CN108017535B - Method for extracting long-chain dicarboxylic acid from fermentation liquor - Google Patents
Method for extracting long-chain dicarboxylic acid from fermentation liquor Download PDFInfo
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Abstract
The invention discloses a method for extracting long-chain dicarboxylic acid from fermentation liquor. The method comprises the following steps: acidifying and crystallizing the pretreated terminated fermentation liquor, adding water, mixing, pulping, adding a pyridine compound, performing membrane filtration, adding a sodium hydroxide solution into the filtrate, mixing the crystal obtained by filtration with water, heating, dissolving, adsorbing, filtering, adding acid into the filtrate, acidifying, and crystallizing to obtain a long-chain dicarboxylic acid product. The long-chain dicarboxylic acid extracted by the method has the advantages of high purity, white color, low protein content, loose product, easy drying and the like.
Description
Technical Field
The invention relates to a compound C10~C18Method for extracting dibasic acids, especially from C10~C18A method for extracting long-chain dicarboxylic acid from normal alkane fermentation liquor.
Background
The general formula of the long-chain dibasic acid molecule is CnH2n-2O4Wherein n is 10-18, is a metabolite obtained by fermenting microorganism with alkane, and exists in fermentation liquor in the form of double salt of long-chain dibasic acid.
The long-chain dibasic acid is a metabolite obtained by fermenting n-alkane with a microorganism. The fermentation liquor is a complex multi-phase system, which contains unreacted normal alkane, microbial cells and fragments, unused culture medium and metabolites, microbial secretion and the like, and particularly contains a large amount of impurities such as protein, pigment and the like, which influence the purity and appearance quality of the product.
The long carbon chain dibasic 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 engineering plastics, high-grade hot melt adhesives and the like. The fermentation method for producing the long-chain dibasic acid gradually replaces the traditional chemical synthesis method with the advantages of strong reaction specificity, mild reaction conditions and the like, receives general attention at home and abroad, and opens up a wide space for the development of new material industry.
At present, the main process for extracting the long-chain dicarboxylic acid commonly used in the industry comprises the following steps: heating and inactivating the fermentation liquor, putting the fermentation liquor into a microfiltration or ultrafiltration device, removing mycoprotein and the like to obtain clear filtrate, adding sulfuric acid to acidify the filtrate until the pH value is 2.0-4.0, heating the fermentation liquor under stirring to obtain a long-chain dibasic acid crystal aqueous solution, cooling the aqueous solution, filtering the aqueous solution, washing the filter cake to be neutral by using water, and drying the filter cake by using air to obtain a long-chain dibasic acid filter cake.
In the process of extracting the long-chain dibasic acid crude acid, insoluble proteins such as thalli and the like in the fermentation liquor can be removed through microfiltration or ultrafiltration, and soluble proteins and long-chain dibasic acid salt enter the filtrate together. In the process of converting long-chain dibasic acid salt into long-chain dibasic acid through acidification and crystallizing, soluble protein precipitated through electro-precipitation or denaturation under acidic conditions is embedded by the precipitated dibasic acid, and cannot be removed even through a filtering and washing mode, so that the content of the protein in the extracted long-chain dibasic acid is high. The long-chain dibasic acid obtained by the method has yellow color, high viscosity, easy caking and high protein content, and is not suitable to be used as a raw material for downstream product production.
CN102191187A discloses a preparation method of long-chain dibasic acid, which uses a method for extracting long-chain dibasic acid: demulsifying after fermentation, filtering with filter membrane to remove thallus and residual hydrocarbon, decolorizing the clear liquid with active carbon, and decolorizing the decolorized liquid with H2SO4Or HCl acidifying crystallization, filter pressing, washing, blow drying and drying to obtain the product long-chain dibasic acid. The method adopts a method for extracting the crude long-chain dicarboxylic acid which is commonly used by production enterprises in the industry, and the nitrogen content of the product obtained by the method is far more than 30 ppm. Although the clear solution is decolorized by using activated carbon, most soluble protein can not be removed, the soluble protein is separated out and embedded in long-chain dibasic acid during acidification and crystallization, the existence of macromolecular protein enables the viscosity of a filter cake of filter-pressed long-chain dibasic acid crystals to be high, the gaps among crystal particles to be extremely small or blocked, and washing difficulty is caused, wherein the embedded impurities such as pigment, ash and the like can not be washed and removed, so that the product quality is poor, and the application is limited.
CN102476990A discloses a method for extracting and refining a long-chain dicarboxylic acid crude product, which comprises the following steps: 1) mixing the filtrate obtained after the fermentation of the long-chain dicarboxylic acid with an extractant, heating the mixture to 40-100 ℃, adding acid for acidification to obtain a mixed solution, adjusting the pH value to 2-6, wherein the extractant is selected fromC4～C10One or more of monohydric alcohol; 2) fully mixing and standing the mixed solution, and then carrying out liquid-liquid separation to obtain an extract phase; 3) cooling and crystallizing the extract phase, removing the solvent, and drying to obtain the purified long-chain dicarboxylic acid product. The method for purifying the long-chain dicarboxylic acid by using an extraction method has the problems of low extraction yield, low product purity and the like. Particularly, the method adopts monohydric alcohol to extract long-chain dibasic acid under acidic condition, esterification reaction can occur, and the generated long-chain dibasic acid ester and the dibasic acid are dissolved in the monohydric alcohol extraction phase together, and the generated long-chain dibasic acid ester and the dibasic acid are adhered to the surface of a crystal or embedded in the crystal inevitably when the dibasic acid is cooled and crystallized, so that the final product inevitably contains dibasic acid ester, and the purity of the product is reduced.
CN1611478A discloses a method for salting out one or more C's by using a single salt10-C18The method for extracting and refining the long-chain dicarboxylic acid from the fermentation liquor of the normal alkane comprises the following steps: I. heating the terminated fermentation liquor to demulsify, separating and recovering alkane, then acidifying, crystallizing and filtering to obtain a long-chain dibasic acid filter cake; II. Alkalifying the dibasic acid wet filter cake obtained in the step I to prepare a dibasic acid single salt solution with the pH value of 6.0-7.0, simultaneously adding a salting-out agent, heating to completely dissolve the dibasic acid single salt solution, preserving the temperature, cooling to room temperature, and filtering to obtain a long-chain dibasic acid single salt crystal filter cake; III, adding alkali into the long-chain dibasic acid monosalt crystal filter cake obtained in the step II to dissolve the long-chain dibasic acid monosalt crystal filter cake completely to generate a long-chain dibasic acid bisalt solution, and filtering solid matters; IV, acidifying the filtrate obtained in the step III to convert all the long-chain dibasic acid double salts into long-chain dibasic acids, and then crystallizing, filtering, washing and drying to obtain a long-chain dibasic acid product. The method is to add a salting-out agent into a system, so that the solubility of protein is reduced and the protein is separated out from the solution along with long-chain dibasic acid salt, and an effective method for removing the protein is not available in subsequent steps, so that the protein cannot be effectively removed, the purity of a product is influenced, and the total nitrogen content is high.
Disclosure of Invention
Aiming at the defects of the extraction process of the long-chain dibasic acid disclosed by the prior art, the invention provides a method for extracting C from C by using a water phase method10~C18Normal alkaneCompared with the prior art, the method for extracting the long-chain dibasic acid from the hydrocarbon fermentation liquor has the advantages of white color, low protein content, loose and easily-dried product and the like.
The method for extracting the long-chain dicarboxylic acid from the fermentation liquor comprises the following steps:
I. pretreating the terminated fermentation liquor to obtain a filtrate containing long-chain dibasic acid salt;
II. Acidifying the long-chain dibasic acid salt filtrate to ensure that the dibasic acid is completely crystallized and separated out, filtering to obtain a long-chain dibasic acid filter cake, and washing;
III, mixing the long-chain dicarboxylic acid filter cake obtained in the step II with water and pulping;
IV, adding a pyridine compound into the mixed slurry obtained in the step III;
v, performing membrane filtration on the mixture obtained in the step IV to obtain filtrate;
VI, adding a sodium hydroxide solution into the filtrate obtained in the step V to form long-chain dibasic acid sodium salt, crystallizing, separating out, filtering and washing to obtain long-chain dibasic acid sodium salt crystals;
VII, mixing the crystals obtained in the step VI with water, heating and dissolving, adding an adsorbent for adsorption and filtering, adding acid into the filtrate for acidification to ensure that the dibasic acid is completely crystallized and separated out, and filtering, washing and drying to obtain the long-chain dibasic acid.
In the method, the fermentation stopping liquid in the step I is a metabolite obtained by fermenting microorganisms by using liquid wax, wherein the molecular general formula of the contained long-chain dibasic acid is CnH2n-2O4Wherein n is 10-18, and can be a single long-chain binary acid or a mixed long-chain binary acid.
In the method of the present invention, the acidification in step II can be performed by a conventional method. The pH value of the acidification is 2.0-4.0. The acid used for the acidification in the present invention may be any concentration of H2SO4、HNO3HCl or H3PO4。
In the method, when the long-chain dicarboxylic acid filter cake is mixed with water and pulped in the step III, the water is 50-500 wt% of the weight of the long-chain dicarboxylic acid filter cake, and preferably 100-300 wt%.
In the method, the water in the step III is deionized water, and the conductivity is less than 0.1 mus.
In the method, the pyridine compound added in the step IV is one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 3-dimethylpyridine, 2, 4-dimethylpyridine and 2, 6-dimethylpyridine.
In the method, the amount of the pyridine compound added in the step IV enables the pH value of the slurry to be 5.0-6.4, and the reaction time of the pyridine compound and the long-chain dibasic acid is 30-120 min.
In the method, the membrane filtration equipment in the step V is microfiltration or ultrafiltration, preferably ultrafiltration, and the aperture of the ultrafiltration membrane is 1000-30000, preferably 1000-5000 of molecular weight cut-off.
In the method, a sodium hydroxide solution is added into the filtrate obtained in the step VI, the mass concentration of the sodium hydroxide solution is 10-40%, the pH value of a regulating system is 6.4-7.0, pyridine is regenerated, the obtained long-chain dibasic acid monosodium salt is crystallized, a long-chain dibasic acid monosodium salt filter cake is obtained through filtration, and the pyridine compound enters the filtrate. Washing the long-chain dibasic acid single salt filter cake with low-temperature deionized water, dissolving the washed long-chain dibasic acid single salt filter cake in fresh deionized water at the dissolving temperature of 85-95 ℃, simultaneously adding an adsorbent, and filtering while hot to obtain a filtrate containing long-chain dibasic acid sodium salt. The temperature of the low-temperature deionized water used in the invention is 5-15 ℃. The adsorbent used in the invention is one or more of particles containing adsorption pore channels, such as activated carbon, diatomite, activated clay and the like. The dosage of the adsorbent is 1-5% of the mass of the fermentation liquid after the termination of the step (1).
In the process of the present invention, the acidification in step VII may be carried out by conventional methods. The pH value of the acidification is 2.0-4.0. The acid used for the acidification in the present invention may be any concentration of H2SO4、HNO3HCl or H3PO4Preferably H2SO4。
The method comprises the steps of reacting a long-chain dibasic acid filter cake obtained by acidification and filtration with a pyridine compound to generate water-soluble long-chain dibasic acid pyridinium, precipitating soluble protein under a proper slightly acidic condition, effectively separating the precipitated protein from the water-soluble long-chain dibasic acid pyridinium by ultrafiltration, more effectively removing the protein by steps of sodium hydroxide alkalization, single-salt sodium salt crystallization, filtration, washing and the like, simultaneously regenerating pyridine, and finally obtaining a qualified long-chain dibasic acid product by acidification.
The invention separates the long-chain dibasic acid from impurities more thoroughly through the steps of acidification of the long-chain dibasic acid salt, generation of dibasic acid pyridinium, ultrafiltration filtration, single salt crystallization filtration, acidification and the like, compared with the conventional extraction process, the product has white color and luster, the dried long-chain dibasic acid product is loose, the product purity is more than 99.5 percent, and the total nitrogen content is less than 30ppm, thus meeting the requirements of downstream application.
Detailed Description
The method of extracting the long chain dicarboxylic acid from the fermentation broth is further illustrated by the following examples. In the present invention, wt% is a mass fraction.
In the method of the present invention, the fermentation liquid contains liquid wax, cells, unused medium, metabolites, microbial secretions and the like, and particularly contains a large amount of impurities such as proteins, pigments and the like. Step I, terminating the fermentation liquor pretreatment, which is generally to remove impurities such as liquid wax and thalli, the pretreatment can be carried out by adopting a microfiltration and/or ultrafiltration method, or the heat inactivation treatment can be carried out before the microfiltration and/or ultrafiltration, for example, at least one of the following schemes can be adopted:
(1) heating the terminated fermentation liquor to 75-90 ℃, introducing the terminated fermentation liquor into a microfiltration or ultrafiltration device, and removing impurities such as thalli, liquid wax and the like to obtain long-chain dibasic acid salt filtrate;
(2) heating the terminated fermentation liquor to 85-100 ℃, adjusting the pH value to 8-10, standing, then removing residual liquid wax on the upper layer, cooling the long-chain dibasic acid salt solution containing the thalli on the lower layer to 30-90 ℃, and filtering to remove impurities such as the thalli through microfiltration and/or ultrafiltration equipment to obtain the long-chain dibasic acid salt filtrate.
Comparative example 1
Fermenting 200mL of Candida tropicalis to obtain C12H22O4Heating the fermentation liquor with the concentration of 160g/L at 95 ℃, adjusting the pH value to 10, standing for about 2 hours, and then separating the upper layer liquid wax. The lower layer of the long-chain dibasic acid salt solution containing the thalli is cooled to 80 ℃, and the filtrate is obtained by membrane filtration. By H2SO4Adjusting the pH of the filtrate to 3.0 to obtain C12H22O4Crystallizing the aqueous solution, filtering, washing with water to neutrality to obtain a wet cake, i.e. C12H22O4A long chain dibasic acid.
Example 1
The filter cake obtained in comparative example 1 was mixed with 90mL of deionized water and slurried, pyridine was added thereto, the pH was adjusted to 5.4, and the reaction was carried out for 60min under stirring. Then, the filtrate is obtained by membrane filtration through ultrafiltration equipment with molecular weight cutoff of 5000. Adding sodium hydroxide into the filtrate to adjust the pH value to 6.5 to form long-chain dibasic acid monosodium salt, crystallizing, filtering, and washing with deionized water at a low temperature of 10 ℃ to obtain the long-chain dibasic acid monosodium salt crystal. Mixing the crystals with fresh deionized water, heating to 95 deg.C, adding 2g of activated carbon for adsorption, filtering, and adding H to the filtrate2SO4Adjusting the pH of the filtrate to 3.0 to obtain C12H22O4Crystallizing the aqueous solution, filtering, washing with water to neutrality to obtain a wet filter cake, and drying to obtain C12H22O4And (5) producing the product.
The experimental data obtained are shown in Table 1.
Example 2
Fermenting 200mL of Candida tropicalis to obtain C13H24O4Heating the fermentation broth with concentration of 154g/L to 85 deg.C, membrane filtering to obtain filtrate, and treating with H2SO4Adjusting the pH of the filtrate to 3.0 to obtain C13H24O4The aqueous solution was crystallized, filtered and washed with water to neutrality to give a wet cake.
Mixing the filter cake with 60mL of deionized water, pulping, addingAdding 3-methylpyridine, adjusting the pH value to 5.6, and reacting for 60min under the stirring condition. Then, the filtrate was subjected to membrane filtration by an ultrafiltration apparatus having a molecular weight cutoff of 30000 to obtain a filtrate. Adding sodium hydroxide into the filtrate to adjust the pH value to 7.0 to form long-chain dibasic acid monosodium salt, crystallizing, filtering, and washing with deionized water at a low temperature of 10 ℃ to obtain the long-chain dibasic acid monosodium salt crystal. Mixing the crystals with fresh deionized water, heating to 90 deg.C, adding 2g of activated carbon for adsorption, filtering, and adding H to the filtrate2SO4Adjusting the pH of the filtrate to 3.0 to obtain C13H24O4Filtering the crystal water solution, washing the crystal water solution to be neutral by water to obtain a wet filter cake, and drying the wet filter cake to obtain C13H24O4And (5) producing the product.
The experimental data are shown in table 1.
Example 3
Fermenting 200mL of Candida tropicalis to obtain C14H26O4Heating the fermentation liquor with the concentration of 176g/L to 80 ℃, filtering by a ceramic microfiltration membrane, and removing thalli and residual liquid wax to obtain long-chain dibasic acid salt filtrate. Adding H to the filtrate2SO4Adjusting the pH to 2.4 to obtain C14H26O4The aqueous solution was crystallized, filtered and washed with water to neutrality to give a wet cake.
And mixing the filter cake with 90mL of deionized water, pulping, adding 2, 4-dimethylpyridine, adjusting the pH value to 5.4, and reacting for 60min under the stirring condition. Then, the filtrate is obtained by membrane filtration through an ultrafiltration device with molecular weight cutoff of 1000. Adding sodium hydroxide into the filtrate to adjust the pH value to 6.8 to form long-chain dibasic acid monosodium salt, crystallizing, filtering, and washing with deionized water at a low temperature of 10 ℃ to obtain the long-chain dibasic acid monosodium salt crystal. Mixing the crystals with fresh deionized water, heating to 85 deg.C, adding 2g of activated carbon for adsorption, filtering, and adding H to the filtrate2SO4Adjusting the pH of the filtrate to 3.0 to obtain C14H26O4Crystallizing the aqueous solution, filtering, washing with water to neutrality to obtain a wet filter cake, and drying to obtain C14H26O4And (5) producing the product.
The experimental data are shown in table 1.
Example 4
Taking 200mL of C obtained by fermenting Candida tropicalis to obtain 155g/L13H24O4And C14H26O4Heating the mixed organic acid fermentation liquor to 80 ℃, filtering by a ceramic microfiltration membrane, and removing thalli and residual liquid wax to obtain an organic acid salt filtrate. Adding H to the filtrate2SO4Adjusting the pH to 3.0 to obtain blend C13H24O4And C14H26O4The aqueous solution was crystallized, filtered and washed with water to neutrality to give a wet cake.
And mixing the filter cake with 90mL of deionized water, pulping, adding pyridine, adjusting the pH value to 6.0, and reacting for 60min under the stirring condition. Then, membrane filtration is carried out by an ultrafiltration device with the molecular weight cutoff of 10000, and filtrate is obtained. Adding sodium hydroxide into the filtrate to adjust the pH value to 7.0 to form long-chain dibasic acid monosodium salt, crystallizing, filtering, and washing with deionized water at a low temperature of 10 ℃ to obtain the long-chain dibasic acid monosodium salt crystal. Mixing the crystals with fresh deionized water, heating to 90 deg.C, adding 2g of activated carbon for adsorption, filtering, and adding H to the filtrate2SO4Adjusting the pH of the filtrate to 3.0 to obtain C13H24O4And C14H26O4Filtering the mixed crystal water solution, washing the mixed crystal water solution to be neutral by water to obtain a wet filter cake, and drying the wet filter cake to obtain C13H24O4And C14H26O4And (4) mixing the products.
The experimental data are shown in table 1.
Comparative example 2
The method for extracting the long-chain dicarboxylic acid in the comparative example is as follows:
200mL of 155g/L C13H24O4And C14H26O4Heating the mixed dibasic acid fermentation liquor to 80 ℃, filtering by a ceramic microfiltration membrane, and removing thalli and residual liquid wax to obtain organic acid salt filtrate. Adding H to the filtrate2SO4Adjusting the pH to 3.0 to obtain blend C13H24O4And C14H26O4The aqueous solution was crystallized, filtered and washed with water to neutrality to give a wet cake.
Mixing 300mL of water with the wet filter cake, adjusting the pH value to 6.0 by using 10mol/L of NaOH solution, simultaneously adding 40g of NaCl, heating to 90 ℃, then cooling to 80 ℃ for 30min, slowly cooling to room temperature, and filtering to obtain the mixed dibasic acid monosodium salt filter cake. Adding 10mol/L NaOH solution into the filter cake to adjust pH value to 9, adding 1wt% powdered activated carbon into the solution, and performing adsorption treatment at 60 deg.C for 30 min. Filtering to obtain clear solution of double salts of long-chain dibasic acid, and adding 3mol/L H2SO4Adjusting pH to 3.0, heating to 80 deg.C, standing, cooling to room temperature, filtering, washing, and drying to obtain C13H24O4And C14H26O4And (3) mixing acid products.
The experimental data are shown in table 1.
Comparative example 3
The method for extracting the long-chain dicarboxylic acid in the comparative example is as follows:
200mL of C with a concentration of 160g/L are taken12H22O4Heating the binary acid fermentation liquor to 90 ℃ to perform demulsification and separation to remove residual liquid wax, filtering the fermentation liquor containing thalli at the lower layer by using an ultrafiltration membrane with the molecular weight cut-off of 1000 to obtain ultrafiltration clear liquid, adding 3g of active carbon to perform decoloration treatment, and using 3mol/L H to decolor the clear liquid2SO4Adjusting pH to 3.0, acidifying, crystallizing, cooling to room temperature, filtering, washing, blow-drying, and oven-drying to obtain C12H22O4A dibasic acid product.
TABLE 1 Properties of the Long chain dibasic acid product
| Item | The total acid content wt% | Ash content wt% | Total nitrogen microgram/g |
| Example 1 | 99.89 | 0.012 | 18 |
| Example 2 | 99.90 | 0.019 | 16 |
| Example 3 | 99.95 | 0.008 | 17 |
| Example 4 | 99.97 | 0.012 | 15 |
| Comparative example 1 | 98.97 | 0.170 | 112 |
| Comparative example 2 | 99.40 | 0.092 | 35 |
| Comparative example 3 | 99.31 | 0.085 | 92 |
Claims (16)
1. A method for extracting long-chain dicarboxylic acid from fermentation liquor comprises the following steps:
I. pretreating the terminated fermentation liquor to obtain a filtrate containing long-chain dibasic acid salt;
II. Acidifying the long-chain dibasic acid salt filtrate to ensure that the dibasic acid is completely crystallized and separated out, filtering to obtain a long-chain dibasic acid filter cake, and washing;
III, mixing the long-chain dicarboxylic acid filter cake obtained in the step II with water and pulping;
IV, adding a pyridine compound into the mixed slurry obtained in the step III;
v, performing membrane filtration on the mixture obtained in the step IV to obtain filtrate;
VI, adding a sodium hydroxide solution into the filtrate obtained in the step V to form long-chain dibasic acid sodium salt, crystallizing, separating out, filtering and washing to obtain long-chain dibasic acid sodium salt crystals;
VII, mixing the crystals obtained in the step VI with water, heating and dissolving, adding an adsorbent for adsorption and filtering, adding acid into the filtrate for acidification to completely crystallize and separate out the dibasic acid, and filtering, washing and drying to obtain the long-chain dibasic acid;
wherein the amount of the pyridine compound added in the step IV enables the pH value of the slurry to be 5.0-6.4; and VI, adding the sodium hydroxide solution in an amount to ensure that the pH value of the filtrate is 6.4-7.0.
2. The method of claim 1, wherein: the fermentation stopping liquid in the step I is a metabolite obtained by fermenting microorganisms with liquid wax, and the molecular general formula of the contained long-chain dibasic acid is CnH2n-2O4Wherein n is 10 to 18.
3. The method of claim 1, wherein: the pyridine compound added in the step IV is one or more of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2, 3-dimethylpyridine, 2, 4-dimethylpyridine and 2, 6-dimethylpyridine.
4. A method according to any of claims 1 to 3, characterized by: and the reaction time of the pyridine compound and the long-chain dicarboxylic acid in the step IV is 30-120 min.
5. The method of claim 1, wherein: and the pH value of the acidification in the step II is 2.0-4.0.
6. The method of claim 1, wherein: and C, mixing the long-chain dicarboxylic acid filter cake and water for pulping in the step III, wherein the water is 50-500 wt% of the weight of the long-chain dicarboxylic acid filter cake.
7. The method of claim 6, wherein: the water consumption is 100-300 wt% of the weight of the long-chain binary acid filter cake.
8. The method of claim 1 or 6 or 7, wherein: and III, the water is deionized water.
9. The method of claim 1, wherein: and V, performing microfiltration or ultrafiltration on the membrane filtration equipment, wherein the aperture of the ultrafiltration membrane is 1000-30000 in molecular weight cut-off.
10. The method of claim 9, wherein: the aperture of the ultrafiltration membrane is 1000-5000 of molecular weight cut-off.
11. The method of claim 1, wherein: and D, adding a sodium hydroxide solution into the filtrate obtained in the step VI, wherein the mass concentration of the sodium hydroxide solution is 10-40%.
12. The method of claim 1, wherein: and VI, washing with low-temperature deionized water, wherein the temperature of the low-temperature deionized water is 5-15 ℃.
13. The method of claim 1, wherein: in the step VII, the crystal obtained in the step VI is mixed with water, heated and dissolved, and the dissolving temperature is 85-95 ℃.
14. The method of claim 1, wherein: in the step VII, the used adsorbent is one or more of activated carbon, diatomite and activated clay; the dosage of the adsorbent is 1-5% of the mass of the fermentation liquid after the termination of the step I.
15. The method of claim 1, wherein: in the step VII, the pH value of the acidification is 2.0-4.0.
16. The method of claim 1, wherein: in step I, the method for terminating the pretreatment of the fermentation broth is at least one selected from the following methods:
(1) heating the terminated fermentation liquor to 75-90 ℃, and introducing the terminated fermentation liquor into a microfiltration or ultrafiltration device to remove thalli and liquid wax impurities to obtain long-chain dibasic acid salt filtrate;
(2) heating the terminated fermentation liquor to 85-100 ℃, adjusting the pH value to 8-10, standing, then removing residual liquid wax on the upper layer, cooling the long-chain dibasic acid salt solution containing the thalli on the lower layer to 30-90 ℃, and filtering to remove thalli impurities through microfiltration and/or ultrafiltration equipment to obtain long-chain dibasic acid salt filtrate.
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| US11999689B2 (en) | 2019-12-19 | 2024-06-04 | Cathay Biotech Inc. | Method and system for extracting long chain dicarboxylic acid |
| CN111138272A (en) | 2019-12-19 | 2020-05-12 | 上海凯赛生物技术股份有限公司 | Extraction method and system of long-chain dibasic acid |
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