leaves standstill 2h, point liquid wax going solution residual, obtains the C of mycetome 12h 22o 4organic acid crystallization liquid.
The C obtaining mycetome 12h 22o 4organic acid crystallization liquid and n-butyl ether (n-butyl ether and C 12h 22o 4weight ratio is 6:1) mixing, add 10wt%KOH aqueous solution 20g to mixed solution, mix and be heated to 135 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 50ml deionized water wash organic phase again, again divide phase of anhydrating; In organic phase, add 0.2g gac insulation decolouring 30min, then cross and filter gac, the organic phase after decolouring is cooled to 30 DEG C of crystallizations and obtains C 12h 22o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 3
Get 200ml and obtain C by Candida tropicalis fermentation 13h 24o 4organic acid fermentation liquid, concentration is the fermented liquid of 154g/l.Be heated to 70 DEG C, through ceramic micro filter membrane filtration, the liquid wax removing thalline and remnants obtains filtrate.H is added in filtrate 2sO 4adjust ph to 2.4, and be heated to 95 DEG C, obtain C 13h 24o 4organic acid crystallization liquid, is cooled to room temperature filtration and obtains organic acid filter cake.
The C obtained 13h 24o 4organic acid filter cake and n-butyl ether (n-butyl ether and C 13h 22o 4weight ratio is 2:1) mixing, add 15wt%Na wherein 2cO 3aqueous solution 50g, mixes and is heated to 100 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 60ml deionized water wash organic phase again, again divide phase of anhydrating; Add 0.15g gac insulation decolouring 30min to organic phase, then cross and filter gac, the organic phase after decolouring is cooled to 18 DEG C of crystallizations and obtains C 13h 24o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 4
Get the C that 200ml concentration is 145g/l 14h 26o 4organic acid fermentation liquid, is heated to 70 DEG C, and through ceramic micro filter membrane filtration, the liquid wax removing thalline and remnants obtains filtrate.H is added in filtrate 2sO 4adjust ph to 2.4, and be heated to 95 DEG C, obtain C 14h 26o 4organic acid crystallization liquid.
The C obtained 14h 26o 4organic acid crystallization liquid and isopropyl ether (isopropyl ether and C 14h 22o 4weight ratio is 6:1) mixing, add 5wt%NaHCO wherein 3aqueous solution 58g, mixes and is heated to 65 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 30ml deionized water wash organic phase again, again divide phase of anhydrating; In organic phase, add 0.20g gac insulation decolouring 30min, then cross and filter gac, the organic phase after decolouring is cooled to 28 DEG C of crystallizations and obtains C 14h 26o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Embodiment 5
Get the C that 200ml concentration is 135g/l 13h 24o 4and C 14h 26o 4organic acid fermentation liquid, is heated to 70 DEG C, and through ceramic micro filter membrane filtration, the liquid wax removing thalline and remnants obtains filtrate.H is added in filtrate 2sO 4adjust ph to 2.4, and be heated to 95 DEG C, obtain mixed C 13h 24o 4and C 14h 26o 4organic acid crystallization liquid.
The C obtained 13h 24o 4and C 14h 26o 4organic acid crystallization liquid and isoamyl oxide (isoamyl oxide and C 13h 24o 4and C 14h 26o 4weight ratio is 7:1) be mixed and heated to 140 DEG C, until completely dissolved, static 60min, point sub-cloud aqueous phase; 10wt%K is added in organic phase 2cO 3aqueous solution 54g, mixes and is heated to 140 DEG C, static 60min, point sub-cloud aqueous phase; In solvent phase, add 80ml deionized water wash organic phase again, again divide phase of anhydrating; In organic phase, add 1.35g gac insulation decolouring 30min, then cross and filter gac, the organic phase after decolouring is cooled to 23 DEG C of crystallizations and obtains mixed C 13h 24o 4and C 14h 26o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Comparative example 1
Get 200ml and obtain C by Candida tropicalis fermentation 13h 24o 4organic acid fermentation liquid, concentration is the fermented liquid of 154g/l.Be heated to 60 DEG C, through ceramic micro filter membrane filtration, the liquid wax removing thalline and remnants obtains filtrate.H is added in filtrate 2sO 4adjust ph to 2.4, and be heated to 80 DEG C, obtain C 13h 24o 4organic acid crystallization liquid.
The C obtained 13h 24o 4organic acid crystallization liquid and positive propyl ether (weight ratio is 1:3) are mixed and heated to 80 DEG C, until completely dissolved, static 60min, after dividing sub-cloud aqueous phase, 3.0g gac insulation decolouring 30min is added in organic phase, then cross and filter gac, the organic phase after decolouring is cooled to 21 DEG C of crystallizations and obtains C 13h 24o 4organic acid, then obtain product through drying step.Quality product is in table 1.
Table 1 organic acid production quality
Project Acid content, wt% Total nitrogen, μ g/g
Example 1 99.93 <30
Example 2 99.90 <30
Example 3 99.95 <30
Example 4 99.97 <30
Example 5 99.94 <30
Comparative example 1 99.33 69

Claims (15)

1. a process for purification for fermentation organic acid, comprising:
I, fermented liquid heat inactivation will be stopped;
II, acidifying make organic acid crystallization separate out, and obtain organic acid crystallization liquid;
III, organic acid filter cake organic acid crystallization liquid or filtration obtained mixes with organic solvent that organic acid is dissolved, described organic solvent to be carbon number be 2 ~ 8 ethers, the weight ratio of organic solvent and organic acid butt is 1:1 ~ 15:1, wherein in above-mentioned system, add the basic solution that mass concentration is 0.5% ~ 30.0%, the add-on of basic solution is 20wt% ~ 500 wt% of organic acid butt weight, carries out organic phase and aqueous phase separation after mixing;
After organic phase washed with water after IV, separation, add sorbent material, filtering and removing solid substance;
The organic phase that V, step IV obtain is cooled to organic acid crystallization and separates out, and after filtration, drying obtains the organic acid production refined.
2. in accordance with the method for claim 1, it is characterized in that described ethers be ether, propyl ether, butyl ether, amyl ether, hexyl ether one or more.
3. in accordance with the method for claim 1, it is characterized in that described ethers be positive propyl ether, isopropyl ether, n-butyl ether, ethyl isobutyl ether, isoamyl oxide one or more.
4. in accordance with the method for claim 1, it is characterized in that described basic solution is selected from one or more the solution in sodium bicarbonate, sodium carbonate, sodium hydroxide, saleratus, salt of wormwood, potassium hydroxide.
5. in accordance with the method for claim 1, it is characterized in that the mass concentration of described basic solution is 1.0 wt% ~ 15.0 wt%.
6. in accordance with the method for claim 1, it is characterized in that the add-on of described basic solution is 50 wt% ~ 200 wt% of organic acid butt weight.
7. in accordance with the method for claim 1, it is characterized in that described organic acid molecule general formula is C nh 2n-2o 4, wherein n is 10-18, and organic acid is single a kind of organic acid or is mixed organic acid.
8. in accordance with the method for claim 1, it is characterized in that step I heat inactivation temperature is 75 DEG C ~ 100 DEG C.
9. in accordance with the method for claim 1, it is characterized in that the pH value of acidifying described in Step II is 2.0 ~ 4.0, Heating temperature is 80 DEG C ~ 100 DEG C, and acidifying acid used is the H of any concentration 2sO 4, HNO 3, HCl or H 3pO 4.
10. in accordance with the method for claim 1, it is characterized in that in Step II I, the weight ratio of organic solvent and organic acid butt is 2:1 ~ 7:1.
11. in accordance with the method for claim 1, it is characterized in that in Step II I, and organic acid crystallization liquid or organic acid filter cake and organic solvent dissolve in a heated condition, and Heating temperature is 80 DEG C ~ 150 DEG C.
12. in accordance with the method for claim 1, and the sorbent material that it is characterized in that in step IV is one or more in gac, atlapulgite, and add-on is the 0.01wt% ~ 2.0wt% of organic acid butt weight, and adsorption time is 30min ~ 60min.
13. in accordance with the method for claim 1, and the sorbent material add-on that it is characterized in that in step IV is the 0.01wt% ~ 1.0wt% of organic acid butt weight.
14. in accordance with the method for claim 1, it is characterized in that in Step II, and organic acid crystallization liquid adopts following at least one scheme:
(1) termination fermented liquid be heated to 75 DEG C ~ 100 DEG C and leave standstill, dividing the liquid wax going to upper strata, then cooling also filtration sterilization, obtains filtrate and is acidified with acid to pH2.0 ~ 4.0, and be heated to 80 DEG C ~ 100 DEG C simultaneously, obtain organic acid crystallization liquid;
(2) termination fermented liquid is heated to 75 DEG C ~ 100 DEG C, and is acidified to pH value 2.0 ~ 4.0, leave standstill, Separation and Recovery liquid wax, obtains organic acid crystallization liquid;
(3) fermented liquid is heated to 75 DEG C ~ 90 DEG C, enters micro-filtration or ultra-filtration equipment, remove thalline and liquid wax, the acidification of filtrate obtained to pH value 2.0 ~ 4.0, and is heated to 80 DEG C ~ 100 DEG C, obtains organic acid crystallization liquid.
15. in accordance with the method for claim 1, and to it is characterized in that in step V that crystallisation by cooling temperature is for till making organic acid sufficient crystallising, temperature is 10 DEG C ~ 30 DEG C.
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CN106673994A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Refining method for long-chain organic acid
CN106478410A (en) * 2015-11-25 2017-03-08 衡阳屹顺化工有限公司 A kind of preparation method of organic acid
CN112299985B (en) * 2019-07-31 2023-05-30 中国石油化工股份有限公司 Method for refining long-chain dicarboxylic acid in fermentation liquor by using aqueous phase
CN112724012B (en) * 2019-10-28 2023-07-28 中国石油化工股份有限公司 Method for refining long-chain dibasic acid
CN114685269B (en) * 2020-12-29 2024-05-03 上海凯赛生物技术股份有限公司 Purification method of long-chain dibasic acid and long-chain dibasic acid product

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CN1928100A (en) * 2006-09-06 2007-03-14 中国科学院微生物研究所 Novel method of biological synthesizing 1,12-dodecanedioic acid
CN101979368A (en) * 2010-10-19 2011-02-23 大连理工大学 Method for extracting and salting organic acids out of fermentation liquor

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Publication number Priority date Publication date Assignee Title
CN1928100A (en) * 2006-09-06 2007-03-14 中国科学院微生物研究所 Novel method of biological synthesizing 1,12-dodecanedioic acid
CN101979368A (en) * 2010-10-19 2011-02-23 大连理工大学 Method for extracting and salting organic acids out of fermentation liquor

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