CN106673995A - Method for refining long-chain dicarboxylic acids - Google Patents
Method for refining long-chain dicarboxylic acids Download PDFInfo
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- CN106673995A CN106673995A CN201510751337.0A CN201510751337A CN106673995A CN 106673995 A CN106673995 A CN 106673995A CN 201510751337 A CN201510751337 A CN 201510751337A CN 106673995 A CN106673995 A CN 106673995A
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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
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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Abstract
The invention discloses a method for refining long-chain dicarboxylic acids. The method comprises the following steps: I. terminated fermentation liquor is heated and demulsified, and unreacted alkane is separated; II. bacterial residues and other solid impurities are removed, and fermentation clear liquid is obtained; III. at least one of acetone and acetonitrile is added into the fermentation clear liquid, and mixing with vibration is carried out in order to filter protein and other impurities which are precipitated; IV. after filtering, a solvent in the step III is added into the system continuously, and sodium salt of diacid is precipitated; V. after filtering, water is added into collected sodium salt of diacid for dissolving, acidifying, cooling, filtering and drying are carried out in order to obtain refined dicarboxylic acid products. A precipitation method by organic solvents is used, in order to effectively reduce content of protein and other impurities in the dicarboxylic acid products, and the dicarboxylic acid products have high purity.
Description
Technical field
The present invention relates to a kind of method of refining long-chain dicarboxylic acids, the method that high purity long chain dicarboxylic acids is particularly obtained from microbial fermentation solution.
Background technology
Long chain dicarboxylic acid general molecular formula is CnH2n-2O4, wherein n is 10-18, is microorganism metabolite obtained from the fermentation such as liquid wax.Its zymotic fluid is complicated heterogeneous system, secretion wherein containing unreacted carbon source, microbial cell and fragment, the culture medium not utilized and metabolite and microorganism etc., especially wherein grade impurity containing a large amount of protein, pigment and ash, purity and the application of product are had a strong impact on, and the extraction to the species dicarboxylic acids brings difficulty with refined.
The method for extracting long chain dicarboxylic acid at present is generally divided into solvent method and Aqueous phase.Although solvent method can solve the above problems, because solvent method is present, investment is big, and equipment corrosion is serious, and the problems such as solvent and alkane and production security and environmental pollution is remained in product, and the use of the method is greatly limited.Although traditional water phase method of purification overcomes the defect of solvent method, but its product purity and yield can not be reached compared with high target.
In long chain dicarboxylic acid process for purification disclosed in CN01142806.6, with long chain dicarboxylic acid dry powder as raw material, using acetone, methyl alcohol and ethanol as solvent refining long-chain dicarboxylic acids.Dicarboxylic acids elder generation in method zymotic fluid first is Jing after charcoal absorption, then acidizing crystal, filters, washes and be dried dicarboxylic acid crystallizates filter cake and obtain long chain dicarboxylic acid dry powder, is then refined using organic solvent.The refined raw material of the method is that aqueous filter cake obtains after drying dicarboxylic acids dry powder, and the restriction to feed moisture content reduces the operating flexibility of the method, increased the equipment that thick acid is dried, and causes this technological process longer, increased production cost.And the method is in the aqueous solution for obtaining the alkaline dicarboxylic acids sodium salt before dicarboxylic acid crystallizates filter cake and in solvent refining processes, the process of charcoal absorption twice has been carried out altogether, those skilled in the relevant art know about, increase an activated carbon processing procedure, equipment investment and production cost can be increased, and activated carbon dosage is directly proportional to the loss of product, and activated carbon dosage is bigger, the yield of product is lower.And in the refined dicarboxylic acids of organic solvent, can typically reach the requirement of decolouring using adsorbent, but still more difficult removing small molecular protein therein, make total nitrogen content undesirable.
CN1255483A discloses a kind of method that Aqueous phase separates dicarboxylic acids：Zymotic fluid heating will be terminated and remove unreacted alkane, then add diatom filtration sterilization；Filtrate Jing adjusts pH value to obtain sour cake and filtrate；Filtrate adds activated carbon decolorizing again, then filters；The sour cake obtained dissolved with the filtrate after decolouring again before, acidifying；Crystallization is finally obtained, drying obtains dicarboxylic acid product.The method complex operation step, running cost is high, and dicarboxylic acid product yield is too low, and purity is not also high, and the alkane rate of recovery is low.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of method of refining long-chain dicarboxylic acids.The inventive method effectively reduces the content of the impurity such as albumen in dicarboxylic acid product, so as to obtain highly purified dicarboxylic acid product using the method for organic solvent deposit.
A kind of method of refining long-chain dicarboxylic acids of the present invention, including herein below：
I, zymotic fluid heating demulsification type will be terminated, separate unreacted alkane；
The solid impurities such as II, removing bacteria residue, obtain fermentation clear liquid；
III, at least one in fermentation clear liquid in addition acetone, acetonitrile, are filtered after concussion mixing；
IV, continue to add in system acetone, at least one in acetonitrile and filter；
V, the binary acid sodium-salt collected is dissolved in water, is acidified, cooled down, filter, being dried to obtain refined dicarboxylic acid product.
In the inventive method, it is microorganism metabolite obtained from liquid wax fermentation that zymotic fluid is terminated described in step I, wherein the dicarboxylic acid molecule formula for containing is CnH2n-2O4, wherein n is 10-18, and dicarboxylic acids can be a kind of single dicarboxylic acids, or mixed dicarboxylic acid.
In the inventive method, step II can adopt the conventional methods such as centrifugation or membrane filtration and equipment to carry out removing the operation of the impurity such as thalline.
In the inventive method, the addition in step III in acetone and/or acetonitrile is the 5% ~ 40% of fermentation clear liquid volume, shakes 20 ~ 60min of incorporation time.
In the inventive method, step III can also add appropriate picric acid, preferably add simultaneously with least one in acetone, acetonitrile, and addition is 2 ~ 5 wt% of the theoretical acid content of zymotic fluid.Picric acid, acetone and/or acetonitrile collective effect, improve the contamination precipitation effects such as albumen, nucleic acid.
In the inventive method, the preferred ultrafiltration of filtration or nanofiltration equipment described in step III is separated.
In the inventive method, the amount that the acetone and/or acetonitrile solvent for adding is continued described in step IV is the 60% ~ 150% of fermentation clear liquid volume.The fermentation mother liquor containing solvent obtained after filtration can carry out the Distillation recovery of organic solvent in heating evaporation equipment, and the organic solvent of recovery can be reused.
In the inventive method, the amount that dissolving binary acid sodium-salt described in step V adds water is the 50% ~ 100% of fermentation clear liquid volume.The pH value of the acidifying is 2.0 ~ 4.0, and temperature is 80 ~ 95 DEG C, atmospheric operation condition.Acid used by the above-mentioned acidifying of the present invention can be the H of any concentration2SO4、HNO3, HCl or H3PO4。
Till crystallisation by cooling temperature generally makes dicarboxylic acids sufficient crystallising in step V, temperature is generally 10 DEG C～30 DEG C.
The inventive method can obtain the dicarboxylic acid product of highly purified single kind, it is also possible to obtain mixed dicarboxylic acid product.
Compared with prior art, the present invention has advantages below：
The inventors discovered that, although terminating zymotic fluid during heat inactivation and breakdown of emulsion by the denaturation of the impurity such as Partial Protein to precipitate, and remove with preliminary filtration, but follow-up acidifying is separated out during dicarboxylic acids, due to the acute variation of pH value, remaining a large amount of water-solubility proteins still can the denaturation during acidifying, separate out in the lump with dicarboxylic acids, be embedded in crystal thus have a strong impact on product quality.
The present invention is initially with impurity such as unmodified albumen, nucleic acid in organic solvent and picric acid co-precipitation zymotic fluid, then precipitation is filtered to remove so that the impurity such as most albumen, nucleic acid in zymotic fluid is removed；Water miscible picric acid can form compound and precipitate with the alkaline functional group of the biomolecule such as albumen, polysaccharide, nucleic acid, then be removed by filtration, will not introduce other impurity.Afterwards by dissolved process, binary acid sodium-salt is separated out from fermentation mother liquor so that binary acid sodium-salt is separated with a small amount of other impurities of the most of pigment in mother liquor and remaining, binary acid sodium-salt is embedded when separating out, the impurity level of carrying is less.Outside fermentation system binary acid sodium-salt dissolved again, be acidified, serve the effect purified again to binary acid sodium-salt, so as to obtain highly purified dicarboxylic acids essence product.
The characteristics of there is the inventive method process is simple to be easily achieved, product yield is high, under less energy consumption input, can obtain the polymer grade product that purity is high, total nitrogen content is low, is more suitable for industrialized production.
Specific embodiment
Further the inventive method is explained below by embodiment.
Embodiment 1
With n-dodecane hydrocarbon as substrate, using the carbon dicarboxylic acids of candida tropicalis fermenting and producing 12.Dicarboxyl acid concentration is 155g/L during fermentation ends, and pH is 7.0.Zymotic fluid 1000ml is taken, 83 DEG C are heated to, is stood to room temperature, divide the liquid wax for going solution to remain, be filtered to remove thalline, 90ml acetonitriles are added in fermentation clear liquid, concussion mixing 60min, is 10 with membrane aperture-2μm membrane filtration, except deproteinized etc. is precipitated.Continue to add 1300ml acetonitriles in system, after binary acid sodium-salt is separated out in a large number, filtered using ultrafiltration apparatus, collect binary acid sodium-salt.The 500ml that adds water in the binary acid sodium-salt collected dissolves it, with the sulphur acid for adjusting pH of 6M to 3,
Stir, be heated to 85 DEG C, then crystallizing at room temperature is at the uniform velocity down to 15 DEG C/h, filter to obtain dicarboxylic acids filter cake, dry cake obtains product.Product quality is shown in Table 1.
Embodiment 2
With n-dodecane hydrocarbon as substrate, using the carbon dicarboxylic acids of candida tropicalis fermenting and producing 12.Dicarboxyl acid concentration is 153g/L during fermentation ends, and pH is 7.1.Zymotic fluid 1000ml is taken, 90 DEG C are heated to, is stood to room temperature, divide the liquid wax for going solution to remain, be filtered to remove thalline, 200ml acetone is added in fermentation clear liquid, concussion mixing 40min, is 10 with membrane aperture-2μm membrane filtration, except deproteinized etc. is precipitated.Continue to add 900ml acetone in system, after binary acid sodium-salt is separated out in a large number, filtered using ultrafiltration apparatus, collect binary acid sodium-salt.The 700ml that adds water in the binary acid sodium-salt collected dissolves it, with the sulphur acid for adjusting pH of 6M to 3,
Stir, be heated to 90 DEG C, then crystallizing at room temperature is at the uniform velocity down to 15 DEG C/h, filter to obtain dicarboxylic acids filter cake, dry cake obtains product.Product quality is shown in Table 1.
Embodiment 3
With n-tridecane hydrocarbon as substrate, using the carbon dicarboxylic acids of candida tropicalis fermenting and producing 13.Dicarboxyl acid concentration is 150g/L during fermentation ends, and pH is 7.3.Zymotic fluid 1000ml is taken, 90 DEG C are heated to, is stood to room temperature, divide the liquid wax for going solution to remain, be filtered to remove thalline, 300ml acetonitriles and 3.3g picric acid are added in fermentation clear liquid, concussion mixing 30min, is 10 with membrane aperture-2μm membrane filtration, except deproteinized etc. is precipitated.Continue to add 1050ml acetonitriles in system, after binary acid sodium-salt is separated out in a large number, filtered using ultrafiltration apparatus, collect binary acid sodium-salt.The 900ml that adds water in the binary acid sodium-salt collected dissolves it, with the sulphur acid for adjusting pH of 6M to 2, stirs, is heated to 95 DEG C, then is at the uniform velocity down to crystallizing at room temperature with 17 DEG C/h, filters to obtain dicarboxylic acids filter cake, and dry cake obtains product.Product quality is shown in Table 1.
Embodiment 4
With n-tridecane hydrocarbon as substrate, using the carbon dicarboxylic acids of candida tropicalis fermenting and producing 13.Dicarboxyl acid concentration is 151g/L during fermentation ends, and pH is 7.4.Zymotic fluid 1000ml is taken, 90 DEG C are heated to, is stood to room temperature, divide the liquid wax for going solution to remain, be filtered to remove thalline, 350ml acetone and 7.4g picric acid are added in fermentation clear liquid, concussion mixing 20min, is 10 with membrane aperture-2μm membrane filtration, except deproteinized etc. is precipitated.Continue to add 550ml acetone in system, after binary acid sodium-salt is separated out in a large number, filtered using ultrafiltration apparatus, collect binary acid sodium-salt.The 650ml that adds water in the binary acid sodium-salt collected dissolves it, with the sulphur acid for adjusting pH of 6M to 2, stirs, is heated to 90 DEG C, then is at the uniform velocity down to crystallizing at room temperature with 20 DEG C/h, filters to obtain dicarboxylic acids filter cake, and dry cake obtains product.Product quality is shown in Table 1.
The long chain dicarboxylic acid product quality of table 1
Claims (13)
1. a kind of method of refining long-chain dicarboxylic acids, it is characterised in that：Including herein below：
I, zymotic fluid heating demulsification type will be terminated, separate unreacted alkane；
II, removing bacteria residue, obtain fermentation clear liquid；
III, at least one in fermentation clear liquid in addition acetone, acetonitrile, are filtered after concussion mixing；
IV, continue to add in system acetone, at least one in acetonitrile and filter；
V, the binary acid sodium-salt collected is dissolved in water, is acidified, cooled down, filter, being dried to obtain refined dicarboxylic acid product.
2. method according to claim 1, it is characterised in that：It is microorganism metabolite obtained from liquid wax fermentation to terminate zymotic fluid described in step I, wherein the dicarboxylic acid molecule formula for containing is CnH2n-2O4, wherein n is 10-18, and dicarboxylic acids is single dicarboxylic acids or mixed dicarboxylic acid.
3. method according to claim 1, it is characterised in that：Step II removes bacteria residue using centrifugation or membrane filtration.
4. method according to claim 1, it is characterised in that：Addition in step III in acetone and/or acetonitrile is the 5% ~ 40% of fermentation clear liquid volume, shakes 20 ~ 60min of incorporation time.
5. method according to claim 1, it is characterised in that：Picric acid is added in step III, addition is 2 ~ 5 wt% of the theoretical acid content of zymotic fluid.
6. method according to claim 5, it is characterised in that：At least one addition simultaneously in step III in picric acid and acetone, acetonitrile.
7. method according to claim 1, it is characterised in that：Described in step III be filtered into ultrafiltration or nanofiltration is separated.
8. method according to claim 1, it is characterised in that：The amount for continuing the acetone and/or acetonitrile solvent for adding described in step IV is the 60% ~ 150% of fermentation clear liquid volume.
9. method according to claim 1, it is characterised in that：The fermentation mother liquor containing solvent that step IV is obtained after filtering carries out the Distillation recovery of organic solvent in heating evaporation equipment.
10. method according to claim 1, it is characterised in that：The amount that dissolving binary acid sodium-salt described in step V adds water is the 50% ~ 100% of fermentation clear liquid volume.
11. methods according to claim 1, it is characterised in that：Step V acidifying pH value is 2.0 ~ 4.0, and temperature is 80 ~ 95 DEG C, atmospheric operation.
12. methods according to claim 10, it is characterised in that：Acidifying acid used is H2SO4、HNO3, HCl or H3PO4。
13. methods according to claim 1, it is characterised in that：Crystallisation by cooling temperature is 10 DEG C～30 DEG C in step V.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147016A (en) * | 1995-10-05 | 1997-04-09 | 中国石油化工总公司 | Method for treatment of alpha, omega dibasic acid fermentation liquor |
| CN1326463A (en) * | 1998-11-20 | 2001-12-12 | 雀巢制品公司 | Method for continuously isolating active proteins |
| CN1388242A (en) * | 2001-05-25 | 2003-01-01 | 广东省微生物研究所 | Method of separating and collecting bacterial cell from fermented liquid |
| CN1460671A (en) * | 2003-06-02 | 2003-12-10 | 大连理工大学 | Method for extracting and separating 1,3-propylene glycol from microbial fermented liquor |
-
2015
- 2015-11-09 CN CN201510751337.0A patent/CN106673995A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147016A (en) * | 1995-10-05 | 1997-04-09 | 中国石油化工总公司 | Method for treatment of alpha, omega dibasic acid fermentation liquor |
| CN1326463A (en) * | 1998-11-20 | 2001-12-12 | 雀巢制品公司 | Method for continuously isolating active proteins |
| CN1388242A (en) * | 2001-05-25 | 2003-01-01 | 广东省微生物研究所 | Method of separating and collecting bacterial cell from fermented liquid |
| CN1460671A (en) * | 2003-06-02 | 2003-12-10 | 大连理工大学 | Method for extracting and separating 1,3-propylene glycol from microbial fermented liquor |
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