CN117342941A - 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 PDFInfo
- Publication number
- CN117342941A CN117342941A CN202210759647.7A CN202210759647A CN117342941A CN 117342941 A CN117342941 A CN 117342941A CN 202210759647 A CN202210759647 A CN 202210759647A CN 117342941 A CN117342941 A CN 117342941A
- Authority
- CN
- China
- Prior art keywords
- solid
- acid
- long
- treatment
- liquid separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000007670 refining Methods 0.000 title claims abstract description 13
- 238000000605 extraction Methods 0.000 title abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 71
- 239000007787 solid Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000706 filtrate Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 238000000855 fermentation Methods 0.000 claims abstract description 38
- 230000004151 fermentation Effects 0.000 claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 238000005374 membrane filtration Methods 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 24
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 230000020477 pH reduction Effects 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000004042 decolorization Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- 238000011282 treatment Methods 0.000 claims description 34
- 238000001471 micro-filtration Methods 0.000 claims description 19
- 238000000108 ultra-filtration Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 5
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 3
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims 2
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000001105 regulatory effect Effects 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C07C55/21—Dicarboxylic acids containing twelve carbon atoms
Abstract
The invention provides a process for extracting and refining long-chain dibasic acid and a product thereof, wherein the process comprises the following steps: (1-1) filtering long-chain dibasic acid fermentation liquor through a membrane to obtain filtrate; decolorizing the filtrate, and performing solid-liquid separation to obtain clear liquid, and performing acidification crystallization and solid-liquid separation on the clear liquid to obtain a solid; (2-1) washing the solid with water at 50-95 ℃ and drying to obtain the product. The process has simple steps and low energy consumption. The extraction and refining process is optimized, the membrane filtration process is used for removing impurities, and the temperature is reduced to 20-45 ℃ before the solid-liquid separation after the decolorization process, so that the impurities are further separated out from the solution and are wrapped and adsorbed by the decolorization agent, and then the impurities are removed through the solid-liquid separation mode. The obtained product has good quality, high purity and low content of impurities such as monoacids. The product has wide application field.
Description
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 long-chain dibasic acid, which effectively reduces the impurity content of fermentation byproducts in the product and obtains a high-quality long-chain dibasic acid product.
The extraction and refining method of the long-chain dibasic acid comprises the following steps:
(1-1) filtering long-chain dibasic acid fermentation liquor through a membrane to obtain filtrate; decolorizing the filtrate, and performing solid-liquid separation to obtain clear liquid, and performing acidification crystallization and solid-liquid separation on the clear liquid to obtain a solid;
(2-1) washing the solid with water at 50-95 ℃ and drying to obtain the product.
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 is from 6.0 to 10, more preferably from 6.5 to 9.5, and still more preferably from 8.5 to 9.5, prior to the membrane filtration treatment.
As is conventional to those skilled in the art, the pH of the long chain dibasic acid fermentation broth may be either a natural pH or an adjusted pH.
In one embodiment, in the step (1-1), the temperature of the filtrate is controlled to be 20-45 ℃ after the filtrate is decolorized and before the solid-liquid separation.
In one embodiment, in step (1-1), the clear solution obtained after the solid-liquid separation is subjected to membrane filtration treatment before being subjected to acidification and crystallization to obtain filtrate, and then the filtrate is subjected to acidification and crystallization, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration.
In a preferred embodiment, the method comprises the steps of (1-2) 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 carrying out acidification crystallization treatment and solid-liquid separation treatment after any one of the treatments (one) - (four) on the long-chain dibasic acid salt solution to obtain a solid; the modes (one) to (four) are as follows:
mode one: filtering by an ultrafiltration membrane;
mode two: decoloring and solid-liquid separation;
mode three: membrane filtration treatment, decolorization treatment and solid-liquid separation treatment, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration;
mode four: decolorizing, solid-liquid separating and membrane filtering, wherein the membrane filtering adopts micro-filtration membrane filtering and/or ultra-filtration membrane filtering.
The alkaline substances include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonia, sodium oxide, potassium oxide.
Further, the number of times of filtration in the first mode is 1 or more, further 1 to 10 times, further 1 to 5 times. When the number of times of filtration is 2 or more, continuous filtration or interval filtration may be used. It is well known to those skilled in the art that the interval filtration is performed with other impurity removal treatments between any optionally two adjacent filtration.
Further, in the second, third or fourth mode, the temperature of the solution is controlled to 20 to 45 ℃ after the decoloring treatment and before the solid-liquid separation.
Further, in the second aspect (ii), the third aspect (iii), or the fourth aspect (iv), the decolorizing agent for the decolorizing treatment is removed by a solid-liquid separation treatment.
Further, the solid-liquid separation mode is centrifugal separation or filtration separation, and further is plate-frame filtration separation.
As is conventional in the art, after the solid is washed with 50 to 95℃water in step (2-1), water may be removed by filtration or centrifugation.
In one embodiment, in step (2-1), the solid is washed with water at 50-95 ℃ in the following manner: washing with 50-95 deg.c water and/or mixing the solid with water and stirring at 50-95 deg.c.
In one embodiment, in step (2-1), the solid is washed with water at 50-95 ℃ in the following manner: mixing the solid with water, stirring at 50-95 ℃, filtering or centrifuging to remove water, and flushing the obtained solid with water at 50-95 ℃.
The stirring time is not particularly limited. In one embodiment, the stirring time is 10 to 300min, more preferably 10 to 180min, still more preferably 10 to 120min. For example 50min, 100min, 150min, 240min. In one embodiment, in step (2-1), the temperature of the water wash is further 50 to 80 ℃.
In the present invention, the temperature of the microfiltration membrane filtration is 50 to 100 ℃, 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 may be 1000 to 100000Da, still further may be 1000 to 10000Da, still further may be 1000 to 7000Da, for example 3000Da, 5000Da, 10000Da, 50000Da.
In one embodiment, the concentration of the filtrate after membrane filtration is controlled to be 2 to 10wt%, preferably 2 to 8wt%, such as 3wt%, 6wt%. The concentration of the filtrate may be controlled by dilution or concentration.
In the present invention, the decoloring agent for the decoloring treatment is preferably activated carbon.
In the invention, the temperature of the decoloring treatment is 70-95 ℃.
In the present invention, the time for the decoloring treatment is 20 to 180 minutes, and further 20 to 100 minutes, for example, 50 minutes, 70 minutes.
In the present invention, the acidification crystallization is performed by adjusting the pH value of the solution to 2 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 percent, and the content of long-chain monobasic acid is less than or equal to 150ppm.
In one embodiment, the long chain monobasic acid has the same number of carbon atoms as the long chain dibasic acid.
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, the membrane filtration process is used for removing impurities, and the temperature is reduced to 20-45 ℃ before the solid-liquid separation after the decolorization process, so that the impurities are further separated out from the solution and are wrapped and adsorbed by the decolorization agent, and then the impurities are removed through the solid-liquid separation mode.
3. The product has good quality, high purity and low content of impurities such as 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.
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 9.3, heating to 86 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 86 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then decolorized with 2.5wt% of activated carbon at 88℃for 35 minutes, cooled to 31℃and removed by plate and frame filtration to give a clear solution.
And (3) regulating the pH value of the clear solution to 3.1 by sulfuric acid, acidifying and crystallizing, and filtering to obtain a solid containing the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve the solid, and filtering twice with ultrafiltration membrane (with molecular weight cut-off of 4000 Da) at 32deg.C to obtain filtrate.
And (3) regulating the pH value of the filtrate to 3.2 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain the solid containing the dodecadiacid.
(3) Washing the solid obtained in the step (2) with water at 55 ℃, centrifuging to remove water, and drying the solid to obtain the dodecadiacid 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 9.3, heating to 86 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 86 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then decolorized with 2.5wt% of activated carbon at 88℃for 35 minutes, cooled to 31℃and removed by plate and frame filtration to give a clear solution.
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 the dodecadiacid.
(2) Adding the solid containing the dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.1 weight percent, decoloring the solution at 90 ℃ for 25 minutes by using 2.5 weight percent of active carbon, cooling to 35 ℃, and filtering and removing the active carbon by a plate frame to obtain decolored liquid.
And (3) regulating the pH value of the decolorized solution to 3.2 by using sulfuric acid, acidifying and crystallizing, and filtering to obtain a solid containing the dodecadiacid.
(3) Washing the solid obtained in the step (2) with water at 55 ℃, centrifuging to remove water, and drying the solid to obtain the dodecadiacid 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 9.3, heating to 87 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 87 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.1wt%, then decolorized with 2.5wt% of activated carbon at 88℃for 35 minutes, cooled to 30℃and removed by plate and frame filtration to give a clear solution.
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 the dodecadiacid.
(2) Adding solid containing dodecadiacid into water, adding sodium hydroxide to dissolve the solid, and filtering with ultrafiltration membrane (with molecular weight cut-off of 4000 Da) at 33deg.C to obtain filtrate.
The concentration of the filtrate is controlled to be 5.2 weight percent, then 2.5 weight percent of active carbon is used for decolorization for 25 minutes at 90 ℃, the temperature is reduced to 37 ℃, the active carbon is removed by plate and frame filtration, decolorization liquid is obtained,
and (3) regulating the pH value of the decolorized solution to 3.2 by using sulfuric acid, acidifying and crystallizing, and filtering to obtain a solid containing the dodecadiacid.
(3) Washing the solid obtained in the step (2) with water at 55 ℃, centrifuging to remove water, and drying the solid to obtain the dodecadiacid product.
Example 4
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 9.3, heating to 86 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 86 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.1wt%, then decolorized with 2.5wt% of activated carbon at 88℃for 35 minutes, cooled to 30℃and removed by plate and frame filtration to give a clear solution.
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 the dodecadiacid.
(2) Adding the solid containing the dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.1 weight percent, decoloring the solution at 90 ℃ for 25 minutes by using 2.5 weight percent of active carbon, cooling to 35 ℃, and filtering and removing the active carbon by a plate frame to obtain decolored liquid.
Then filtered through an ultrafiltration membrane (molecular weight cut-off 4000 Da) at a filtration 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) Washing the solid obtained in the step (2) with water at 55 ℃, centrifuging to remove water, and drying the solid to obtain the dodecadiacid product.
Example 5
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 9.3, heating to 86 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 86 ℃ to obtain filtrate.
The concentration of the filtrate was controlled to 6.2wt%, and then decolorized with 2.5wt% of activated carbon at 88℃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 3.0 by sulfuric acid, performing acidification crystallization, and filtering through a plate frame to obtain a solid containing the dodecadiacid.
(2) Adding the solid containing the dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.3 weight percent, decoloring the solution at 90 ℃ for 25 minutes by using 2.5 weight percent of active carbon, and filtering the solution by a plate frame to remove the active carbon to obtain decolored solution.
Then filtered through an ultrafiltration membrane (molecular weight cut-off 4000 Da) at a filtration 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) Washing the solid obtained in the step (2) with water at 55 ℃, centrifuging to remove water, and drying the solid to obtain the dodecadiacid 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 9.3, heating to 86 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 86 ℃ to obtain filtrate.
The concentration of the filtrate is controlled to be 6.2wt%, then 2.5wt% of active carbon is used for decoloring at 88 ℃ for 35 minutes, the temperature is reduced to 31 ℃, the active carbon is removed through plate and frame filtration to obtain clear liquid, then an ultrafiltration membrane (with the molecular weight cut-off of 4000 Da) is used for continuous filtration twice, the filtration temperature is 31 ℃, the pH value of the obtained filtrate is regulated to 3.2 through sulfuric acid for acidification crystallization, and the solid containing the dodecadiacid is obtained through plate and frame filtration.
(2) Washing the solid obtained in the step (1) with water at 55 ℃, centrifuging to remove water, and drying the solid to obtain the dodecadiacid product.
Example 7
With reference to the fermentation method of example 8 of patent document CN1570124a, a hexadecanoic diacid fermentation broth was obtained.
(1) Adding alkali into fermentation broth of hexadecanoic dibasic acid to adjust pH to 8.7, heating to 90deg.C, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 90deg.C to obtain filtrate.
The concentration of the filtrate was controlled at 6.2wt%, then decolorized with 2.5wt% activated carbon at 92℃for 35 minutes, cooled to 35℃and removed by plate and frame filtration to give a clear solution.
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 the solid to obtain 5.3wt% solution, decolorizing with 2.5wt% active carbon at 90deg.C for 30min, cooling to 32deg.C, and filtering to remove active carbon to obtain decolorized solution.
Then filtered through an ultrafiltration membrane (molecular weight cut-off 4000 Da) at a filtration temperature of 32℃to give a filtrate.
And (3) regulating the pH value of the filtrate to 3.4 by sulfuric acid, acidifying and crystallizing, and filtering to obtain a solid containing hexadecanoic dibasic acid.
(3) Washing the solid obtained in the step (2) with water at 70 ℃, centrifuging to remove water, and drying the solid to obtain the hexadecanoic diacid 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 9.3, heating to 87 ℃, and filtering with ceramic microfiltration membrane (pore diameter of 0.05 um) at 87 ℃ to obtain filtrate.
The concentration of the filtrate was controlled at 6.1wt%, then decolorized with 2.5wt% of activated carbon at 87℃for 35 minutes, cooled to 30℃and removed by plate and frame filtration to give 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 the dodecadiacid.
(2) Adding the solid containing the dodecadiacid into water, adding sodium hydroxide to dissolve the solid to obtain a solution with the concentration of 5.1 weight percent, decoloring the solution at 88 ℃ for 25 minutes by using 2.5 weight percent of active carbon, cooling to 38 ℃, and filtering the solution by a plate frame to remove the active carbon to obtain decolored solution.
Then filtered through an ultrafiltration membrane (molecular weight cut-off 4000 Da) at a filtration temperature of 35℃to give a filtrate.
And (3) regulating the pH value of the filtrate to 3.3 by sulfuric acid, acidifying and crystallizing, and filtering to obtain the solid containing the dodecadiacid.
(3) Mixing the solid obtained in the step (2) with water, stirring for 30min at 65 ℃, centrifuging to remove water, flushing the obtained solid with water at 65 ℃, centrifuging to remove water, 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 index test results for Long chain dibasic acid products of examples 1-8
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 through a membrane to obtain filtrate; decolorizing the filtrate, and performing solid-liquid separation to obtain clear liquid, and performing acidification crystallization and solid-liquid separation on the clear liquid to obtain a solid;
(2-1) washing the solid with water at 50-95 ℃ and drying to obtain the product.
2. 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.
3. The method according to claim 1, wherein in the step (1-1), the temperature is controlled to 20 to 45 ℃ after the filtrate is decolorized and before the solid-liquid separation; and/or the number of the groups of groups,
in the step (1-1), the clear liquid obtained after solid-liquid separation is subjected to membrane filtration treatment before acidification and crystallization to obtain filtrate, and then the filtrate is subjected to acidification and crystallization, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration.
4. The method according to claim 1, comprising the steps of (1-2) 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 subjecting the long-chain dibasic acid salt solution to any one of the treatments (one) to (four) and then to acidification crystallization treatment and solid-liquid separation treatment to obtain a solid;
the modes (one) to (four) are as follows:
mode one: filtering by an ultrafiltration membrane;
mode two: decoloring and solid-liquid separation;
mode three: membrane filtration treatment, decolorization treatment and solid-liquid separation treatment, wherein the membrane filtration treatment adopts microfiltration membrane filtration and/or ultrafiltration membrane filtration;
mode four: decolorizing, solid-liquid separating and membrane filtering, wherein the membrane filtering adopts micro-filtration membrane filtering and/or ultra-filtration membrane filtering.
5. The method according to claim 4, wherein the temperature of the solution after the decoloring treatment and before the solid-liquid separation is controlled to 20 to 45 ℃.
6. The method according to claim 3 or 4, wherein the temperature of microfiltration membrane filtration is 50-100 ℃ and/or the temperature of ultrafiltration membrane filtration is 20-45 ℃.
7. The process according to claim 1, wherein in step (2-1) the solid is washed with water at 50-95 ℃ by rinsing and/or the solid is mixed with water and stirred at 50-95 ℃.
8. The method according to claim 1, wherein in step (1-1), the long-chain dibasic acid fermentation broth has a pH of 6.0 to 10, further 6.5 to 9.5, further 8.5 to 9.5, before the membrane filtration treatment; and/or the number of the groups of groups,
in the step (1-1), the acidification crystallization is carried out by adjusting the pH value of the clear liquid to 2-5.5 and further 2-4.
9. The method according to claim 1 or 3 or 4 or 5, wherein the temperature of the decoloring treatment is 70 to 95 ℃; and/or the number of the groups of groups,
the time of the decoloring treatment is 20-180 min, and further 20-100 min; and/or the decoloring agent for the decoloring treatment is activated carbon.
10. A long-chain binary acid product is characterized in that the purity is more than or equal to 98 percent, and the content of long-chain monobasic acid is less than or equal to 150ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210759647.7A CN117342941A (en) | 2022-06-29 | 2022-06-29 | Extraction and refining process and product of long-chain dibasic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210759647.7A CN117342941A (en) | 2022-06-29 | 2022-06-29 | Extraction and refining process and product of long-chain dibasic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117342941A true CN117342941A (en) | 2024-01-05 |
Family
ID=89369837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210759647.7A Pending CN117342941A (en) | 2022-06-29 | 2022-06-29 | Extraction and refining process and product of long-chain dibasic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117342941A (en) |
-
2022
- 2022-06-29 CN CN202210759647.7A patent/CN117342941A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109516913B (en) | Aqueous phase melting crystallization process of long-chain dicarboxylic acid | |
| CN108017535B (en) | Method for extracting long-chain dicarboxylic acid from fermentation liquor | |
| CN102329212B (en) | Refining method for long-chain binary acid | |
| JP2021098685A (en) | Long chain dibasic acid extraction method and system | |
| CN105712887B (en) | A kind of production method of long-chain nylon salt | |
| CN105712871A (en) | Purification method of long chain dicarboxylic acid | |
| CN108947809B (en) | Method for extracting and refining long-chain dicarboxylic acid from fermentation liquor | |
| CN111039808A (en) | Method for extracting tyrosine from fermentation liquor | |
| CN1221510C (en) | Refining method for long-chain biatomic acid | |
| CN103804172A (en) | Method for improving organic acid product quality | |
| CN111592453A (en) | Method for removing/recovering organic solvent in long-chain dicarboxylic acid | |
| CN103772186B (en) | A kind of process for purification of fermentation organic acid | |
| CN110256238B (en) | Refining method of long-chain mixed dibasic acid | |
| CN104592004B (en) | A kind of method of refining long-chain organic acid | |
| CN117342941A (en) | Extraction and refining process and product of long-chain dibasic acid | |
| CN113461514A (en) | Method for extracting long-chain dicarboxylic acid from fermentation liquor | |
| CN109485558B (en) | Purification method of long-chain dibasic acid | |
| CN103804174A (en) | Organic acid refining method | |
| CN117342947A (en) | Extraction and refining method of long-chain dibasic acid and product | |
| CN106554273B (en) | Method for purifying long-chain dicarboxylic acid in fermentation liquor | |
| CN105712888B (en) | A kind of preparation method of long-chain nylon salt | |
| CN114249645A (en) | Extraction method of sebacic acid and sebacic acid product | |
| CN110683947B (en) | Long-chain dibasic acid with low content of hydroxy acid impurities and method for reducing content of hydroxy acid impurities | |
| CN117342943A (en) | Extraction and refining method of long-chain dibasic acid and product | |
| CN111533651A (en) | Method for preparing long-chain dicarboxylic acid by aqueous phase method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |