CN118324625A - Refining and purifying method for producing long-chain dibasic acid through biological fermentation - Google Patents
Refining and purifying method for producing long-chain dibasic acid through biological fermentation Download PDFInfo
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- CN118324625A CN118324625A CN202311730574.XA CN202311730574A CN118324625A CN 118324625 A CN118324625 A CN 118324625A CN 202311730574 A CN202311730574 A CN 202311730574A CN 118324625 A CN118324625 A CN 118324625A
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- Prior art keywords
- ether
- dibasic acid
- long
- acid
- organic solvent
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
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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
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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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a refining and purifying method for producing long-chain dibasic acid by biological fermentation, belonging to the technical field of microbiology and derivative biochemical industry. The refining and purifying method of the invention comprises the following steps: dissolving a long-chain binary acid crude product prepared by a biological fermentation method in an organic solvent, standing and separating to obtain an oil phase, adding an adsorbent A, filtering to obtain a solution clear liquid A, cooling, crystallizing and filtering the solution clear liquid A to obtain a filter cake which is long-chain binary acid; the molecular general formula of the long-chain dibasic acid is as follows: the method for refining and purifying the organic solution can save energy and reduce solvent loss.
Description
Technical Field
The invention relates to the technical field of microbiology and derivative biochemical industry, in particular to a refining and purifying method for producing long-chain dibasic acid by biological fermentation.
Background
The long carbon chain dibasic acid (DCN) refers to aliphatic dibasic acid containing more than 10 carbon atoms in a carbon chain, and comprises saturated and unsaturated long chain dibasic acid, and is a fine chemical product with important and wide industrial application. The preparation of the long-chain dibasic acid is generally carried out by taking alkane as raw material and utilizing a biological oleaginous bacteria fermentation oxidation method, and the content of the long-chain dibasic acid in fermentation liquor is 13% -17%. The long-chain dibasic acid is extracted and purified from the fermentation broth, and is generally processed by the processes of fermentation broth sterilization, decolorization, acidification crystallization, filtration and the like. However, the fermentation period is generally longer than 140-145 hours, the content of mycoprotein and mycelium generated by autolysis of thalli in fermentation liquor is more, the quality of long-chain binary acid crude products obtained by single sterilization by stainless steel film or ceramic film, decolorization by activated carbon and primary acidification crystallization separation is not high, and soluble proteins remain in the products, so that the purity of the products is further improved, the requirements of customers are met, and a refining process is usually added after the crude products are extracted and purified by acid.
Various technical schemes such as high-temperature melting refining, low-temperature extraction refining, aqueous phase refining and the like are formed around the long-chain dibasic acid refining process at the present stage. CN114917850a discloses a refined diacid and its preparation method, which is to remove thallus from fermentation liquor through stainless steel film or ceramic film to obtain clear liquid, adding active carbon to decolorize, after nanofiltration and ultrafiltration to intercept substances with molecular weight greater than 1500, acidifying and crystallizing to obtain long chain diacid crude product, mixing the diacid crude product with softened water according to proportion, heating steam to 65 deg.c, adding liquid alkali to adjust pH to about 7.5, making the crude diacid completely dissolve, then after nanofiltration to obtain clear liquid, adding sulfuric acid or hydrochloric acid to crystallize and separate diacid. And (3) obtaining semi-finished product diacid through a plate-and-frame filter press, mixing the semi-finished product diacid with softened water according to a proportion, heating to 120 ℃, standing for 30min, cooling to 60 ℃, and performing flash evaporation drying to obtain the product. The refining method comprises the steps of primary liquid alkali dissolution, twice acid precipitation, four steam heating, overlong process route, high consumption of sulfuric acid or hydrochloric acid, liquid alkali and steam, and overlarge amount of byproduct sodium sulfate or sodium chloride. Therefore, the reaction period is long, the productivity is low, and the comprehensive refining cost is high.
In contrast, the solvent refining method utilizes the characteristic that long-chain dibasic acid can be dissolved in an organic solvent, so that impurity components such as water-soluble protein are converted into a solid phase under the action of the organic solvent, and the long-chain dibasic acid is separated from an aqueous phase system, thereby achieving the effect of refining the long-chain dibasic acid. At present, some solvent refining methods have been industrially applied, and patent solvent refining methods of different systems have been formed by utilizing single solvents such as glacial acetic acid, ethanol, acetone and the like. However, the above solvent refining method can generate secondary crystallization mother liquor in practical application, the mother liquor mainly comprises solvent, long-chain diacid, water and impurities, if the diacid, water and impurities in the mother liquor are not removed, accumulation is caused, and the crystallization mother liquor cannot be recycled. Therefore, distillation is generally adopted to recover the solvent from the crystallization mother liquor at present, so that the energy consumption is high, the investment is high, the solvent loss is high, and the production cost is high.
Disclosure of Invention
Aiming at the problems, the invention provides a refining and purifying method for producing long-chain dibasic acid by biological fermentation, which saves energy, reduces solvent loss and lowers production cost.
The invention aims to provide a refining and purifying method for producing long-chain dibasic acid by biological fermentation, which comprises the following steps:
Dissolving a long-chain binary acid crude product prepared by a biological fermentation method in an organic solvent, standing and separating to obtain an oil phase, adding an adsorbent A, filtering to obtain a solution clear liquid A, cooling, crystallizing and filtering the solution clear liquid A to obtain a filter cake which is long-chain binary acid; the molecular general formula of the long-chain dibasic acid is as follows: HOOC- (CH 2)n -COOH, n is 8-20);
the filtrate obtained by filtration is crystallization mother liquor, adsorbent B is added into the crystallization mother liquor for adsorption treatment, and solution clear liquid B obtained by filtration is used as organic solution for recycling.
In one example, the ratio of crude long chain dibasic acid to organic solvent is 1kg:7-11L.
In one embodiment, the organic solvent is two or more of an ester organic solvent, an ether organic solvent, a ketone organic solvent, an alcohol organic solvent, a furan organic solvent, an acid organic solvent, an aromatic organic solvent, a sulfur-containing organic solvent, and a halogenated hydrocarbon organic solvent.
In one embodiment, the organic solvent is toluene, xylene, benzene chloride, dichlorobenzene, nitrobenzene, ethyl acetate, isopropyl acetate, methyl acetate, butyl acetate, octyl acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol dipentyl ether, ethylene glycol dihexyl ether, ethylene glycol diheptyl ether, ethylene glycol dioctyl ether, ethylene glycol dinonyl ether, ethylene glycol didecyl ether, ethylene glycol dilauryl ether, methyl chloride, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid, adipic acid, terephthalic acid, diethyl ether, propyl ether, pentyl ether, hexyl ether, heptyl ether, octyl ether, nonyl ether, decyl ether, lauryl ether, methyl t-butyl ether, acetone, butanone, methanol, ethanol, butanol, propanol, ethylene glycol, propylene glycol, 1, 4-butanediol, tetrahydrofuran, 1, 4-dioxane, methyl ethyl ether, methyl butyl ether, methyl octyl ether, ethyl ether, ethyl butyl ether, ethyl octyl ether, anisole, benzene butyl ether, benzene octyl ether, chloroform, or two or more of these.
In one embodiment, the crude long chain diacid is prepared by the steps of: and (3) performing degerming, decoloring, acidifying crystallization and filtering on long-chain binary acid fermentation liquor obtained by fermenting the microorganism by utilizing alkane.
In one embodiment, the dissolution temperature is 93-96 ℃.
In one embodiment, the resting time is 20-90 minutes.
In one embodiment, both adsorbent A and adsorbent B are 200-500 mesh activated carbon;
the addition amount of the adsorbent A is 0.1-0.15% of the oil phase mass;
The adding amount of the adsorbent B is 0.1-0.15% of the mass of the crystallization mother liquor.
In one embodiment, the filtration pressure is 0.4-0.6MPa.
In one embodiment, the cooling crystallization is crystallization to separate long chain dibasic acid after cooling to 10-20 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The long-chain dibasic acid is refined by using an organic solvent, and a high-purity product can be obtained by using an extraction principle, but the treatment of crystallization mother liquor can influence the refining yield and the product purity due to the fact that the used solvent has higher solubility to the long-chain dibasic acid at normal temperature. Aiming at the characteristic of refining long-chain diacid by the solvent system, the invention dissolves the long-chain diacid crude product prepared by a biological fermentation method into an organic solvent, stands for separation, reduces the temperature for crystallization, and filters the long-chain diacid to obtain the required product, and the obtained crystallization mother liquor is treated by an adsorbent and filtered to finish filtering impurity components in the crystallization mother liquor, so that the long-term recycling requirement is met. After repeated recycling, the quality of the product is not affected, and the total extraction yield of the long-chain dibasic acid is improved.
Compared with the traditional method which adopts a single solution and distills the crystallization mother liquor, the invention does not need to distill the crystallization mother liquor, not only can save energy, but also can improve the recovery rate of the organic solvent, and simultaneously, the long-chain dibasic acid in the crystallization mother liquor can be recovered, thereby better improving the refining yield of the product.
(2) According to the conventional refining production method for long-chain dibasic acid, the steam consumption is 10 tons per ton of dibasic acid produced, and by adopting the refining production method disclosed by the invention, the steam consumption is 6 tons per ton of dibasic acid produced, and the steam consumption is reduced by 40%. In addition, the recovery rate of the organic solvent in the invention reaches more than 98 percent.
(3) The main reason for influencing the purity of the refined long-chain dibasic acid product is that the small molecular soluble protein in the product is utilized by the water contained in the crude acid, so that the residual soluble protein in the crude acid forms a milk hydration layer, and the milk hydration layer is added with an adsorbent and adsorbed and removed. The crystallization of protein along with the dibasic acid in the cooling crystallization process of the long-chain dibasic acid solvent solution is avoided, and the nitrogen content in the refined product is reduced.
Drawings
FIG. 1 is a flow chart of refining and purifying long-chain dibasic acid produced by biological fermentation.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a refining and purifying method for producing long-chain dibasic acid by biological fermentation, which comprises the following steps:
Dissolving a long-chain dibasic acid crude product in an organic solvent, standing and separating to obtain an oil phase, adding an adsorbent A, filtering to obtain a solution clear liquid A, cooling and crystallizing the solution clear liquid A, and filtering to obtain a filter cake which is the long-chain dibasic acid; the molecular general formula of the long-chain dibasic acid is as follows: HOOC- (CH 2)n -COOH) (n.gtoreq.8);
the filtrate obtained by filtration is crystallization mother liquor, adsorbent B is added into the crystallization mother liquor for adsorption treatment, and solution clear liquid B obtained by filtration is used as organic solution for recycling.
In some preferred embodiments, the ratio of crude long chain dibasic acid to organic solvent is 1kg:7-11L.
In some preferred embodiments, the organic solvent is two or more of an ester organic solvent, an ether organic solvent, a ketone organic solvent, an alcohol organic solvent, a furan organic solvent, an acid organic solvent, an aromatic organic solvent, a sulfur-containing organic solvent, and a halogenated hydrocarbon organic solvent.
In some preferred embodiments, the organic solvent is toluene, xylene, benzene chloride, dichlorobenzene, nitrobenzene, ethyl acetate, isopropyl acetate, methyl acetate, butyl acetate, octyl acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol dipentyl ether, ethylene glycol dihexyl ether, ethylene glycol diheptyl ether, ethylene glycol dioctyl ether, ethylene glycol dinonyl ether, ethylene glycol didecyl ether, ethylene glycol dilauryl ether, methyl chloride, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid, adipic acid, terephthalic acid, diethyl ether, propyl ether, pentyl ether, hexyl ether, heptyl ether, octyl ether, nonyl ether, decyl ether, lauryl ether, methyl t-butyl ether, acetone, butanone, methanol, ethanol, butanol, propanol, ethylene glycol, propylene glycol, 1, 4-butanediol, tetrahydrofuran, 1, 4-dioxane, methyl ethyl ether, methyl butyl ether, methyl octyl ether, ethyl ether, ethyl butyl ether, ethyl octyl ether, anisole, benzene butyl ether, benzene octyl ether, chloroform, or two or more of these.
The organic solvent used in the invention has moderate solubility in water or is slightly soluble in water, and the solubility of the long-chain dibasic acid in the organic solvent is very high. The use of the mixed solvent makes up for the short plates of a single solution, such as mutual compensation for the precipitation and the damage of the soluble protein, and the quality of the crude product of the long-chain dibasic acid is different in each batch, so that the protein content is different, and the use of the mixed solvent ensures the stability of the product quality and the production stability.
In some preferred embodiments, the crude long chain diacid is prepared by the steps of: and (3) performing degerming, decoloring, acidifying crystallization, filtering and drying on long-chain binary acid fermentation liquor obtained by fermenting the microorganism by utilizing alkane.
In the invention, the bacteria are generally removed by passing fermentation liquor through a stainless steel membrane or ceramic membrane system to intercept the bacteria and obtain clear liquid; the decoloring step is to add activated carbon to adsorb macromolecular proteins such as pigment and the like into the clear liquid; the acidification crystallization is to separate out long-chain dibasic acid in the filtrate through acid regulation, and the pH value of the controlled acid is 3.5-5.8, and it is understood that the acid adopted in the acid regulation can be sulfuric acid or hydrochloric acid. And (3) filtering and drying after acidification and crystallization, wherein the filtering pressure is 0.4-0.6 MPa. The drying temperature is 80-125 ℃.
In some preferred embodiments, the dissolution temperature is 93-96 ℃. When the long-chain binary acid crude product and the organic solvent are mixed in a decoloring tank, the long-chain binary acid crude product is dissolved by adopting a heating mode.
In some preferred embodiments, the resting time is 20-90 minutes. Standing for 20-90min at constant temperature after dissolving long-chain dibasic acid crude product, discharging lower water phase under heat preservation, adding adsorbent A into the rest oil phase for adsorption and filtration, and filtering with plate-and-frame filter press. The use of adsorbent A can remove pigments and proteins from the crude product.
The addition amount of the adsorbent A is 0.1-0.15% of the oil phase mass;
The adding amount of the adsorbent B is 0.1-0.15% of the mass of the crystallization mother liquor,
The adsorbent A and the adsorbent B are 200-500 meshes of active carbon.
The filtering pressure is 0.4-0.6MPa.
The cooling crystallization is to crystallize and separate out long chain dibasic acid after cooling to 10-20 deg.c.
Specifically, the invention adopts cooling water to circularly reduce to 10-20 ℃ to separate out long-chain diacid, and long-chain diacid filter cakes and solution clear liquid B are collected after filtration, wherein the long-chain diacid filter cakes are the required products of the invention.
The solution clear liquid B can be used as the organic solvent of the step (1) for recycling, the solution clear liquid B contains the organic solvent, a small amount of water, dissolved long-chain dibasic acid and the like, the micro-fine dibasic acid particles and the very small amount of protein in the solvent are removed through the adsorbent B, and the long-chain dibasic acid in the solution clear liquid B can enter the product during the next round of refining of the long-chain dibasic acid crude product.
The following experimental methods and detection methods, if not specified, are all conventional methods; the following reagents and raw materials are commercially available ones unless otherwise specified, and the present invention is not particularly limited herein. The collection of the invention is detected by a dry weight method, and the detection of nitrogen content is determined by a Kjeldahl nitrogen determination method. Long chain dibasic acid purity was determined by liquid chromatography tandem mass spectrometry (LCMS) in combination with standards. The microbial strain used in the invention is candida tropicalis strain (candida) variant strain, the preservation number of the strain is CGMCC No.0356, and the strain is derived from China petrochemical company Limited to smooth the petrochemical institute.
The long-chain dibasic acid is prepared by the following steps:
Culturing organisms by adopting a two-stage seed tank, wherein the growth density (OD 620) of the thalli after the culture of the first-stage seed tank is more than or equal to 0.5;
the method comprises the following specific steps:
(1) Primary seed tank culture: an alkaline water boiling tank: the pH is approximately equal to 12 and 120 ℃ for 4 hours; empty and eliminate: 130 ℃ for 1h; actual elimination: the pH is properly regulated before elimination, so that the pH before planting is in the range of 6.7-7.0. Preserving heat for 30 minutes at the temperature of 121-123 ℃, wherein the volume after actual elimination is 1.4-1.6m 3; and after the actual elimination is finished, rapidly cooling, and inoculating and culturing candida tropicalis when the temperature is reduced to 30+/-0.5 ℃.
In the primary culture procedure, the early stage normal culture is performed, when the dissolved oxygen is close to 40%, the air quantity is increased, the dissolved oxygen is ensured to be kept between 40 and 50%, and the air quantity is gradually increased; when the growth density (OD 620) of the bacterial cells is 0.540, the bacterial liquid is dissolved with oxygen and the pH is rebound, and the primary culture is finished.
(2) Culturing in a secondary seed tank: an alkaline water boiling tank: the pH is approximately equal to 12 and 120 ℃ for 4 hours; empty and eliminate: 130 ℃ for 1h; volume is fixed for 17.5t before actual elimination, actual elimination: the pH is properly regulated before elimination, so that the pH before planting is in the range of 6.7-7.0. The temperature is 121-123 ℃, and the temperature is kept for 30 minutes; and after the actual elimination is finished, rapidly cooling. Wherein, when the carbon source is glucose, the single constant volume is 1.5t, the constant volume of the secondary seed tank is 16t, the temperature is 113-115 ℃, the heat is preserved for 30 minutes, and the secondary seed tank is pressed in before inoculation.
The secondary culture process is controlled as follows: the early-stage normal culture is performed, when the dissolved oxygen is close to 40%, the air quantity is increased, the dissolved oxygen is ensured to be kept at 40% -50%, and the air quantity is gradually increased; and (5) dissolving oxygen in the bacterial liquid, rebounding PH, and finishing the secondary culture.
After the second-level seed tank is cultured, inoculating the bacterial liquid into a fermentation tank for fermentation, (wherein the fermentation tank contains a culture medium of 2% of sucrose, 0.3% of corn steep liquor, 0.5% of yeast extract, 0.8% of monopotassium phosphate and 0.3% of urea), the ventilation ratio is 1:0.7 during fermentation, the dissolved oxygen is controlled to be about 30%, and the pH value is continuously regulated along with the time in the fermentation process, so that the pH value is gradually increased from 6.0 to 8.0 at the end point. During the process of controlling pH value, alkane is fed in 10% at 24hr, 5% at 48hr, 10% at 72hr and 5% at 96 hr. The percentage of alkane fed-batch refers to the mass percentage according to the fermentation broth. Which diacid is produced and which alkane is added, for example, DC13 diacid is produced in the example of example 1, n-tridecane alkane is added, and DC12 diacid is produced in the example of example 3, n-dodecane is added. And fermenting for 158 hours to obtain the dibasic acid fermentation liquor.
Example 1
The crude long-chain dibasic acid used in the example is prepared according to the following steps:
1000L of tridecanedioic acid fermentation liquor is taken, wherein the concentration of the tridecanedioic acid is 145g/L. Filtering with 0.02 μm stainless steel membrane with membrane inlet pressure of 0.6MPa to obtain fermentation liquor clear liquid a, collecting fermentation liquor clear liquid a 1500L, decolorizing with 6% active carbon, filtering to obtain decolorized clear liquid b, adjusting pH to 4.5 with hydrochloric acid, heating to 95deg.C for 45min, cooling to 20deg.C, and standing until tridecanedioic acid in the acidified crystal solution is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain crude dibasic acid with water content of about 2%. The single acid purity of the crude dibasic acid was 97.51% as measured.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
Mixing 7.626kg of crude dibasic acid with 30L of chloroform and 30L of methyl tertiary butyl ether in a decoloring container, heating to 93 ℃, allowing the crude dibasic acid to be completely dissolved, keeping the constant temperature and standing for 25min, discharging water at the lower layer (the density of water is higher than that of a solvent) in a heat-preserving state, adding active carbon into an oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing the oil phase and the active carbon for 30min, and filtering to obtain a solvent clear liquid A.
Cooling the solvent clear liquid A to 20 ℃ with the aid of jacket water, crystallizing and separating out long-chain binary acid, and filtering by a plate frame under the pressure of 0.4MPa to obtain a long-chain binary acid filter cake and a crystallization mother liquor. Long chain diacid filter cake
And (2) conveying the crystallized mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallized mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, filtering under the pressure of 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch for recycling.
The filtered clear liquid B is used as the organic solvent in the next batch step (1), fresh organic solvent is not added in the treatment process, the same amount of crude dibasic acid is added according to the same processes and conditions of the steps (1) - (2) for 5 batches of circulation, and the total treatment of crude acid is about 38.13kg. And (3) collecting the long-chain diacid refined filter cake obtained in the step (2) in each batch, and drying at 100 ℃ to obtain 37.435kg of long-chain diacid refined product, wherein the purity of the single acid is 99.21%, the nitrogen content is 4.12 mug/g, and the refining yield is 98.17%.
Example 2
Taking 6.355kg of DC13 crude dibasic acid, stirring and mixing the obtained product with 30L of octyl acetate and 30L of butyl acetate in a decoloring tank, heating to 92 ℃, allowing the crude dibasic acid to be completely dissolved, keeping the constant temperature and standing for 30min, discharging water at the lower layer under the heat-preserving state, adding active carbon into an oil phase, wherein the addition amount of the active carbon is 0.1% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A.
Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain binary acid, and filtering by a plate frame under the pressure of 0.4MPa to obtain a long-chain binary acid crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.1% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame under the filtration pressure of 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent in the next batch step (1), and no new solvent is added in the treatment process. Adding the same amount of crude dibasic acid according to the same process and conditions of the steps (1) - (2) to carry out 5 batches of circulation, and co-processing 31.78kg of crude dibasic acid. And (3) collecting the refined diacid filter cakes obtained in the step (2) in each batch, and drying at 102 ℃ to obtain 31.10kg of diacid refined products, wherein the purity of the diacid is 99.08%, the nitrogen content is 5.07 mug/g, and the refining yield is 97.86%.
Example 3
The crude long-chain dibasic acid used in the example is prepared according to the following steps:
500L of DC12 dibasic acid fermentation broth is taken, wherein the concentration of the DC12 dibasic acid is 130g/L. Filtering with 0.5 μm stainless steel membrane or ceramic membrane, and collecting 650L clear fermentation liquid a at membrane inlet pressure of 0.4MPa, decolorizing with 1% active carbon to obtain decolorized clear liquid b, adjusting pH to 4.6 with sulfuric acid, heating to 95deg.C for 45min, cooling to 20deg.C, and standing until DC12 dibasic acid in the acidified crystal liquid is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain crude dibasic acid with water content of about 2%. After detection, the mono-acid purity of the crude DC12 diacid was 97.3%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) Mixing 8.261kg of DC12 dibasic acid with 30L of n-octyl ether and 30L of isopropyl acetate in a decoloring tank, heating to 95 ℃ to completely dissolve the crude dibasic acid, keeping the constant temperature for 25min, discharging water at the lower layer under the state of heat preservation, adding active carbon into the oil phase, wherein the addition amount of the active carbon is 1% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 20 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC12 diacid crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallized mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the adding amount of the active carbon is 0.1% of the mass of the crystallized mother liquor, fully stirring and mixing for about 30min, filtering by a plate-and-frame filter press, filtering under the pressure of 0.4MPa, collecting a filtered clear liquid B to a decoloring tank, and recycling the filtered clear liquid B as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent in the next batch step (1), no new solvent is added in the treatment process, and 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), so that 41.3kg of crude dibasic acid is co-treated. And (3) collecting the refined diacid filter cakes obtained in the step (2) in each batch, and drying at 103 ℃ to obtain 40.43kg of diacid refined products. The purity of the monoacid is 99.33%, the nitrogen content is 4.87 mug/g, and the refining yield is 97.89%.
Example 4
Taking 5.51kg of DC12 crude dibasic acid, 30L of ethylene glycol dimethyl ether and 30L of n-octyl ether, stirring and mixing in a decoloring tank, heating to 92 ℃ to enable the crude dibasic acid to be completely dissolved, keeping constant temperature and standing for 30min, discharging water at the lower layer under a heat-preserving state, adding active carbon into an oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A.
Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC12 diacid crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon into the crystallization mother liquor, wherein the addition amount of the active carbon is 0.15% of the oil phase mass, fully stirring and mixing for about 30min, filtering by a plate-and-frame filter press, filtering under the pressure of 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as the refining organic solvent of the next batch.
The filtered clear liquid B is used as the organic solvent in the next batch step (1), no new solvent is added in the treatment process, and 5 batches of circulation are carried out according to the same processes and conditions in the steps (1) - (2), so that 27.55kg of crude dibasic acid is co-treated. And (3) collecting the refined diacid filter cakes obtained in the step (2) in each batch, and drying at 100 ℃ to obtain 27.05kg of diacid refined products. The purity of the monoacid is 99.1%, the nitrogen content is 6.07 mug/g, and the refining yield is 98.18%.
Example 5
Taking 500L of DC16 dibasic acid fermentation liquor, wherein the concentration of the DC16 dibasic acid is 16%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC16 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC16 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
Step (1), stirring and mixing 5.816kg of crude DC16 dibasic acid, 30L of acetic acid and 30L of isooctyl ether in a decoloring tank, heating to 95 ℃ to completely dissolve the crude dibasic acid, keeping the constant temperature and standing for 25min, discharging water at the lower layer under the heat-preserving state, adding active carbon into an oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A.
Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC16 diacid refined crystallization filter cake and crystallization mother liquor.
And (2) conveying the crystallized mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallized mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, filtering under the pressure of 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as the organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.04kg of crude DC16 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.49kg of diacid refined product, the purity of the diacid is 99.33%, the nitrogen content is 5.91 mug/g, and the refined yield is 98.10%.
Example 6
Taking 500L of DC11 dibasic acid fermentation liquor, wherein the concentration of the DC11 dibasic acid is 12%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, decoloring by adding 0.15% active carbon, filtering to obtain decolored clear liquor, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, cooling to 20 ℃ and standing until the DC11 dibasic acid in the acidized crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC11 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) 5.816kg of crude DC11 dibasic acid, 50L of diisopropyl ether and 10L of n-octyl ether mixed solvent are stirred and mixed in a decoloring tank, heated to 95 ℃ to enable the crude dibasic acid to be completely dissolved, kept at a constant temperature and kept stand for 25min, and after the water at the lower layer is discharged in a heat-preserving state, activated carbon is added into an oil phase, the addition amount of the activated carbon is 0.15% of the mass of the oil phase, and the solvent clear liquid A is obtained by filtering after the mixture is fully stirred and mixed for 30 min. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC11 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.073kg of crude DC11 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.49kg of diacid refined product, the purity of the monoacid is 99.03%, the nitrogen content is 6.02 mug/g, and the refined yield is 97.99%.
Example 7
Taking 500L of DC12 dibasic acid fermentation liquor, wherein the concentration of the DC12 dibasic acid is 16%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC12 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC12 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) 5.816kg of crude DC12 dibasic acid, 50L of butanone and 10L of diethyl ether are stirred and mixed in a decoloring tank, heated to 95 ℃ to enable the crude dibasic acid to be completely dissolved, kept at a constant temperature and kept for 25min, after the water at the lower layer is discharged in a heat-preserving state, activated carbon is added into an oil phase, the addition amount of the activated carbon is 0.15% of the mass of the oil phase, and the mixture is sufficiently stirred and mixed for 30min and filtered to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC12 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added, 5 batches of circulation are carried out according to the same process and conditions of the steps (1) - (2), 29.038kg of crude DC12 diacid is co-processed, each batch of refined diacid filter cake obtained in the step (2) is collected and dried at 100 ℃ to obtain 28.47kg of diacid refined product, the purity of the monoacid is 99.25%, the nitrogen content is 5.89 mug/g, and the refining yield is 98.04%.
Example 8
Taking 500L of DC13 dibasic acid fermentation liquor, wherein the concentration of the DC13 dibasic acid is 15%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining a membrane clear liquor a with the inlet pressure of 0.4MPa, collecting clear liquor a695L altogether, decoloring the clear liquor a by adding 0.15% active carbon, filtering to obtain decolored clear liquor b, adding sulfuric acid to adjust the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC13 dibasic acid in the acidized crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC13 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) Mixing 5.816kg of crude DC13 dibasic acid with 50L of methyl tertiary butyl ether and 10L of butanone in a decoloring tank under stirring, heating to 95 ℃ to completely dissolve the crude dibasic acid, keeping the temperature and standing for 25min, discharging water at the lower layer under the state of heat preservation, adding active carbon into the oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC13 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added, 5 batches of circulation are carried out according to the same process and conditions of the steps (1) - (2), 29.03kg of crude DC13 dibasic acid is co-processed, the refined dibasic acid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.47kg of dibasic acid refined product, the purity of the monobasic acid is 99.13%, the nitrogen content is 4.98 mug/g, and the refining yield is 98.08%.
Example 9
Taking 500L of DC15 dibasic acid fermentation liquor, wherein the concentration of the DC15 dibasic acid is 16%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC15 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC15 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) Mixing 5.816kg of crude DC15 dibasic acid with 50L of isooctyl ether and 10L of acetic acid in a decoloring tank under stirring, heating to 95 ℃ to completely dissolve the crude dibasic acid, keeping the temperature and standing for 25min, discharging water at the lower layer under the state of heat preservation, adding active carbon into the oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A.
Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC15 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.04kg of crude DC15 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.47kg of diacid refined product, the purity of the diacid is 99.18%, the nitrogen content is 5.61 mu g/g, and the refined yield is 98.03%.
Example 10
Taking 500L of DC16 dibasic acid fermentation liquor, wherein the concentration of the DC16 dibasic acid is 16%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC16 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC16 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) Mixing 5.816kg of crude DC16 dibasic acid with a mixed solvent of 50L of dibutyl ether and 10L of acetic acid in a decoloring tank, heating to 95 ℃ to completely dissolve the crude dibasic acid, keeping the constant temperature and standing for 25min, discharging water at the lower layer under the heat-preserving state, adding active carbon into an oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC16 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.01kg of crude DC16 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.47kg of diacid refined product, the purity of the monoacid is 99.07%, the nitrogen content is 5.65 mu g/g, and the refined yield is 98.14%.
Example 11
Taking 500L of DC12 dibasic acid fermentation liquor, wherein the concentration of the DC12 dibasic acid is 15%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC12 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC12 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) Mixing 5.816kg of crude DC12 dibasic acid with 50L of ethylene glycol dioctyl ether and 10L of acetic acid in a decoloring tank under stirring, heating to 95 ℃ to completely dissolve the crude dibasic acid, keeping the temperature and standing for 25min, discharging water at the lower layer under the heat-preserving state, adding active carbon into the oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC12 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.015kg of crude DC12 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.47kg of diacid refined product, the purity of the monoacid is 99.11%, the nitrogen content is 5.90 mu g/g, and the refined yield is 98.12%.
Example 12
Taking 500L of DC13 dibasic acid fermentation liquor, wherein the concentration of the DC13 dibasic acid is 16%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC13 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC13 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) Mixing 5.816kg of crude DC13 dibasic acid with 50L of dibutyl ether and 10L of isooctyl acetate in a decoloring tank, heating to 95 ℃ to completely dissolve the crude dibasic acid, keeping the temperature and standing for 25min, discharging water at the lower layer under the state of heat preservation, adding active carbon into the oil phase, wherein the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC13 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.08kg of crude DC13 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.51kg of diacid refined product, the purity of the monoacid is 99.08%, the nitrogen content is 5.72 mu g/g, and the refined yield is 98.04%.
Example 13
Taking 500L of DC18 dibasic acid fermentation liquor, wherein the concentration of the DC18 dibasic acid is 17%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC18 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC18 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.35%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) 5.821kg of crude DC18 dibasic acid and a mixed solvent of 50L of dibutyl ether and 10L of isooctyl acetate are stirred and mixed in a decoloring tank, heated to 95 ℃ to enable the crude dibasic acid to be completely dissolved, kept at a constant temperature and kept for 25min, discharged water at the lower layer under a heat-preserving state, added with active carbon, the addition amount of the active carbon is 0.15% of the mass of the oil phase, fully stirred and mixed for 30min, and filtered to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC18 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.10kg of crude DC18 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.51kg of diacid refined product, the purity of the diacid is 99.12%, the nitrogen content is 4.92 mu g/g, and the refining yield is 97.97%.
Example 14
Taking 500L of DC12 dibasic acid fermentation liquor, wherein the concentration of the DC12 dibasic acid is 15%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC12 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC12 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) Mixing 5.32kg of crude DC12 dibasic acid with 15L of dimethylbenzene and 12.24L of propylene glycol in a decoloring tank under stirring, heating to 93 ℃ to completely dissolve the crude dibasic acid, keeping the temperature and standing for 90min, discharging water at the lower layer under the heat-preserving state, adding active carbon into the oil phase, wherein the addition amount of the active carbon is 0.13% of the mass of the oil phase, fully stirring and mixing for 30min, and filtering to obtain a solvent clear liquid A. Cooling the solvent clear liquid A to 20 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC12 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the adding amount of the active carbon is 0.13% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.6MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 26.6kg of crude DC12 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain diacid refined product 26.02, the purity of single acid is 99.06%, the nitrogen content is 5.14 mug/g, and the refining yield is 97.82%.
Example 15
Taking 500L of DC15 dibasic acid fermentation liquor, wherein the concentration of the DC15 dibasic acid is 16%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC15 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC15 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) 5.745kg of crude DC15 dibasic acid and a mixed solvent of 30LDMSO, 20L of phenylbutyl ether and 13.2L of octyl ether are stirred and mixed in a decoloring tank, heated to 96 ℃ to completely dissolve the crude dibasic acid, kept at a constant temperature and kept for 25min, and then activated carbon is added into an oil phase after water at the lower layer is discharged in a heat-preserving state, wherein the addition amount of the activated carbon is 0.15% of the mass of the oil phase, and the solvent clear liquid A is obtained by filtering after full stirring and mixing for 20 min.
Cooling the solvent clear liquid A to 10 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC15 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the addition amount of the active carbon is 0.15% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.5MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same process and condition of the steps (1) - (2), 28.725kg of crude DC15 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.12kg of diacid refined product, the purity of the monoacid is 99.14%, the nitrogen content is 5.03 mug/g, and the refined yield is 97.89%.
Example 16
Taking 500L of DC16 dibasic acid fermentation liquor, wherein the concentration of the DC16 dibasic acid is 16%, filtering the fermentation liquor by a stainless steel membrane or a ceramic membrane with the aperture of 0.5 mu m, obtaining fermentation liquor clear liquor a with the inlet pressure of 0.4MPa, collecting the fermentation liquor clear liquor a 695L altogether, adding 0.15% active carbon for decolorization, filtering to obtain decolorized clear liquor b, adding sulfuric acid, adjusting the pH to 4.5, heating to 95 ℃ for 45min, then cooling to 20 ℃ for standing until the DC16 dibasic acid in the acidified crystal liquor is completely separated out. Filtering by a plate-and-frame filter press under the filtering pressure of 0.4MPa, drying at 100 ℃ in a drying box to obtain a DC16 crude dibasic acid with the water content of about 2%. After detection, the mono-acid purity of the crude dibasic acid was 97.25%.
Purifying and refining the long-chain dibasic acid crude product, which comprises the following steps:
(1) 5.314kg of crude DC16 dibasic acid and a mixed solvent of 40L of ethanol and 10L of glycol dinonyl ether are stirred and mixed in a decoloring tank, heated to 93 ℃ to enable the crude dibasic acid to be completely dissolved, kept at a constant temperature and kept stand for 25min, and after water at the lower layer is discharged in a heat-preserving state, active carbon is added into an oil phase, the addition amount of the active carbon is 0.1% of the mass of the oil phase, and the solvent clear liquid A is obtained after the mixture is fully stirred and mixed for 50min and filtered. Cooling the solvent clear liquid A to 15 ℃ with the aid of jacket water, crystallizing and separating out long-chain diacid, and filtering by a plate-and-frame filter press to obtain a DC16 diacid refined crystallization filter cake and crystallization mother liquor.
(2) And (3) conveying the crystallization mother liquor obtained in the step (1) to a mother liquor recovery tank, adding active carbon, wherein the adding amount of the active carbon is 0.1% of the mass of the crystallization mother liquor, fully stirring and mixing for about 30min, filtering by a plate frame, wherein the filtering pressure is 0.4MPa, and collecting a filtered clear liquid B to a decoloring tank to be used as an organic solvent for refining of the next batch.
The filtered clear liquid B is used as the organic solvent of the next batch step (1), no new organic solvent is added in the treatment process, 5 batches of circulation are carried out according to the same processes and conditions of the steps (1) - (2), 29.01kg of crude DC16 diacid is co-processed, the refined diacid filter cake obtained in each batch step (2) is collected and dried at 100 ℃ to obtain 28.44kg of diacid refined product, the purity of the monoacid is 99.05%, the nitrogen content is 5.29 mug/g, and the refined yield is 98.03%.
TABLE 1 quality of refined diacid product
At present, a distillation method is generally adopted to recover a solvent from a crystallization mother liquor, and as CN104447274B discloses a method for recovering and utilizing a crystallization mother liquor of purification and refining of long-chain carbon diacid, when solvent methanol is recovered, the crystallization mother liquor is put into a methanol recovery distillation kettle for recovery. The distillation method is used for recycling the long-chain dibasic acid, and the problems of high energy consumption, high investment, high solvent loss, high production cost and the like are solved.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A refining and purifying method for producing long-chain dibasic acid by biological fermentation is characterized by comprising the following steps:
Dissolving a long-chain binary acid crude product prepared by a biological fermentation method in an organic solvent, standing and separating to obtain an oil phase, adding an adsorbent A, filtering to obtain a solution clear liquid A, cooling, crystallizing and filtering the solution clear liquid A to obtain a filter cake which is long-chain binary acid; the molecular general formula of the long-chain dibasic acid is as follows: HOOC- (CH 2)n -COOH, n is 8-20);
the filtrate obtained by filtration is crystallization mother liquor, adsorbent B is added into the crystallization mother liquor for adsorption treatment, and solution clear liquid B obtained by filtration is used as organic solution for recycling.
2. The method for refining and purifying long-chain dibasic acid produced by biological fermentation according to claim 1, wherein the ratio of the crude long-chain dibasic acid to the organic solvent is 1kg:7-11L.
3. The method for purifying and refining long-chain dibasic acid by biological fermentation according to claim 1, wherein the organic solvent is two or more of an ester organic solvent, an ether organic solvent, a ketone organic solvent, an alcohol organic solvent, a furan organic solvent, an acid organic solvent, an aromatic organic solvent, a sulfur-containing organic solvent, and a halogenated hydrocarbon organic solvent.
4. The method for refining and purifying long-chain dibasic acid produced by biological fermentation according to claim 3, the organic solvent is toluene, xylene, benzene chloride, dichlorobenzene, nitrobenzene, ethyl acetate, isopropyl acetate, methyl acetate, butyl acetate, octyl acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol dipentyl ether, ethylene glycol dihexyl ether, ethylene glycol diheptyl ether, ethylene glycol dioctyl ether, ethylene glycol dinonyl ether, ethylene glycol didecyl ether, ethylene glycol dilauryl ether, methyl chloride, acetic acid, propionic acid, butyric acid, malonic acid, succinic acid, adipic acid, terephthalic acid, diethyl ether, propyl ether, amyl ether, hexyl ether, heptyl ether, octyl ether, nonyl ether, decyl ether, lauryl ether, methyl tert-butyl ether, acetone, butanone, methanol, ethanol, butanol, propanol, ethylene glycol, propylene glycol, 1, 4-butanediol, tetrahydrofuran, 1, 4-dioxane, DMSO, methyl ethyl ether, methyl butyl ether, methyl octyl ether, ethyl butyl ether, ethyl octyl ether, anisole, phenethyl ether, phenylbutyl ether, octyl ether, chloroform.
5. The method for refining and purifying long-chain dibasic acid produced by biological fermentation according to claim 1, wherein the crude long-chain dibasic acid is prepared by the following steps: and (3) performing degerming, decoloring, acidifying crystallization and filtering on long-chain binary acid fermentation liquor obtained by fermenting the microorganism by utilizing alkane.
6. The method for purifying and refining long-chain dibasic acid produced by biological fermentation according to claim 1, wherein the dissolution temperature is 93-96 ℃.
7. The method for refining and purifying long-chain dibasic acid produced by biological fermentation according to claim 1, wherein the standing time is 20-90min.
8. The method for refining and purifying long-chain dibasic acid produced by biological fermentation according to claim 1, wherein the adsorbent A and the adsorbent B are 200-500 meshes of activated carbon;
the addition amount of the adsorbent A is 0.1-0.15% of the oil phase mass;
The adding amount of the adsorbent B is 0.1-0.15% of the mass of the crystallization mother liquor.
9. The method for refining and purifying long-chain dibasic acid produced by biological fermentation according to claim 1, wherein the filtration pressure is 0.4-0.6MPa.
10. The method for refining and purifying long-chain dicarboxylic acid by biological fermentation according to claim 1, wherein the cooling crystallization is crystallization to separate out long-chain dicarboxylic acid after cooling to 10-20 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911036A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for obtaining high pure dicarboxylic 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 |
| CN103965035A (en) * | 2013-01-30 | 2014-08-06 | 上海凯赛生物技术研发中心有限公司 | Refining method of long-chain binary acid |
| CN109809982A (en) * | 2019-01-25 | 2019-05-28 | 中国石油化工股份有限公司 | A kind of long-chain biatomic acid indudstrialized refining system and process for refining |
| CN112321418A (en) * | 2020-11-24 | 2021-02-05 | 淮安清江石油化工有限责任公司 | Refining method of long-chain dibasic acid |
| CN114426476A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Refining method and device for long-chain dibasic acid |
| CN115028530A (en) * | 2021-03-03 | 2022-09-09 | 上海凯赛生物技术股份有限公司 | Extraction process of long-chain dicarboxylic acid and long-chain dicarboxylic acid product |
-
2023
- 2023-12-15 CN CN202311730574.XA patent/CN118324625A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911036A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for obtaining high pure dicarboxylic 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 |
| CN103965035A (en) * | 2013-01-30 | 2014-08-06 | 上海凯赛生物技术研发中心有限公司 | Refining method of long-chain binary acid |
| CN109809982A (en) * | 2019-01-25 | 2019-05-28 | 中国石油化工股份有限公司 | A kind of long-chain biatomic acid indudstrialized refining system and process for refining |
| CN114426476A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Refining method and device for long-chain dibasic acid |
| CN112321418A (en) * | 2020-11-24 | 2021-02-05 | 淮安清江石油化工有限责任公司 | Refining method of long-chain dibasic acid |
| CN115028530A (en) * | 2021-03-03 | 2022-09-09 | 上海凯赛生物技术股份有限公司 | Extraction process of long-chain dicarboxylic acid and long-chain dicarboxylic acid product |
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