CN112299985A - Method for refining long-chain dicarboxylic acid in fermentation liquor by using water phase - Google Patents
Method for refining long-chain dicarboxylic acid in fermentation liquor by using water phase Download PDFInfo
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- 238000001471 micro-filtration Methods 0.000 claims description 5
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- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- POEDHWVTLBLWDA-UHFFFAOYSA-N 1-butylindole-2,3-dione Chemical compound C1=CC=C2N(CCCC)C(=O)C(=O)C2=C1 POEDHWVTLBLWDA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- 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
Abstract
The invention relates to a method for refining long-chain dicarboxylic acid in fermentation liquor in an aqueous phase, which comprises the steps of pretreating the long-chain dicarboxylic acid fermentation liquor, adding alkali to adjust the pH value to be not less than 8, and reacting for a certain time; adding a small amount of ether solvent, fully back-mixing at 80-95 ℃, and then standing for layering; and cutting out the lower water phase, acidifying at 80-95 ℃, cooling, filtering, cleaning and drying to obtain the product. Compared with the prior art, the invention is based on the aqueous phase method, and obtains the polymer grade product with high purity and low total nitrogen corresponding to the solvent method on the premise of low cost, low loss, environmental protection, safety, simple flow and the like.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a method for refining long-chain dicarboxylic acid in fermentation liquor in an aqueous phase.
Background
The long-chain dicarboxylic acid refers to aliphatic dicarboxylic acid (DCn or DCA for short) with more than 10 carbon atoms in the carbon chain, and comprises saturated and unsaturated dicarboxylic acid, is a fine chemical product with important and wide industrial application, and is an important raw material for synthesizing high-grade spices, high-performance nylon engineering plastics, high-grade nylon hot melt adhesives, high-temperature dielectrics, high-grade paints and coatings, high-grade lubricating oil, cold-resistant plasticizers, resins, medicines, pesticides and the like in the chemical industry.
The preparation of long-chain dicarboxylic acid usually adopts alkane as a substrate, and is obtained by a microbial conversion mode, the components of fermentation liquor are complex, and besides the dicarboxylic acid, the fermentation liquor mainly comprises thalli, protein, macromolecular pigment, inorganic salt and other intermediate metabolites. The long-chain dicarboxylic acid is extracted from the fermentation liquor, and generally subjected to unit operations such as demulsification, acidification, filtration and the like, so that the process flow is relatively complex, and the separation cost accounts for a large share of the production cost.
At present, the separation and purification processes of long-chain dicarboxylic acid mainly comprise a solvent method and a water phase method. Wherein, the solvent method involves using a large amount of organic solvent, so the cost is higher, the solvent loss during the evaporation process is considerable, in addition, the solvent needs to be treated and recycled, and the whole process flow is longer. Most of domestic enterprises mainly producing long-chain dicarboxylic acid use an acetic acid method solvent refining process, but due to the strong corrosivity of acetic acid, the process equipment investment and solvent recycling treatment section have high energy consumption, the process flow is complex, and the solvent harm is large.
The separation and purification of the dicarboxylic acid by the aqueous phase method is carried out in a medium using water as a solvent. The following processing means are typically included: microfiltering and ultrafiltering dicarboxylic acid fermentation liquor, decolorizing and removing impurities by using active carbon, activated clay and the like, adding inorganic acid to separate out dicarboxylic acid, and filtering, washing and drying to obtain a dicarboxylic acid product. The existing water phase method dicarboxylic acid refining and purifying technology has poor removing capability for water-soluble protein/protein pigment remained in fermentation liquor, and the heating operation in the later half process of the technology can promote the oxidative denaturation of the pigment/protein, and the pigment/protein can be adsorbed in dicarboxylic acid crystal along with the temperature reduction, so that the quality of the final product is reduced. Although the purification technology by the aqueous phase method is simple and safe in process, low in investment and free from pollution, the refining process needs to be further improved to obtain a high-quality long-chain dicarboxylic acid product.
Patent CN102911036A discloses a process for obtaining high purity dicarboxylic acids comprising: i, heating and inactivating terminated fermentation liquor; II, acidifying to crystallize and separate out dicarboxylic acid, and filtering to obtain a dicarboxylic acid filter cake; III, mixing the dicarboxylic acid filter cake with an ether solvent to dissolve the dicarboxylic acid, and separating an organic phase from a water phase, wherein the ether solvent is diethyl ether, propyl ether, butyl ether, amyl ether or hexyl ether; IV, adding an adsorbent into the organic phase obtained in the step III, and filtering to remove solid matters; and V, cooling the organic phase obtained in the step IV until dicarboxylic acid is crystallized and separated out, filtering to obtain a dicarboxylic acid crystallization filter cake, and drying the dicarboxylic acid crystallization filter cake to obtain a dicarboxylic acid product with the dicarboxylic acid purity of more than 98.5% by weight. The method is a solvent recrystallization method, the usage amount of the solvent in the refining process is large, the volatilization/evaporation amount of the solvent is considerable, and the corresponding recovery mode occupies certain cost in industrial amplification. And the product refined by the method contains solvent taste because no effective cleaning means is available at present due to the inclusion of the solvent in the crystallization process.
CN108947809A discloses a method for extracting and refining long-chain dicarboxylic acid from fermentation broth, which comprises (1) fermentation broth pretreatment: adding an alkaline pH regulator into the fermentation liquor to control the pH of the system in an alkaline range, and heating to promote the dissolution of the intracellular long-chain dicarboxylic acid; (2) collecting fermentation clear liquid: filtering to obtain a fermented clear liquid after the treatment in the step (1), and taking a water phase clear liquid layer after standing and layering; (3) extracting and refining long-chain dicarboxylic acid: controlling the temperature of the clear liquid of the water phase to be 70-85 ℃, adding an organic solvent according to a proportion, heating to 80-90 ℃, then adding an acidic pH regulator to control the pH of the system to be in an acidic range, heating to 90-100 ℃ until the long-chain dicarboxylic acid in the system is completely dissolved, standing for layering to separate out the water phase, and filtering and drying the organic phase to obtain a refined product of the long-chain dicarboxylic acid. The method has the advantages that a mixed state of a water phase and an organic phase is formed in a system by adding an organic solvent, and then long-chain dicarboxylic acid is directly transferred from the water phase to the organic phase by using the pH change and temperature control of the system, so that the extraction process is completed in one reactor, the refining of the long-chain dicarboxylic acid can be realized by only using one process unit, the refining process of the long-chain dicarboxylic acid from a liquid phase to a solid-phase crude acid and from the solid-state crude acid to an organic extraction phase in the traditional process is simplified, the crude acid extraction process in the traditional process is reduced, the loss in the extraction process is reduced, the operation steps are reduced, and the yield is improved. However, in this process, the dicarboxylic acid is finally extracted in the organic phase, the amount of organic solvent used is relatively large and a portion is lost with evaporation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for refining long-chain dicarboxylic acid in fermentation liquor in an aqueous phase. Compared with the prior art, the invention is based on the aqueous phase method, and obtains the polymer grade product with high purity and low total nitrogen corresponding to the solvent method on the premise of low cost, low loss, environmental protection, safety, simple flow and the like.
The method for refining the long-chain dicarboxylic acid in the fermentation liquor by using the water phase comprises the following steps:
(1) pretreating the long-chain dicarboxylic acid fermentation liquor to remove thalli and part of pigment;
(2) adding alkali to adjust the pH value to be not less than 8, and reacting for a certain time;
(3) adding a small amount of ether solvent, fully back-mixing at 80-95 ℃, and then standing for layering;
(4) and cutting out the lower water phase, acidifying at 80-95 ℃, cooling, filtering, cleaning a filter cake, and drying to obtain the product.
The long-chain dicarboxylic acid fermentation broth in the step (1) is a fermentation broth for preparing long-chain dicarboxylic acid by fermenting microorganisms with alkane and the like, wherein the molecular general formula of the contained long-chain dicarboxylic acid is CnH2n-2O4Wherein n is 10 to 18.
The pretreatment of the fermentation liquid in the step (1) adopts a method which is conventionally used in the field and is used for removing thalli and pigment, for example, methods such as heating, filtering, decoloring and the like can be adopted, and specifically, the following methods can be adopted: heating the long-chain dicarboxylic acid fermentation liquor to 70-80 ℃, carrying out microfiltration, ultrafiltration and the like, and then carrying out activated carbon decoloration and filtration to remove thalli and partial pigments.
And (3) adding alkali to adjust the pH value to be not less than 8, preferably 9-11 in the step (2). The alkali can be at least one of potassium hydroxide, sodium hydroxide and the like, and in view of equipment and field operation, alkali liquor with certain concentration is preferably used, and the mass concentration of the alkali liquor is 30-40%.
And (3) adding alkali to adjust the pH value in the step (2), and reacting for 10-60 min.
The ether solvent in the step (3) may be at least one selected from the group consisting of ethyl ether, propyl ether, butyl ether, pentyl ether, hexyl ether, heptyl ether, etc., preferably at least one selected from the group consisting of butyl ether, pentyl ether, hexyl ether, etc.
The adding volume of the ether solvent is 2-5% of the volume of the fermentation liquor.
And (3) adding an ether solvent in the step (3), back-mixing at 80-95 ℃ for not less than 45min, and standing for layering. And the standing layering does not need heat preservation, and the standing time is 60-90 min.
The acid used in the acidification in the step (4) is any one or more of inorganic acids, such as at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and the like, and preferably sulfuric acid. The acidification pH value is 2-4, the acidification temperature is 80-95 ℃, and the acidification time is 1.5-2.5 h.
Cooling to not higher than 40 ℃ in the step (4) and then filtering; the filtration adopts conventional filtration forms such as plate-and-frame filtration and the like.
The washing solution in the step (4) is desalted water, and the washing is stopped until the pH of the filtrate is above 5.5, preferably 5.5-6.5. The drying temperature is 95-100 ℃, the drying time is 1.5-2 h, and the drying can be carried out by adopting a conventional method, such as hot air drying.
Furthermore, the residual water phase and the residual solvent phase are naturally cooled and then are conveyed to a storage tank for storage, and after multiple batches of water phases are accumulated, such as 4-6 batches of water phases, the water phases and the solvent phases can be uniformly treated and recycled. The specific method comprises the following steps: heating the mixed solution to 85-90 ℃, standing for 30-60 min, cutting off the lower aqueous phase, treating the aqueous phase in the step (4), naturally cooling and cooling the residual solvent phase, and centrifuging at a low temperature of-15-5 ℃, wherein a high-speed centrifuge is usually adopted, the centrifugal speed is not less than 9500rpm, and the centrifugal time is not less than 10min, so as to ensure the separation effect. The centrifugal clear liquid component can be directly returned to the solvent storage tank for continuous use, and the residual liquid is treated as waste liquid and waste solid.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adds alkali into the pretreated fermentation liquor to make the pH value of the fermentation liquor higher than 8 and raise the temperature, under the condition, part of water-soluble protein can be promoted to denature and is easy to dissolve in a small amount of added ether solvent, so that the pigment and impurities enter an organic phase, and then the water phase in which the product is dissolved is separated by cutting water, thereby realizing the high-efficiency removal of the pigment and the impurities. The dicarboxylic acid salt is extracted in the water phase, the crystallization environment is clean, and therefore the long-chain dicarboxylic acid with high purity and meeting the requirements of polymer-grade products is easily obtained.
(2) Compared with the traditional solvent recrystallization method, the invention changes the traditional concept of solvent extraction of target products, but uses the solvent to directly extract impurities in the fermentation liquor, thereby omitting the process of preparing crude products from the fermentation liquor, shortening the flow, and greatly reducing the solvent consumption and the process loss. The product of the invention is crystallized in the water phase, the solvent included in the crystallization process is water, salt or inorganic acid aqueous solution, and can be removed by a simple washing method, such as pulping and leaching, so that the risks of inclusion of organic solvent and impurities dissolved in the organic solvent are avoided, the polymer-grade product is favorably obtained, and the technical problem that the high-quality long-chain dicarboxylic acid cannot be refined by the existing water phase method is solved.
(3) The invention adopts ether solvent as impurity carrier, the thermal stability and chemical stability of the solvent are good, the dosage is very small, the reaction process does not need pressurization operation, and the loss amount of the solvent is small. And the solvent and the long-chain dicarboxylic acid do not generate side reaction, and the product can be directly applied to downstream polymerization reaction. Short solvent using flow, less single-pass loss, simple operation and small potential safety hazard.
Detailed Description
The following examples are provided to further illustrate the method and effect of refining long-chain dicarboxylic acids in fermentation broth in aqueous phase according to the present invention. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments. In the present invention, wt% is a mass fraction and vt% is a volume fraction.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The test materials used in the following examples were purchased from biochemical reagent stores unless otherwise specified.
In the invention, the total acid content is measured and calculated by adopting an acid-base titration method, the monoacid content is measured and calculated by adopting a gas chromatography peak area normalization method, and the total nitrogen content is detected by adopting a boat sample injection chemiluminescence method.
Example 1
(1) 2000mL of C with a concentration of 160g/L12H22O4Pretreating fermentation liquor: heating the fermentation liquor to 75 ℃ for inactivation, then carrying out microfiltration and ultrafiltration membrane filtration, and then decoloring and filtering by active carbon.
(2) And (2) adding a NaOH solution with the mass concentration of 32% into the fermentation liquor obtained in the step (1) until the pH value reaches 9.5, and reacting for 30 min.
(3) 100mL of n-amyl ether was added, the reaction was stirred at 91.5 ℃ for 45min, and then stopped, the mixture was allowed to stand for 60min, and the lower aqueous phase was cut off.
(4) After the cut aqueous phase was collected, 95% sulfuric acid was slowly added and stirring was turned on, and the addition was stopped when the pH dropped to 2.8 and acidified at 85 ℃ for 2 hours. Naturally cooling to 40 ℃, performing plate-frame filtration, then cleaning a filter cake by using desalted water, stopping cleaning when the pH value of the cleaning liquid is increased to 6.0, removing the filter cake after purging, conveying the filter cake to a hot air dryer for drying, wherein the drying temperature is 100 ℃, and the drying time is 1.5 hours, thus obtaining the product. The results are shown in Table 1.
Example 2
(1) 2000mL of C with a concentration of 150g/L10H18O4Fermentation liquor, pretreatment: heating the fermentation liquor to 70 ℃ for inactivation, then carrying out microfiltration and ultrafiltration membrane filtration, and then decoloring and filtering by active carbon to remove thalli and pigments.
(2) And (2) adding the fermentation liquor obtained in the step (1) into a NaOH solution with the mass concentration of 30% until the pH value reaches 8.1, and reacting for 20 min.
(3) Adding 100mL of n-amyl ether, stirring at 85 deg.C, reacting for 60min, standing for 45min, and cutting off the lower aqueous phase.
(4) After the cut aqueous phase was collected, 95% sulfuric acid was slowly added and stirring was turned on, and the addition was stopped when the pH dropped to 2.6 and acidified at 90 ℃ for 2 hours. Naturally cooling to 35 ℃, conveying to a plate-and-frame filter, cleaning a filter cake by using desalted water, stopping cleaning when the pH value of a cleaning solution is increased to 5.5, removing the filter cake after purging, conveying to a hot air dryer for drying, wherein the drying temperature is 95 ℃, and the drying time is 2 hours, thus obtaining the product. The results are shown in Table 1.
Example 3
(1) 2000mL of C with a concentration of 140g/L16H30O4Fermentation liquor, pretreatment: heating the fermentation liquor to 80 ℃ for inactivation, then carrying out microfiltration and ultrafiltration membrane filtration, and then decoloring and filtering by active carbon.
(2) And (2) adding the fermentation liquor obtained in the step (1) into a NaOH solution with the mass concentration of 40% until the pH value reaches 11, and reacting for 10 min.
(3) Adding 100mL of n-amyl ether, stirring at 93 ℃ for reaction for 30min, stopping, standing for 75min, cutting off a lower water phase, preserving heat and conveying to an acidifier.
(4) After the cut aqueous phase was collected, 95% sulfuric acid was slowly added and stirring was turned on, and the addition was stopped when the pH dropped to 3.0 and acidified at 90 ℃ for 1.5 hours. Naturally cooling to 30 ℃, conveying to a plate-and-frame filter, cleaning a filter cake by using desalted water, stopping cleaning when the pH value of a cleaning solution is increased to 6.5, removing the filter cake after purging, conveying to a hot air dryer for drying, wherein the drying temperature is 100 ℃, and the drying time is 1.5 hours, thus obtaining the product. The results are shown in Table 1.
Example 4
The purification process and the operating conditions were the same as in example 1, except that: and (2) replacing sodium hydroxide with potassium hydroxide with the mass concentration of 32%, and adjusting the pH value to 9.5.
Example 5
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with a mixed solvent of n-butyl ether and n-heptyl ether (the volume ratio is 1: 1).
Example 6
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with diethyl ether.
Example 7
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with n-propyl ether.
Example 8
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with n-butyl ether.
Example 9
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with n-hexyl ether.
Example 10
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with n-heptyl ether.
Example 11
The purification process and the operating conditions were the same as in example 1, except that: and (4) replacing sulfuric acid with nitric acid for acidification.
Example 12
The purification process and the operating conditions were the same as in example 1, except that: and (4) replacing sulfuric acid with hydrochloric acid for acidification.
Comparative example 1
The purification process and the operating conditions were the same as in example 1, except that: and (2) adjusting the pH value to 7.8.
Comparative example 2
The purification process and the operating conditions were the same as in example 1, except that: the reaction temperature in the step (3) is 75 ℃.
Comparative example 3
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with n-butanol.
Comparative example 4
The purification process and the operating conditions were the same as in example 1, except that: and (3) replacing n-amyl ether with ethyl acetate.
And (3) naturally cooling the residual water phase and solvent phase in each embodiment and comparative example, and then conveying the water phase and solvent phase to a storage tank for storage, accumulating 6 batches, and uniformly treating and recycling. The specific method comprises the following steps: and (3) heating the mixed solution to 85 ℃, standing for 45min, cutting off a lower water phase, treating the water phase in the step (4), naturally cooling and cooling the residual solvent phase, and centrifuging at the low temperature of 0 ℃ for 10min at a high-speed centrifuge at the rotation speed of 12000rpm to ensure the separation effect.
TABLE 1 Effect of the products of examples and comparative examples
As can be seen from table 1, the total nitrogen content in the product obtained by the technical scheme of the present application is significantly reduced, while the total nitrogen content in the comparative examples 1 to 4 lacking the technical features of the present application is relatively high.
Claims (16)
1. A method for refining long-chain dicarboxylic acid in fermentation liquor in an aqueous phase is characterized by comprising the following steps:
(1) pretreating the long-chain dicarboxylic acid fermentation liquor to remove thalli and part of pigment;
(2) adding alkali to adjust the pH value to be not less than 8, and reacting for a certain time;
(3) adding a small amount of ether solvent, fully back-mixing at 80-95 ℃, and then standing for layering;
(4) and cutting out the lower water phase, acidifying at 80-95 ℃, cooling, filtering, cleaning a filter cake, and drying to obtain the product.
2. The method of claim 1, wherein: the long-chain dicarboxylic acid fermentation liquor in the step (1) is fermentation liquor for preparing long-chain dicarboxylic acid by utilizing alkane fermentation of microorganisms, wherein the molecular general formula of the contained long-chain dicarboxylic acid is CnH2n-2O4Wherein n is 10 to 18.
3. The method according to claim 1 or 2, characterized in that: the pretreatment method of the fermentation liquor in the step (1) comprises the following steps: heating the long-chain dicarboxylic acid fermentation liquor to 70-80 ℃, carrying out microfiltration and ultrafiltration, and then carrying out activated carbon decoloration and filtration to remove thalli and partial pigment.
4. The method of claim 1, wherein: and (3) adding alkali to adjust the pH value to 9-11 in the step (2).
5. The method according to claim 1 or 4, characterized in that: the alkali in the step (2) is at least one of potassium hydroxide and sodium hydroxide.
6. The method according to claim 1 or 4, characterized in that: and (3) adding alkali to adjust the pH value in the step (2), and reacting for 10-60 min.
7. The method of claim 1, wherein: the ether solvent in the step (3) is at least one of ethyl ether, propyl ether, butyl ether, amyl ether, hexyl ether or heptyl ether.
8. The method of claim 7, wherein: and (3) the ether solvent is at least one of butyl ether, amyl ether and hexyl ether.
9. The method of claim 1, 7 or 8, wherein: in the step (3), the ether solvent is added according to the ratio of the volume of the solvent to the volume of the fermentation liquor of 2-5%.
10. The method of claim 1, wherein: adding an ether solvent into the mixture obtained in the step (3), and then back-mixing the mixture at the temperature of 80-95 ℃ for not less than 45 min; and (4) standing and layering are carried out without heat preservation, and the standing time is 60-90 min.
11. The method of claim 1, wherein: the acid added in the step (4) is any one or more of inorganic acids, preferably at least one of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and more preferably sulfuric acid.
12. The method of claim 1, wherein: in the step (4), the pH value of acidification is 2-4, the acidification temperature is 80-95 ℃, and the acidification time is 1.5-2.5 h.
13. The method of claim 1, wherein: cooling to a temperature not higher than 40 ℃ in the step (4), and then filtering; the filtration is plate and frame filtration.
14. The method of claim 1, wherein: and (4) cleaning the desalted water serving as the cleaning liquid in the step (4) until the pH value of the filtrate is more than 5.5.
15. The method of claim 1, wherein: and (4) drying at the temperature of 95-100 ℃ for 1.5-2 h, wherein hot air type drying is adopted for drying.
16. The method of claim 1, wherein: and (3) naturally cooling the residual water phase and the residual solvent phase, conveying the cooled residual water phase and the residual solvent phase to a storage tank for storage, heating the mixed solution accumulated in multiple batches to 85-90 ℃, standing for 30-60 min, cutting off the lower water phase, treating the water phase by the process in the step (4), naturally cooling and cooling the residual solvent phase, centrifuging at the low temperature of-15-5 ℃, and directly returning the centrifuged clear liquid component to the solvent storage tank for continuous use.
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| CN1255483A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for refining long-chain biatomic acid |
| CN103772186A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Refining method of fermented organic acid |
| CN103804173A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Fermentation organic acid refining method |
| CN108947809A (en) * | 2017-05-18 | 2018-12-07 | 中国石油化工股份有限公司 | A method of extracting simultaneously refining long-chain dicarboxylic acids from fermentation liquid |
| CN109485558A (en) * | 2017-09-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of method of purification of long-chain biatomic acid |
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| CN1255483A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for refining long-chain biatomic acid |
| CN103772186A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Refining method of fermented organic acid |
| CN103804173A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Fermentation organic acid refining method |
| CN108947809A (en) * | 2017-05-18 | 2018-12-07 | 中国石油化工股份有限公司 | A method of extracting simultaneously refining long-chain dicarboxylic acids from fermentation liquid |
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