CN117342942A - Extraction and refining process and product of long-chain dibasic acid - Google Patents

Extraction and refining process and product of long-chain dibasic acid Download PDF

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Publication number
CN117342942A
CN117342942A CN202210818311.3A CN202210818311A CN117342942A CN 117342942 A CN117342942 A CN 117342942A CN 202210818311 A CN202210818311 A CN 202210818311A CN 117342942 A CN117342942 A CN 117342942A
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groups
treatment
resin
solid
long
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杨晨
杜建华
刘修才
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Cathay R&D Center Co Ltd
CIBT America Inc
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Cathay R&D Center Co Ltd
CIBT America Inc
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/21—Dicarboxylic acids containing twelve carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

The invention provides a process for extracting and refining long-chain dibasic acid and a product thereof, comprising the following steps: (1-1) filtering long-chain dibasic acid fermentation liquor and/or long-chain dibasic acid fermentation treatment liquor by a membrane to obtain filtrate; decolorizing the filtrate, and performing acidification crystallization and solid-liquid separation on the decolorized solution to obtain a solid; (2-1) mixing the solid with water to form a mixture, carrying out heat preservation treatment on the mixture at 70-150 ℃, then cooling treatment and solid-liquid separation treatment, and drying the obtained solid to obtain a product; the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration. The process has simple steps and low energy consumption. The extraction and refining process is optimized, and the impurities are further separated out from the solution and adsorbed and removed by a decolorizing agent by using a membrane filtration process and combining the active carbon decolorizing and resin decolorizing procedures. The product has good quality, high purity and wide application field.

Description

Extraction and refining process and product of long-chain dibasic acid
Technical Field
The invention relates to an extraction and refining process of long-chain dibasic acid produced by a biological fermentation method.
Background
The long chain dicarboxylic acid is aliphatic dicarboxylic acid (DCn for short, n is more than or equal to 10) containing more than 10 carbon atoms in a carbon chain, is a fine chemical product with important and wide industrial application, and is an important raw material for synthesizing high-grade perfume, high-performance engineering plastics, high-temperature dielectrics, high-grade hot melt adhesives, cold-resistant plasticizers, high-grade lubricating oil, high-grade paint, coating and the like in chemical industry. The production method of long-chain dibasic acid includes chemical synthesis and biological fermentation.
The biological fermentation method for producing long-chain dibasic acid is an application of a microbial fermentation technology which is emerging in seventies in the petrochemical industry field, takes petroleum byproduct wax oil as a raw material, has the advantages of wide raw material source, simple production process, mild production conditions and the like, and is widely focused at home and abroad. The extraction and refining of long-chain binary acid in industrial production mainly uses solvent treatment and water treatment. Compared with the solvent method, the water-phase crystallization method has the advantages of high water-phase crystallization yield, low cost, simple and easily obtained materials, no toxicity, less three wastes, simple recovery, low environmental protection pressure and labor intensity of workers, and capability of overcoming a series of defects of the solvent method due to extremely low solubility of long-chain dibasic acid in water, so that the water treatment method becomes a preferred technical scheme for replacing the solvent method.
The patent with publication No. CN102329212A provides a method for refining aqueous phase by using microchannel equipment, wherein the fermented clear liquid after demulsification, filtration and decoloration is reacted with dilute sulfuric acid by a microchannel reactor, crystal slurry enters a crystallization kettle for curing, the growth speed and the size of the crystal are controlled by gradient temperature, crystals with uniform particle size are formed, long-chain binary acid crystals are obtained through filtration, washing and drying, the method has the advantages that the equipment is difficult to select and clean, the refined product is easy to pollute after long-term scaling, and the impurity index is difficult to meet the index requirement of a polymerization grade product.
The patent with publication number CN102976917A discloses a water phase refining method of long-chain dibasic acid, wherein C12-C15 straight-chain alkane is used for stopping fermentation liquid or heating and demulsification the stopping fermentation liquid, and then unconverted alkane, saccharomycetes and pigment macromolecules are removed by filtration through a ceramic microfiltration membrane; coupling and blocking the clear solution of the microfiltration membrane to obtain fermented clear solution; and (3) under the conditions of heating the fermentation clear liquid and adjusting the pH value to be reasonable, adding a trace crystallization aid, adding a small amount of sulfuric acid to form trace DCA water phase crystal nucleus, repeatedly adjusting the pH value to a critical point, and raising the crystallization temperature to gradually grow DCA crystals to prepare the high-quality long-chain dibasic acid. The method has the advantages of high operation difficulty, high energy consumption and difficult industrialization.
Disclosure of Invention
In order to solve the problems of complex process, high energy consumption, low product purity and the like in the extraction and refining of long-chain dibasic acid in the prior art, the invention provides the extraction and refining process of the long-chain dibasic acid, which has high product purity, effectively reduces the content of impurities such as fermentation byproduct long-chain monobasic acid in the product, and obtains a high-quality long-chain dibasic acid product.
The invention firstly provides a method for extracting and refining long-chain dibasic acid, which comprises the following steps:
(1-1) filtering long-chain dibasic acid fermentation liquor and/or long-chain dibasic acid fermentation treatment liquor by a membrane to obtain filtrate; decolorizing the filtrate, and performing acidification crystallization and solid-liquid separation on the decolorized solution to obtain a solid;
(2-1) mixing the solid with water to form a mixture, carrying out heat preservation treatment on the mixture at 70-150 ℃, then cooling treatment and solid-liquid separation treatment, and drying the obtained solid to obtain a product;
wherein in the step (1-1), the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration.
In one embodiment of the present invention, the long-chain dicarboxylic acid is any one or a combination of two or more of sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedioic acid, tetradecanedicarboxylic acid, pentadecanoic acid, hexadecanedicarboxylic acid, heptadecanoic acid, octadecanedioic acid, or 9-ene-octadecanedioic acid.
In one embodiment, in step (1-1), the pH of the long-chain dibasic acid fermentation broth and/or the long-chain dibasic acid fermentation broth is 5.7 to 13, further 6.0 to 10.5, further 6.5 to 10.5, further 7.5 to 10.5, before the membrane filtration treatment.
The long-chain dibasic acid fermentation treatment liquid is liquid obtained by treating the long-chain dibasic acid fermentation liquid, and the treatment comprises the following steps: and (5) alkalizing treatment.
It is conventionally known to those skilled in the art that the alkalization treatment can be performed by adding an alkaline substance to the long-chain dibasic acid fermentation treatment liquid. The alkaline substance is not particularly limited, and includes, but is not limited to, sodium hydroxide, potassium hydroxide, ammonia, sodium oxide, potassium oxide, and the like.
The pH of the long chain diacid fermentation broth, long chain diacid fermentation treatment broth may be a natural pH or an adjusted pH, as is conventionally known to those skilled in the art.
In a preferred embodiment, the method comprises a step (1-2) located between step (1-1) and step (2-1):
mixing the solid obtained in the step (1-1) with an alkaline substance and water to form a long-chain dibasic acid salt solution, and performing acidification crystallization treatment and solid-liquid separation treatment after any one of the modes (one) - (three) is carried out on the long-chain dibasic acid salt solution to obtain a solid;
the modes (one) to (three) are as follows:
mode one: decoloring;
mode two: membrane filtration treatment and decoloration treatment, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration;
mode three: decolorizing treatment and membrane filtration treatment, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration.
In one embodiment, the alkaline substance includes, but is not limited to, sodium hydroxide, potassium hydroxide, ammonia, sodium oxide, potassium oxide.
In the present invention, the decoloring treatment is selected from any one or a combination of two of activated carbon decoloring and resin decoloring.
In one embodiment, the temperature of the decolorization treatment is 20 to 99 ℃, such as 20 to 55 ℃ or 56 to 99 ℃.
In one embodiment, the time for the decoloring treatment is 20 to 180min, and further 20 to 100min.
In a preferred embodiment, the activated carbon decolorization treatment is carried out at a temperature of 70 to 99 ℃.
In a preferred embodiment, the amount of activated carbon is 0.05wt% to 3wt%, further 0.1wt% to 1.5wt%.
In a preferred embodiment, the activated carbon decolorization treatment is carried out for 20 to 180 minutes, and further for 20 to 100 minutes.
In one embodiment, the pH value of the liquid to be decolorized before the activated carbon decolorization treatment is controlled to be 7-12, more preferably 7-10, and still more preferably 7.5-9.7.
The person skilled in the art is generally aware that the decolorized solution is generally obtained by removing activated carbon by solid-liquid separation after a decolorization treatment. The solid-liquid separation mode comprises centrifugation and filtration.
In a preferred embodiment, the resin is decolorized by passing a solution to be decolorized through a resin column to obtain a decolorized solution.
In one embodiment, the resin is deposited to form a resin column for the decolorization process.
In one embodiment, the resin skeleton is selected from any one of styrene-divinylbenzene copolymer and acrylonitrile-divinylbenzene copolymer.
In one embodiment, the resin is selected from acidic, basic or neutral ion exchange resins, preferably basic anion exchange resins, such as strongly basic anion exchange resins, weakly basic anion exchange resins.
In one embodiment, the resin is a macroporous basic anion exchange resin, such as macroporous strongly basic anion exchange resin, macroporous weakly basic anion exchange resin.
In one embodiment, the particle size of 90% or more of the resin is 0.3 to 1.3mm, and further, the particle size of 95% or more of the resin is 0.3 to 1.3mm.
In one embodiment, the water content of the resin is 45 to 65wt%, such as 50wt%, 55wt%, 60wt%.
In one embodiment, the resin has a wet apparent density of 0.5 to 0.8g/ml, further 0.65 to 0.75g/ml, for example 0.68g/ml, 0.70g/ml, 0.72g/ml.
In one embodiment, the resin has a mass exchange capacity of 4.0mmol/g or more.
In one embodiment, the height to diameter ratio of the resin column is 1:1 or more, and further (4 to 15): 1.
In one embodiment, the temperature of the resin decolorization treatment is 20 to 45 ℃.
In one embodiment, the pH of the liquid to be decolorized before the resin decolorization treatment is controlled to be 7 to 12, more preferably 7 to 10, still more preferably 7.5 to 9.7.
In the present invention, the manner of controlling the pH of the liquid to be decolorized in the above range is not particularly limited, and the pH of the liquid to be decolorized may be adjusted by adding an acid (e.g., sulfuric acid, hydrochloric acid) or a base (e.g., sodium hydroxide) to bring the pH in the above range. When the pH value of the liquid to be decolorized naturally falls within the above range, no additional regulation and control operation is required.
In one embodiment, the resin decolorization treatment is carried out at a feed rate of 0.05 to 10BV/h, more preferably 0.1 to 5BV/h, still more preferably 0.5 to 2BV/h.
In one embodiment, the resin is regenerated after washing with an alkaline solution, such as sodium hydroxide solution.
In one embodiment, the resin comprises any one or a combination of more than two of LSD-396 (Sesamia blue technology), LX-300C (Sesamia blue technology), LSD-296 (Sesamia blue technology), and D-301 (Ji Yue organism).
In the present invention, LSD-396 is a macroporous strong base anion exchange resin. The skeleton of LSD-396 resin is styrene-divinylbenzene copolymer. The water content is 48-58 wt%, the wet apparent density is 0.65-0.75 g/ml, the particle size of the resin with more than 95% is 0.315-1.25 mm, and the mass total exchange capacity is more than or equal to 4.2mmol/g.
In the invention, LX-300C is a macroporous weak base anion exchange resin. The skeleton of LX-300C resin is styrene-divinylbenzene copolymer. The water content is 55-60 wt%, the wet apparent density is 0.68-0.75 g/ml, the particle size of the resin with more than 95% is 0.315-1.25 mm, and the mass total exchange capacity is more than or equal to 4.5mmol/g.
In the present invention, LSD-296 is a macroporous strong base anion exchange resin. The LSD-296 resin skeleton is a styrene-divinylbenzene copolymer. The water content is 48-58 wt%, the wet apparent density is 0.65-0.75 g/ml, the particle size of the resin with more than 90% is 0.40-1.25 mm, and the mass total exchange capacity is more than or equal to 4.8mmol/g.
In the invention, D-301 is weak base amine anion exchange resin, which is macroporous adsorption resin. The skeleton of the resin D301 is styrene-divinylbenzene copolymer, the water content is 48-58 wt%, the wet apparent density is 0.65-0.72 g/ml, the particle size of the resin with more than 95% is 0.315-0.630 mm, and the mass total exchange capacity is more than or equal to 4.8mmol/g.
It is generally known to those skilled in the art that basic anion exchange resins can be pretreated prior to use, for example by subjecting the resin column to a column treatment with 3-5% sodium hydroxide solution and then washing the resin column with water to remove residual alkali from the resin cells.
In one embodiment, in the step (2-1), the mass ratio of the solid to the water may be 1 (2-20), further 1 (3-15), and further 1 (3-10).
In one embodiment, in the step (2-1), the temperature of the heat-retaining treatment is 105 to 150 ℃, and further 120 to 140 ℃.
In one embodiment, in the step (2-1), the temperature of the cooling treatment is at an end point temperature of 25-65 ℃.
In one embodiment, the concentration of the filtrate after membrane filtration is controlled to be 2wt% to 10wt%, further 2wt% to 8wt%, such as 3wt% and 6wt%. The concentration of the filtrate may be controlled by dilution or concentration.
In the present invention, the temperature of the microfiltration membrane filtration is 50 to 110 ℃, further 50 to 100 ℃, further 50 to 95 ℃, for example 70 ℃, 80 ℃,90 ℃.
In the present invention, the temperature of the ultrafiltration membrane filtration is 20 to 45℃such as 30℃and 35℃and 40 ℃.
In the present invention, the pore diameter of the microfiltration membrane may be 0.01 to 1. Mu.m, more preferably 0.01 to 0.2. Mu.m, still more preferably 0.01 to 0.1. Mu.m.
In the present invention, the molecular weight cut-off of the ultrafiltration membrane is 1000 to 200000Da, further 1000 to 100000Da, further 1000 to 10000Da, further 1000 to 7000Da, for example 3000Da, 5000Da, 10000Da, 50000Da.
In the present invention, the acidification crystallization is performed by adjusting the pH value of the solution to 1 to 5.5, and further 2 to 4.
The invention also provides a long-chain binary acid product, the purity is more than or equal to 98%, the content of long-chain monobasic acid is less than or equal to 150ppm, further less than or equal to 100ppm, further less than or equal to 50ppm, further less than or equal to 25ppm.
In one embodiment, the long chain monobasic acid has 10 to 18 carbon atoms.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
1. the process steps are simple, and the energy consumption is low.
2. The extraction and refining process is optimized, and the impurities are further separated out from the solution and adsorbed and removed by a decolorizing agent by using a membrane filtration process and combining the active carbon decolorizing and resin decolorizing procedures.
3. The product has good quality, high purity and low impurity content of long-chain monobasic acid and the like. The product has wide application field.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
LSD-296 type resin (West Ann blue technology) is a macroporous strong base anion exchange resin. The LSD-296 resin skeleton is a styrene-divinylbenzene copolymer. The water content is 48-58 wt%, the wet apparent density is 0.65-0.75 g/ml, the particle size of the resin with more than 90% is 0.40-1.25 mm, and the mass total exchange capacity is more than or equal to 4.8mmol/g.
LX-300C resin (well known in the art of Siemens blue) is a macroporous weak base anion exchange resin. The skeleton of LX-300C resin is styrene-divinylbenzene copolymer. The water content is 55-60 wt%, the wet apparent density is 0.68-0.75 g/ml, the particle size of the resin with more than 95% is 0.315-1.25 mm, and the mass total exchange capacity is more than or equal to 4.5mmol/g.
The method for detecting the purity of the product and the content of the long-chain monobasic acid comprises the following steps: gas chromatography.
Example 1
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 35 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.3wt%, regulating the pH of the solution to 9.5, adding 0.5wt% of active carbon to decolorize at 90 ℃ for 25 minutes, filtering to remove the active carbon through a plate frame, allowing the obtained filtrate (with the pH of 9.5 controlled) to flow through a resin column (the resin is LSD-296 and the height-diameter ratio of the resin column is 8:1) at the feeding speed of 1BV/h at the temperature of 30 ℃, and collecting effluent.
And (3) regulating the pH value of the effluent liquid to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 2
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 35 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve to obtain 5.3wt% solution, adjusting pH to 9.5, and filtering with ultrafiltration membrane (molecular weight cut-off of 3000 Da) at 30deg.C to obtain filtrate.
The filtrate was passed through a resin column (LSD-296 for resin, 8:1 for height to diameter) at 30℃at a feed rate of 1BV/h, and the effluent was collected.
And (3) regulating the pH value of the effluent liquid to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 3
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 35 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve to obtain 5.3wt% solution, adjusting pH to 9.5, and filtering with ultrafiltration membrane (molecular weight cut-off of 3000 Da) at 33deg.C to obtain filtrate.
The concentration of the filtrate was controlled at 5.3wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 25 minutes, the activated carbon was removed by plate and frame filtration, the obtained filtrate (pH 9.5) was passed through a resin column (LSD-296 as resin, height to diameter ratio of resin column: 8:1) at 30℃at a feed rate of 1BV/h, and the effluent was collected.
And (3) regulating the pH value of the effluent liquid to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 4-A
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 35 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.3wt%, regulating the pH of the solution to 9.5, adding 0.5wt% of active carbon to decolorize at 90 ℃ for 25 minutes, filtering to remove the active carbon through a plate frame, allowing the obtained filtrate (with the pH of 9.5 controlled) to flow through a resin column (the resin is LSD-296 and the height-diameter ratio of the resin column is 8:1) at the feeding speed of 1BV/h at the temperature of 30 ℃, and collecting effluent.
The effluent was filtered through an ultrafiltration membrane (molecular weight cut-off 3000 Da) at a temperature of 33℃to give a filtrate.
And (3) regulating the pH value of the filtrate to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 4-B
(1) The fermentation broth of dodecadiacid (pH 6.2) was heated to 100deg.C and filtered through ceramic microfiltration membrane (pore size 0.05 um) at 100deg.C to give filtrate.
The concentration of the filtrate was controlled at 5.2wt%, then 0.7wt% of activated carbon was added to decolorize at 90℃for 50 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.3wt%, regulating the pH of the solution to 9.3, adding 0.5wt% of active carbon to decolorize at 90 ℃ for 25 minutes, filtering to remove the active carbon through a plate frame, allowing the obtained filtrate (with the pH of 9.3 controlled) to flow through a resin column (the resin is LSD-296 and the height-diameter ratio of the resin column is 8:1) at the feeding speed of 1BV/h at 30 ℃, and collecting effluent.
The effluent was filtered through an ultrafiltration membrane (molecular weight cut-off 3000 Da) at a temperature of 35℃to give a filtrate.
And (3) regulating the pH value of the filtrate to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 5
With reference to the fermentation method of example 8 of patent document CN1570124a, a hexadecanoic diacid fermentation broth was obtained.
(1) Adding alkali into the fermentation broth of hexadecanoic dibasic acid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 5.2wt%, then 0.7wt% of activated carbon was added to decolorize at 90℃for 40 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.0 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing hexadecanediacid.
(2) Adding solid containing hexadecanoic dibasic acid into water, adding sodium hydroxide to dissolve to obtain 5.0wt% solution, adjusting pH to 9.2, and filtering with microfiltration membrane (pore size of 0.05 um) at 33deg.C to obtain filtrate.
The concentration of the filtrate was controlled at 5.3wt%, then 0.4wt% of activated carbon was added to decolorize at 90℃for 25 minutes, the activated carbon was removed by plate and frame filtration, the obtained filtrate (pH 9.2) was passed through a resin column (LSD-296 as resin, 8:1 ratio of height to diameter of the resin column) at 30℃at a feed rate of 0.5BV/h, and the effluent was collected.
And (3) regulating the pH value of the effluent liquid to 3.1 by sulfuric acid, acidifying and crystallizing, and filtering to obtain a solid containing hexadecane diacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 135 ℃ for 57 minutes after the mass ratio of the solid to the water is 1:10, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the hexadecanoic diacid product.
Example 6
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 30 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve to obtain 5.3wt% solution, adjusting pH to 9.6, and filtering with ultrafiltration membrane (molecular weight cut-off of 3000 Da) at 33deg.C to obtain filtrate.
The concentration of the filtrate was controlled at 5.3wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 25 minutes, the activated carbon was removed by plate and frame filtration, the obtained filtrate (pH 9.6) was passed through a resin column (resin: LX-300C, height to diameter ratio of the resin column: 12:1) at a feed rate of 3BV/h at 30℃and the effluent was collected.
And (3) regulating the pH value of the effluent liquid to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 80 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 7
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 35 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.3wt%, regulating the pH value of the solution to 11, adding 0.5wt% of active carbon to decolorize at 90 ℃ for 25 minutes, filtering to remove the active carbon through a plate frame, allowing the obtained filtrate (with the pH value of 11 controlled) to flow through a resin column (the resin is LSD-296 and the height-diameter ratio of the resin column is 8:1) at the temperature of 30 ℃ at the feed rate of 1BV/h, and collecting effluent.
The effluent was filtered through an ultrafiltration membrane (molecular weight cut-off 3000 Da) at a temperature of 33℃to give a filtrate.
And (3) regulating the pH value of the filtrate to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 8
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 35 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve to obtain 5.3wt% solution, adjusting pH to 11, and filtering with ultrafiltration membrane (molecular weight cut-off of 3000 Da) at 33deg.C to obtain filtrate.
The concentration of the filtrate was controlled at 5.3wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 25 minutes, the activated carbon was removed by plate and frame filtration, the obtained filtrate (pH 11) was passed through a resin column (LSD-296 as resin, height to diameter ratio of resin column: 8:1) at 30℃at a feed rate of 1BV/h, and effluent was collected.
And (3) regulating the pH value of the effluent liquid to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
Example 9
The fermentation process of example 4 of patent document CN1570124a was followed to obtain a dodecandioic acid fermentation broth.
(1) Adding alkali into the fermentation broth of dodecadiacid to adjust pH to 9.0, heating to 88 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 88 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 35 minutes, and the activated carbon was removed by plate and frame filtration to obtain a clear liquid.
And (3) regulating the pH value of the clear solution to 3.3 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve to obtain 5.3wt% solution, adjusting pH to 9.6, and filtering with ultrafiltration membrane (molecular weight cut-off of 3000 Da) at 33deg.C to obtain filtrate.
The concentration of the filtrate was controlled at 5.3wt%, then 0.5wt% of activated carbon was added to decolorize at 90℃for 25 minutes, and the activated carbon was removed by plate and frame filtration to obtain a filtrate.
And (3) regulating the pH value of the filtrate to 3.2 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Adding the solid obtained in the step (2) into water, keeping the temperature at 120 ℃ for 65 minutes, cooling to 42 ℃, filtering to obtain the solid, and drying the solid to obtain the dodecandioic acid product.
The test results of the long chain diacid products prepared in the above examples are shown in table 1.
TABLE 1 long chain diacid product test results Table

Claims (10)

1. A method for extracting and refining long-chain dibasic acid comprises the following steps:
(1-1) filtering long-chain dibasic acid fermentation liquor and/or long-chain dibasic acid fermentation treatment liquor by a membrane to obtain filtrate; decolorizing the filtrate, and performing acidification crystallization and solid-liquid separation on the decolorized solution to obtain a solid;
(2-1) mixing the solid with water to form a mixture, carrying out heat preservation treatment on the mixture at 70-150 ℃, then cooling treatment and solid-liquid separation treatment, and drying the obtained solid to obtain a product;
wherein in the step (1-1), the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration.
2. The method according to claim 1, wherein in step (1-1), the long-chain dibasic acid fermentation broth and/or the long-chain dibasic acid fermentation broth has a pH of 5.7 to 13, further 6.0 to 10.5, further 6.5 to 10.5, further 7.5 to 10.5, before the membrane filtration treatment; and/or the number of the groups of groups,
the long-chain dibasic acid fermentation treatment liquid is liquid obtained by treating the long-chain dibasic acid fermentation liquid, and the treatment comprises the following steps: and (5) alkalizing treatment.
3. The method according to claim 1, comprising a step (1-2) between the step (1-1) and the step (2-1), wherein the solid obtained in the step (1-1) is mixed with an alkaline substance and water to form a long-chain dibasic acid salt solution, and the long-chain dibasic acid salt solution is subjected to any one of the modes (one) to (three) and then is subjected to acidification crystallization treatment and solid-liquid separation treatment to obtain a solid;
the modes (one) to (three) are as follows:
mode one: decoloring;
mode two: membrane filtration treatment and decoloration treatment, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration;
mode three: decolorizing treatment and membrane filtration treatment, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration.
4. A method according to claim 1 or 3, wherein the decolorizing treatment is selected from any one or a combination of two of activated carbon decolorizing, resin decolorizing; and/or the number of the groups of groups,
the temperature of the decoloring treatment is 20-99 ℃, such as 20-55 ℃ or 56-99 ℃; and/or the number of the groups of groups,
the time of the decoloring treatment is 20-180 min, and further 20-100 min.
5. The method according to claim 4, wherein the activated carbon decolorization treatment is carried out at a temperature of 70 to 99 ℃; and/or the number of the groups of groups,
the dosage of the activated carbon is 0.05 to 3 weight percent, and further 0.1 to 1.5 weight percent; and/or the number of the groups of groups,
the time of the activated carbon decoloring treatment is 20-180 min, and further 20-100 min; and/or the number of the groups of groups,
removing active carbon through solid-liquid separation after the decoloring treatment to obtain decoloring liquid; and/or the number of the groups of groups,
controlling the pH value of the liquid to be decolorized to 7-12, further 7-10, further 7.5-9.7 before resin decolorization; and/or the number of the groups of groups,
the pH value of the liquid to be decolorized before the activated carbon decolorization is controlled to be 7-12, further 7-10, and further 7.5-9.7.
6. The method according to claim 4, wherein the resin is decolorized by passing a liquid to be decolorized through a resin column to obtain a decolorized liquid; and/or the number of the groups of groups,
the skeleton of the resin is selected from any one of styrene-divinylbenzene copolymer and acrylonitrile-divinylbenzene copolymer, and/or,
the resin is selected from acidic, basic or neutral ion exchange resins, preferably basic anion exchange resins; and/or, more than 90% of the resin has a particle size of 0.3-1.3 mm; and/or the number of the groups of groups,
the water content of the resin is 45-65wt%; and/or the number of the groups of groups,
the wet apparent density of the resin is 0.5-0.8 g/ml, and further 0.65-0.75 g/ml; and/or the number of the groups of groups,
the mass total exchange capacity of the resin is more than or equal to 4.0mmol/g; and/or the number of the groups of groups,
the ratio of the height to the diameter of the resin column is more than 1:1, further (4-15): 1, and/or,
the temperature of the resin decoloring treatment is 20-45 ℃, and/or,
the feeding speed of the resin decoloring treatment is 0.05-10 BV/h, further 0.1-5 BV/h, further 0.5-2 BV/h; and/or the number of the groups of groups,
after the decolorization treatment, the resin is washed with an alkaline solution and regenerated.
7. The method of claim 4 or 6, wherein the resin comprises any one or a combination of two or more of LX-300C, LSD-296, LSD-396, D-301.
8. A method according to claim 1 or 3, wherein the concentration of the filtrate after membrane filtration is controlled to be 2-10 wt%, further 2-8 wt%; and/or the number of the groups of groups,
the temperature of the microfiltration membrane filtration is 50-110 ℃, further 50-100 ℃, further 50-95 ℃, and/or the temperature of the ultrafiltration membrane filtration is 20-45 ℃; and/or the number of the groups of groups,
the aperture of the microfiltration membrane is 0.01-1 micron, further 0.01-0.2 micron, further 0.01-0.1 micron; and/or the number of the groups of groups,
the molecular weight cut-off of the ultrafiltration membrane is 1000-200000 Da, more preferably 1000-100000 Da, still more preferably 1000-10000 Da, still more preferably 1000-7000 Da.
9. The method of claim 1, wherein the long chain diacid is any one or a combination of two or more of sebacic acid, undecanedioic acid, dodecadioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanodioic acid, hexadecanedioic acid, heptadecanodioic acid, octadecanedioic acid, or 9-ene-octadecanedioic acid; and/or the number of the groups of groups,
in the step (1-1), the pH value of the solution is adjusted to be 1-5.5, and further 2-4 for crystallization; and/or the number of the groups of groups,
in the step (2-1), the mass ratio of the solid to the water is 1 (2-20), further 1 (3-15), further 1 (3-10); and/or the number of the groups of groups,
in the step (2-1), the temperature of the heat preservation treatment is 105-150 ℃, and further 120-140 ℃; and/or the number of the groups of groups,
in the step (2-1), the end temperature of the cooling treatment is 25-65 ℃.
10. The long-chain diacid product is characterized in that the purity is more than or equal to 98 percent, the content of long-chain monoacid is less than or equal to 150ppm, further less than or equal to 100ppm, further less than or equal to 50ppm, further less than or equal to 25ppm.
CN202210818311.3A 2022-06-29 2022-07-12 Extraction and refining process and product of long-chain dibasic acid Pending CN117342942A (en)

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