CN103804173A - Fermentation organic acid refining method - Google Patents

Fermentation organic acid refining method Download PDF

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Publication number
CN103804173A
CN103804173A CN201210442787.8A CN201210442787A CN103804173A CN 103804173 A CN103804173 A CN 103804173A CN 201210442787 A CN201210442787 A CN 201210442787A CN 103804173 A CN103804173 A CN 103804173A
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organic acid
organic
accordance
ether
solution
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CN103804173B (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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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a fermentation organic acid refining method. The method is as follows: I, heating for inactivation of a terminate fermentation liquid; II, performing acidification for separate out organic acids by crystallization to obtain an organic acid crystallization liquid; III, mixing the organic acid crystallization liquid or a water-containing organic acid filter cake obtained by filtering with an ether organic solvent to dissolve the organic acids, adding a proper amount of an alkaline solution, then separating an organic phase and a water phase; IV, after washing of the separated organic phase, adding an adsorbent, filtering and removing solids; V, cooling the organic phase obtained by the step IV until the organic acids are separated out by crystallization, filtering, and drying to obtain a refined organic acid product. According to the method, the ether organic solvent and the alkaline solution are used for organic acid refining, the technical process is shortened, equipment, time and energy consumption and other investments can be saved, a polymerization-level product with high purity and low total nitrogen content can be obtained, and the method is more suitable for industrial 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, particularly from fermented liquid, 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 fermentations such as liquid wax and the meta-bolites that obtains.Its fermented liquid is complicated heterogeneous system, the substratum and the secretory product of meta-bolites and microorganism etc. that wherein contain unreacted carbon source, microorganism cells and fragment, do not utilize, especially wherein contain a large amount of protein, pigment and the ash impurity that grades, have a strong impact on purity and the application of product, and extract and the refining difficulty of having brought to this kind organic acid.
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 more than 98.5wt%, total nitrogen < 30 μ g/g, only have at present with organic solvent method and purify and could obtain the polymerization-grade product that meets this requirement, and generally, even if purity reaches requirement, its total nitrogen content is still more difficult reaches requirement.
In the disclosed long-chain biatomic acid process for purification of CN01142806.6, take long-chain biatomic acid dry powder as raw material, use alcohols to make solvent treatment long-chain biatomic acid.First the diprotic acid in fermented liquid is first after charcoal absorption for this method, then acidizing crystal, filtration, washing and dry diprotic acid crystallization filter 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 in the time of heating for dissolving, alcohol easily and diprotic acid generation esterification, causes the reduction of the finished product purity, has limited the application aspect polymerization.The refining raw material of the method is that moisture filter cake obtains diprotic acid dry powder after drying, and to raw material, moisture quantitative limitation has reduced the turndown ratio of the method, has increased the dry equipment of thick acid, causes this technical process longer, has increased production cost.In the time of the refining diprotic acid of organic solvent, employing sorbent material generally can reach the requirement of decolouring, but still the more difficult small molecular protein removing wherein makes total nitrogen content undesirable.
In the disclosed long-chain biatomic acid process for purification of CN200410018255.7, first fermentation method reaction solution is carried out to pre-treatment, to remove thalline and residual alkane or lipid acid wherein, 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 obtaining refined under high vacuum condition by wiped film vaporization, short course distillation device or adopted organic solvent refining.After the diprotic acid crude product that the method obtains and solvent are dissolved, do not take filtration to wait the operation steps that removes insoluble impurities, in decrease temperature crystalline process, insoluble impurities must adsorb crystal surface like this, has affected product purity, has brought bad impact to the application of product.And solvent treatment diprotic acid process in the method, comprise the solvent recrystallization operation of twice, the solvent amount of expending is larger, increase the refining burden of solvent recuperation, cause operating process comparatively complicated, and adopt that the refining diprotic acid purity obtaining of solvent method is the highest only a 98.75wt%, producing while slightly fluctuating, 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 obtaining is high, and the foreign matter contents such as small protein and pigment are low, are suitable for suitability for industrialized production.
Organic acid process for purification of the present invention, comprising:
I, will stop fermented liquid heat inactivation;
II, acidifying make organic acid crystallization, obtain organic acid crystal solution;
III, the organic acid filter cake that organic acid crystal solution or filtration are obtained mix with organic solvent dissolves organic acid, described organic solvent is that carbon number is 2 ~ 8 ethers, be wherein 0.5% ~ 30.0% basic solution to adding mass concentration in above-mentioned system, 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;
Organic phase after IV, separation, after water washing, adds sorbent material, filtering and removing solid substance;
The organic phase that V, step IV obtain is cooled to organic acid crystallization, after filtration, is dried and obtains refining organic acid production.
In the inventive method, stop fermented liquid described in step I and be microorganism and utilize the liquid wax meta-bolites obtaining that ferments, the organic acid molecule general formula wherein containing is C nh 2n-2o 4, wherein n is 10-18, organic acid can be single a kind of organic acid, can be also mixed organic acid.Stop, after fermented liquid heat inactivation, can carrying out the impurity such as filtering and removing thalline, filtration can adopt the ordinary methods such as membrane filtration and equipment.Also can be in Step II I the impurity such as filtering and removing thalline.Heat inactivation temperature is generally 75 ℃～100 ℃.
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 ℃.The above-mentioned acidifying acid used of the present invention 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., more preferably one or more of 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 crystal solution or organic acid filter cake and organic solvent preferably dissolve under heating condition, and Heating temperature is generally 80 ℃ ~ 150 ℃, and preferably 90 ~ 120 ℃, concrete definite according to selecting the boiling point of solvent, the general boiling temperature lower than 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, in step IV, can add deionized water wash organic phase once or once, and isolate water.
In the inventive method, sorbent material in step IV is one or more in gac, atlapulgite etc., is preferably gac, and 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 ℃～30 ℃.
In the inventive method, the organic solvent filtrate obtaining 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 refining this kind organic acid of organic solvent method is this area ordinary method, but the optimum solvent using in existing method and best operational path, also can only obtain purity requires (98.5%) purity a little more than product quality indicator, this stably manufactured to full scale plant is disadvantageous, in the time that production is slightly fluctuateed, just may can not get qualified product.The ether solvent that the inventive method adopts belongs to dipole moment compound, a little less than polarity, high molecular weight protein does not dissolve therein, the insoluble solid forming is easy to remove by filter, then to adding appropriate basic solution containing in organic acid ethers organic phase, make wherein part organic acid change into organic acid salt and in being soluble in the aqueous phase, under the effect of salt effect, make small molecules organonitrogen and pigment in solvent phase 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, 0.1 percentage point of the every raising of purity and 1 μ g/g of total nitrogen reduction are very difficult on this basis, and be all also significant and value, this is to guaranteeing full scale plant steady running, improving the aspects such as conforming product rate, have important effect, is also very obvious to the quality influence of the polymerization products such as follow-up synthesizing engineering plastic.
The advantages such as the inventive method, in obtaining high purity organic acid production, also has technological process simple, and energy consumption is low, and supplies consumption is few.
Embodiment
Further illustrate process for purification of the present invention below by embodiment.In the present invention, wt% is massfraction.
In the inventive method, in fermented liquid, contain substratum, meta-bolites and the microorganism secretion thing etc. of liquid wax, thalline, utilization, especially wherein contain the impurity such as a large amount of protein, pigment.Organic acid crystal solution can adopt this area usual method to obtain, as adopted following at least one scheme:
(1) will stop fermented liquid and heat and leave standstill, and divide the liquid wax that goes to upper strata, then cooling filtration sterilization, obtain filtrate and be acidified with acid to pH2.0 ~ 4.0, and heating simultaneously, obtains organic acid crystal solution, or organic acid solution is filtered and obtains filter cake;
Actual conditions is: will stop 75 ℃ ~ 100 ℃ of fermented liquid heating, leave standstill, then divide upper strata residual liquid wax, be cooled to again 60 ℃ ~ 90 ℃, through micro-filtration and/or ultrafiltration apparatus, remove by filter the impurity such as thalline and obtain clear liquid, the clear liquid obtaining is added to acid for adjusting pH value to 2.0 ~ 4.0, and be heated to 80 ℃ ~ 100 ℃, obtain organic acid crystal solution, or organic acid solution is filtered and obtains filter cake.
(2) fermented liquid is heated to 75 ℃ ~ 100 ℃, and is acidified to pH value 2.0 ~ 4.0, leave standstill, Separation and Recovery liquid wax, obtains organic acid crystal solution.
(3) fermented liquid is heated to 75 ℃ ~ 90 ℃, enters micro-filtration or ultra-filtration equipment, remove thalline and liquid wax etc., the filtrate obtaining is acidified to pH value 2.0 ~ 4.0, and is heated to 80 ℃ ~ 100 ℃, obtains organic acid crystal solution, or aqueous solutions of organic acids is filtered and obtains filter cake.
Embodiment 1
Get 200ml and obtain C by Candida tropicalis fermentation 12h 22o 4organic acid fermentation liquid, the fermented liquid that concentration is 160g/l.Be heated to 80 ℃, use H 2sO 4pH value is adjusted to 3.0, leaves standstill 2h, divide and remove the residual liquid wax of solution, obtain the C of mycetome 12h 22o 4organic acid crystal solution.
The C that obtains mycetome 12h 22o 4organic acid crystal solution and positive propyl ether (positive propyl ether and C 12h 22o 4weight ratio is 7:1) mix after, add 1wt%NaOH aqueous solution 32g, and be heated to 85 ℃, static 60min, point sub-cloud water; In solvent phase, add 30ml deionized water wash organic phase again, again divide the phase of anhydrating; With adding 0.3g gac insulation decolouring 30min in backward organic phase, then remove by filter gac, the organic phase after decolouring is cooled to 30 ℃ 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, the fermented liquid that concentration is 160g/l.Be heated to 80 ℃, use H 2sO 4pH value is adjusted to 3.0, leaves standstill 2h, divide and remove the residual liquid wax of solution, obtain the C of mycetome 12h 22o 4organic acid crystal solution.
The C that obtains mycetome 12h 22o 4organic acid crystal solution and n-butyl ether (n-butyl ether and C 12h 22o 4weight ratio is 6:1) mix, add 10wt%KOH aqueous solution 20g to mixed solution, mix and be heated to 135 ℃, static 60min, point sub-cloud water; In solvent phase, add 50ml deionized water wash organic phase again, again divide the phase of anhydrating; In organic phase, add 0.2g gac insulation decolouring 30min, then remove by filter gac, the organic phase after decolouring is cooled to 30 ℃ 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, the fermented liquid that concentration is 154g/l.Be heated to 70 ℃, through ceramic micro filter membrane filtration, the liquid wax that removes thalline and remnants obtains filtrate.In filtrate, add H 2sO 4regulate pH value to 2.4, and be heated to 95 ℃, obtain C 13h 24o 4organic acid crystal solution, is cooled to room temperature filtration and obtains organic acid filter cake.
The C obtaining 13h 24o 4organic acid filter cake and n-butyl ether (n-butyl ether and C 13h 22o 4weight ratio is 2:1) mix, add wherein 15wt%Na 2cO 3aqueous solution 50g, mixes and is heated to 100 ℃, static 60min, point sub-cloud water; In solvent phase, add 60ml deionized water wash organic phase again, again divide the phase of anhydrating; Add 0.15g gac insulation decolouring 30min to organic phase, then remove by filter gac, the organic phase after decolouring is cooled to 18 ℃ 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 ℃, and through ceramic micro filter membrane filtration, the liquid wax that removes thalline and remnants obtains filtrate.In filtrate, add H 2sO 4regulate pH value to 2.4, and be heated to 95 ℃, obtain C 14h 26o 4organic acid crystal solution.
The C obtaining 14h 26o 4organic acid crystal solution and isopropyl ether (isopropyl ether and C 14h 22o 4weight ratio is 6:1) mix, add wherein 5wt%NaHCO 3aqueous solution 58g, mixes and is heated to 65 ℃, static 60min, point sub-cloud water; In solvent phase, add 30ml deionized water wash organic phase again, again divide the phase of anhydrating; In organic phase, add 0.20g gac insulation decolouring 30min, then remove by filter gac, the organic phase after decolouring is cooled to 28 ℃ 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 ℃, and through ceramic micro filter membrane filtration, the liquid wax that removes thalline and remnants obtains filtrate.In filtrate, add H 2sO 4regulate pH value to 2.4, and be heated to 95 ℃, obtain mixed C 13h 24o 4and C 14h 26o 4organic acid crystal solution.
The C obtaining 13h 24o 4and C 14h 26o 4organic acid crystal solution and isoamyl oxide (isoamyl oxide and C 13h 24o 4and C 14h 26o 4weight ratio is 7:1) be mixed and heated to 140 ℃, until completely dissolved, static 60min, point sub-cloud water; In organic phase, add 10wt%K 2cO 3aqueous solution 54g, mixes and is heated to 140 ℃, static 60min, point sub-cloud water; In solvent phase, add 80ml deionized water wash organic phase again, again divide the phase of anhydrating; In organic phase, add 1.35g gac insulation decolouring 30min, then remove by filter gac, the organic phase after decolouring is cooled to 23 ℃ 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, the fermented liquid that concentration is 154g/l.Be heated to 60 ℃, through ceramic micro filter membrane filtration, the liquid wax that removes thalline and remnants obtains filtrate.In filtrate, add H 2sO 4regulate pH value to 2.4, and be heated to 80 ℃, obtain C 13h 24o 4organic acid crystal solution.
The C obtaining 13h 24o 4organic acid crystal solution and positive propyl ether (weight ratio is 1:3) are mixed and heated to 80 ℃, until completely dissolved, static 60min, divide after sub-cloud water, in organic phase, add 3.0g gac insulation decolouring 30min, then remove by filter gac, the organic phase after decolouring is cooled to 21 ℃ 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 (16)

1. a process for purification for fermentation organic acid, comprising:
I, will stop fermented liquid heat inactivation;
II, acidifying make organic acid crystallization, obtain organic acid crystal solution;
III, the organic acid filter cake that organic acid crystal solution or filtration are obtained mix with organic solvent dissolves organic acid, described organic solvent is that carbon number is 2 ~ 8 ethers, be wherein 0.5% ~ 30.0% basic solution to adding mass concentration in above-mentioned system, 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;
Organic phase after IV, separation, after water washing, adds sorbent material, filtering and removing solid substance;
The organic phase that V, step IV obtain is cooled to organic acid crystallization, after filtration, is dried and obtains refining organic acid production.
2. in accordance with the method for claim 1, it is characterized in that described ethers is one or more of ether, propyl ether, isopropyl ether, butyl ether, ethyl isobutyl ether, amyl ether, isoamyl oxide, hexyl ether.
3. in accordance with the method for claim 1, it is characterized in that described ethers is one or more of positive propyl ether, isopropyl ether, n-butyl ether, ethyl isobutyl ether, isoamyl oxide.
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. the mass concentration that in accordance with the method for claim 1, it is characterized in that described basic solution is 1.0 wt% ~ 15.0 wt%.
6. the add-on that in accordance with the method for claim 1, it is characterized in that 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, 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 ℃～100 ℃.
9. in accordance with the method for claim 1, it is characterized in that the pH value of acidifying is 2.0 ~ 4.0 described in Step II, Heating temperature is 80 ℃ ~ 100 ℃, 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 1:1 ~ 15:1.
11. in accordance with the method for claim 1, it is characterized in that in Step II I, and the weight ratio of organic solvent and organic acid butt is 2:1 ~ 7:1.
12. in accordance with the method for claim 1, it is characterized in that in Step II I, and organic acid crystal solution or organic acid filter cake and organic solvent dissolve under heating condition, and Heating temperature is 80 ℃ ~ 150 ℃.
13. in accordance with the method for claim 1, it is characterized in that sorbent material 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.
14. in accordance with the method for claim 1, it is characterized in that the sorbent material add-on in step IV is the 0.01wt% ~ 1.0wt% of organic acid butt weight.
15. in accordance with the method for claim 1, it is characterized in that in Step II, and organic acid crystal solution adopts following at least one scheme:
(1) termination fermented liquid is heated to 75 ℃ ~ 100 ℃ and standing, divides the liquid wax that goes to upper strata, then cooling filtration sterilization, obtain filtrate and be acidified with acid to pH2.0 ~ 4.0, and be heated to 80 ℃ ~ 100 ℃ simultaneously, obtains organic acid crystal solution;
(2) termination fermented liquid is heated to 75 ℃ ~ 100 ℃, and is acidified to pH value 2.0 ~ 4.0, leave standstill, Separation and Recovery liquid wax, obtains organic acid crystal solution;
(3) fermented liquid is heated to 75 ℃ ~ 90 ℃, enters micro-filtration or ultra-filtration equipment, remove thalline and liquid wax, the filtrate obtaining is acidified to pH value 2.0 ~ 4.0, and is heated to 80 ℃ ~ 100 ℃, obtains organic acid crystal solution.
16. in accordance with the method for claim 1, it is characterized in that in step V, crystallisation by cooling temperature is for till making organic acid sufficient crystallising, and temperature is 10 ℃～30 ℃.
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Cited By (5)

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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
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
CN112299985A (en) * 2019-07-31 2021-02-02 中国石油化工股份有限公司 Method for refining long-chain dicarboxylic acid in fermentation liquor by using water phase
CN112724012A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Method for refining long-chain dicarboxylic acid
CN114685269A (en) * 2020-12-29 2022-07-01 上海凯赛生物技术股份有限公司 Purification method of long-chain dicarboxylic acid and long-chain dicarboxylic acid product

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WO2007077568A1 (en) * 2005-12-30 2007-07-12 Council Of Scientific And Industrial Research Process for preparing long-chain dicarboxylic acids
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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WO2007077568A1 (en) * 2005-12-30 2007-07-12 Council Of Scientific And Industrial Research Process for preparing long-chain dicarboxylic acids
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

Cited By (8)

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Publication number Priority date Publication date Assignee Title
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
CN112299985A (en) * 2019-07-31 2021-02-02 中国石油化工股份有限公司 Method for refining long-chain dicarboxylic acid in fermentation liquor by using water phase
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
CN112724012A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Method for refining long-chain dicarboxylic acid
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
CN114685269A (en) * 2020-12-29 2022-07-01 上海凯赛生物技术股份有限公司 Purification method of long-chain dicarboxylic acid and long-chain dicarboxylic acid product
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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