CN112299985B - Method for refining long-chain dicarboxylic acid in fermentation liquor by using aqueous phase - Google Patents
Method for refining long-chain dicarboxylic acid in fermentation liquor by using aqueous phase Download PDFInfo
- Publication number
- CN112299985B CN112299985B CN201910702770.3A CN201910702770A CN112299985B CN 112299985 B CN112299985 B CN 112299985B CN 201910702770 A CN201910702770 A CN 201910702770A CN 112299985 B CN112299985 B CN 112299985B
- Authority
- CN
- China
- Prior art keywords
- dicarboxylic acid
- ether
- solvent
- acid
- long
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 81
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000855 fermentation Methods 0.000 title claims abstract description 45
- 230000004151 fermentation Effects 0.000 title claims abstract description 45
- 238000007670 refining Methods 0.000 title claims abstract description 31
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012071 phase Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000005520 cutting process Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 8
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 7
- 241001052560 Thallis Species 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 230000020477 pH reduction Effects 0.000 claims description 7
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001471 micro-filtration Methods 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000032798 delamination Effects 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000013557 residual solvent Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- POEDHWVTLBLWDA-UHFFFAOYSA-N 1-butylindole-2,3-dione Chemical compound C1=CC=C2N(CCCC)C(=O)C(=O)C2=C1 POEDHWVTLBLWDA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010977 unit operation Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a method for refining long-chain dicarboxylic acid in fermentation liquor in aqueous phase, which comprises the steps of pretreating long-chain dicarboxylic acid fermentation liquor, adding alkali to adjust pH to be not less than 8, and reacting for a certain time; adding a small amount of ether solvent, fully back mixing at 80-95 ℃, and standing for layering; cutting out the lower water phase, acidifying at 80-95 deg.c, cooling, filtering, washing and stoving to obtain the product. Compared with the prior art, the invention is based on the aqueous phase method, and obtains the polymer grade product with high purity and low total nitrogen corresponding to the solvent method on the premise of low cost, low loss, environmental protection, safety, simple flow and the like.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a method for refining long-chain dicarboxylic acid in fermentation liquor by using a water phase.
Background
The long-chain dicarboxylic acid refers to aliphatic dicarboxylic acid (DCn or DCA for short) containing more than 10 carbon atoms in a carbon chain, and the aliphatic dicarboxylic acid comprises saturated and unsaturated dicarboxylic acid, is a fine chemical product with important and wide industrial application, and is an important raw material for synthesizing high-grade perfume, high-performance nylon engineering plastics, high-grade nylon hot melt adhesives, high-temperature dielectrics, high-grade paints and coatings, high-grade lubricating oil, cold-resistant plasticizers, resins, medicines, pesticides and the like in the chemical industry.
The long-chain dicarboxylic acid is prepared by taking alkane as a substrate and adopting a microbial transformation mode, and the fermentation liquor has complex components and mainly comprises thalli, proteins, macromolecular pigments, inorganic salts and other intermediate metabolites besides the dicarboxylic acid. The long-chain dicarboxylic acid is extracted from the fermentation broth, and generally subjected to unit operations such as demulsification, acid precipitation, filtration and the like, so that the process flow is complex, and the separation cost of the long-chain dicarboxylic acid accounts for a large proportion of the production cost.
At present, the separation and refining process of long-chain dicarboxylic acid mainly comprises a solvent method and a water phase method. The solvent method has the advantages of high cost due to the fact that a large amount of organic solvents are used, considerable solvent loss is caused by evaporation in the process, and the solvents are needed to be treated and recycled. The enterprises mainly producing long-chain dicarboxylic acid in China mostly use an acetic acid solvent refining process, but because of the strong corrosiveness of acetic acid, the process equipment investment and the solvent recycling treatment section have higher energy consumption, the process flow is complex, and the solvent hazard is larger.
The aqueous phase method for separating and refining dicarboxylic acid is carried out in a medium using water as a solvent. The method generally comprises the following treatment means: and (3) carrying out microfiltration and ultrafiltration on the dicarboxylic acid fermentation liquor, decolorizing and removing impurities by using active carbon, activated clay and the like, adding inorganic acid to precipitate dicarboxylic acid, and filtering, washing and drying to obtain a dicarboxylic acid product. The existing technology for refining and purifying dicarboxylic acid by an aqueous phase method has poor removal capability of water-soluble protein/protein pigment remained in fermentation liquor, and the heating operation in the latter half of the process can promote the oxidative denaturation of pigment/protein, and can be adsorbed in dicarboxylic acid crystallization crystals along with temperature drop, so that the quality of a final product is reduced. The aqueous refining and purifying technology has simple and safe process, less investment and no pollution, but needs to further improve the refining process to obtain high-quality long-chain dicarboxylic acid products.
Patent CN102911036a discloses a process for obtaining high purity dicarboxylic acids comprising: i, heating and inactivating the fermentation stopping liquid; II, acidifying to crystallize and separate out the dicarboxylic acid, and filtering to obtain a dicarboxylic acid filter cake; III, mixing the dicarboxylic acid filter cake with an ether solvent to dissolve dicarboxylic acid, and separating an organic phase from a water phase, wherein the ether solvent is diethyl ether, propyl ether, butyl ether, amyl ether or hexyl ether; IV, adding an adsorbent into the organic phase obtained in the step III, and filtering to remove solids; and V, cooling the organic phase obtained in the step IV until the dicarboxylic acid is crystallized and separated out, filtering to obtain a dicarboxylic acid crystal filter cake, and drying the dicarboxylic acid crystal filter cake to obtain a dicarboxylic acid product with the dicarboxylic acid purity of more than 98.5% by weight. The method is a solvent recrystallization method, the solvent consumption in the refining process is large, the solvent volatilization/evaporation amount is considerable, and the corresponding recovery mode occupies a certain cost in industrial scale-up. The product refined by the method contains solvent taste because the solvent is entrapped in the crystallization process, and no effective cleaning means is found at present.
CN108947809a discloses a method for extracting and refining long-chain dicarboxylic acid from fermentation broth, comprising (1) pretreatment of fermentation broth: adding an alkaline pH regulator into the fermentation broth to control the pH of the system in an alkaline range, and heating to promote dissolution of the intracellular long-chain dicarboxylic acid; (2) collecting fermentation clear liquid: filtering to obtain fermentation clear liquid after the treatment of the step (1), and taking a water phase clear liquid layer after standing and layering; (3) extracting and refining long-chain dicarboxylic acid: controlling the temperature of the clear liquid of the water phase to be 70-85 ℃, adding an organic solvent according to a proportion, heating to 80-90 ℃, then adding an acidic pH regulator to control the pH of the system to be in an acidic range, heating to 90-100 ℃, standing and layering to separate the water phase after long-chain dicarboxylic acid in the system is completely dissolved, and filtering and drying the organic phase to obtain a long-chain dicarboxylic acid refined product. According to the method, a state of mixing a water phase and an organic phase is formed in a system through the addition of an organic solvent, and then the long-chain dicarboxylic acid is directly transferred into the organic phase from the water phase by utilizing the pH change and temperature control of the system, so that the extraction process is completed in one reactor, the refining of the long-chain dicarboxylic acid can be realized by only one process unit, the refining process of the long-chain dicarboxylic acid from the liquid phase to the solid phase and from the solid crude acid to the organic extraction phase in the traditional process is simplified, the crude acid extraction process in the traditional process is reduced, the loss in the extraction process is reduced, and the operation steps and the yield are reduced. However, the dicarboxylic acid is finally extracted in the organic phase, the amount of organic solvent is relatively large, and a part of the dicarboxylic acid is lost with evaporation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for refining long-chain dicarboxylic acid in fermentation liquor by using a water phase. Compared with the prior art, the invention is based on the aqueous phase method, and obtains the polymer grade product with high purity and low total nitrogen corresponding to the solvent method on the premise of low cost, low loss, environmental protection, safety, simple flow and the like.
The method for refining long-chain dicarboxylic acid in fermentation liquor in aqueous phase comprises the following steps:
(1) Pretreating long-chain dicarboxylic acid fermentation liquor to remove thalli and partial pigment;
(2) Adding alkali to regulate pH to not less than 8 and reacting for certain time;
(3) Adding a small amount of ether solvent, fully back mixing at 80-95 ℃, and standing for layering;
(4) Cutting out the lower water phase, acidifying at 80-95 deg.c, cooling, filtering, washing filter cake and stoving to obtain the product.
The long-chain dicarboxylic acid fermentation broth in the step (1) is fermentation broth obtained by fermenting microorganisms with alkane and the like to prepare long-chain dicarboxylic acid, wherein the long-chain dicarboxylic acid has a molecular formula of C n H 2n-2 O 4 Wherein n is 10 to 18.
The pretreatment of the fermentation broth in the step (1) adopts a method for removing thalli and pigment conventionally used in the field, for example, a method such as heating, filtering, decoloring and the like can be adopted, and specifically, the following steps can be adopted: heating the long-chain dicarboxylic acid fermentation liquor to 70-80 ℃, carrying out microfiltration, ultrafiltration and the like, and then carrying out active carbon decolorization and filtration to remove thalli and partial pigment.
And (3) adding alkali in the step (2) to adjust the pH value to be not less than 8, preferably 9-11. The alkali can be at least one of potassium hydroxide, sodium hydroxide and the like, and for equipment and field operation, alkali liquor with a certain concentration is preferably used, and the mass concentration of the alkali liquor is 30-40%.
And (3) adding alkali to adjust the pH value in the step (2), and reacting for 10-60 min.
The ether solvent in the step (3) may be at least one of diethyl ether, propyl ether, butyl ether, pentyl ether, hexyl ether, heptyl ether, etc., preferably at least one of butyl ether, pentyl ether, hexyl ether, etc.
The added volume of the ether solvent is 2-5% of the volume of the fermentation liquor.
And (3) adding an ether solvent, then carrying out back mixing at 80-95 ℃ for at least 45min, and standing for layering. The standing delamination does not need to preserve heat, and the standing time is 60-90 min.
The acid used for the acidification in the step (4) is any one or more of inorganic acids, such as at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and the like, and sulfuric acid is preferred. The pH value of acidification is 2-4, the acidification temperature is 80-95 ℃, and the acidification time is 1.5-2.5 h.
Cooling to not higher than 40 ℃ in the step (4), and filtering; the filtration adopts a conventional filtration form such as plate-and-frame filtration.
The washing liquid in the step (4) is desalted water, and the washing is stopped when the pH of the filtrate is above 5.5, preferably 5.5-6.5. The drying temperature is 95-100 ℃, the drying time is 1.5-2 h, and the drying can be performed by adopting a conventional method, such as hot air type drying.
Further, the residual water phase and solvent phase are naturally cooled and then are conveyed to a storage tank for storage, and after a plurality of batches are accumulated, for example, 4-6 batches can be treated and recycled uniformly. The specific method comprises the following steps: heating the mixed solution to 85-90 ℃, standing for 30-60 min, cutting off a lower water phase, naturally cooling the remaining solvent phase after the water phase is treated in the step (4), and centrifuging at a low temperature of-15-5 ℃, wherein a high-speed centrifuge is usually selected, the centrifugal speed is not less than 9500rpm, and the centrifugal duration is not more than 10min, so as to ensure the separation effect. The components of the centrifugal clear liquid can be directly returned to a solvent storage tank for continuous use, and the residual liquid is treated by waste liquid and waste solid.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adds alkali into the pretreated fermentation liquor, so that the pH of the fermentation liquor is higher than 8, and the temperature is raised, under the condition, partial water-soluble protein is promoted to be denatured, and the fermentation liquor is easy to dissolve in a small amount of ether solvent, so that pigment and impurities enter an organic phase, and then are separated from water phase in which the product is dissolved by cutting water, thereby realizing the efficient removal of the pigment and the impurities. The dicarboxylic acid salt is extracted in the water phase, and the crystallization environment is cleaner, so that the long-chain dicarboxylic acid with higher purity and meeting the requirements of polymer-grade products is easy to obtain.
(2) Compared with the traditional solvent recrystallization method, the method changes the traditional concept of solvent extraction of the target product, uses the solvent to directly extract impurities in the fermentation broth, omits the process of preparing the crude product by the fermentation broth, shortens the flow, and greatly reduces the solvent consumption and the process loss. The product is crystallized in the water phase, the solvent entrapped in the crystallization process is water, salt or inorganic acid aqueous solution, and the solvent can be removed by a simple washing method, such as pulping and leaching, so that the risks of entrapping organic solvent and impurities dissolved in the organic solvent are avoided, the polymerization grade product is obtained, and the technical problem that the high-quality long-chain dicarboxylic acid cannot be refined by the current water phase method is solved.
(3) The invention adopts the ether solvent as the impurity carrier, has good thermal stability and chemical stability, and has little dosage, no need of pressurizing operation in the reaction process and little solvent loss. And the solvent and the long-chain dicarboxylic acid do not have side reaction, and the product can be directly applied to downstream polymerization reaction. The solvent has short use flow, less single-pass loss, simple operation and small potential safety hazard.
Detailed Description
The method and effect of the long-chain dicarboxylic acid in the aqueous-phase refined fermentation broth of the present invention will be further described below with reference to examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments. In the invention, wt% is mass fraction and vt% is volume fraction.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below were purchased from biochemical reagent stores unless otherwise specified.
In the invention, the total acid content is measured and calculated by an acid-base titration method, the monoacid content is measured and calculated by a gas chromatography peak area normalization method, and the total nitrogen content is detected by a boat sample injection chemiluminescence method.
Example 1
(1) 2000mL of 160g/L C was taken 12 H 22 O 4 Pretreatment of fermentation liquor: heating the fermentation liquor to 75 ℃ for inactivation, then carrying out microfiltration and ultrafiltration membrane filtration, and then decolorizing and filtering by activated carbon.
(2) And (3) adding a NaOH solution with the mass concentration of 32% into the fermentation broth obtained in the step (1) until the pH value reaches 9.5, and stopping reacting for 30min.
(3) 100mL of n-amyl ether was added, the reaction was stopped after stirring at 91.5℃for 45min, and left to stand for 60min, and the lower aqueous phase was cut out.
(4) After the cut aqueous phase was collected, 95% sulfuric acid was slowly added and stirring was turned on, and the addition was stopped when the pH was lowered to 2.8, and the mixture was acidified at 85℃for 2 hours. Naturally cooling to 40 ℃, carrying out plate-frame filtration, then using desalted water to wash the filter cake, stopping washing when the pH value of the washing liquid is raised to 6.0, discharging the filter cake after purging, and conveying the filter cake into a hot air dryer for drying at 100 ℃ for 1.5h to obtain the product. The results are shown in Table 1.
Example 2
(1) 2000mL of C with 150g/L concentration is taken 10 H 18 O 4 Fermentation broth, pretreatment: heating the fermentation liquor to 70 ℃ for inactivation, then carrying out microfiltration and ultrafiltration membrane filtration, and then decolorizing and filtering by activated carbon to remove thalli and pigment.
(2) And (3) adding the fermentation liquor obtained in the step (1) into a NaOH solution with the mass concentration of 30% until the pH value reaches 8.1, and stopping reacting for 20min.
(3) 100mL of n-amyl ether was added, the reaction was stopped after stirring at 85℃for 60min, and left to stand for 45min, and the lower aqueous phase was cut out.
(4) After the cut aqueous phase was collected, 95% sulfuric acid was slowly added and stirring was turned on, and the addition was stopped when the pH was lowered to 2.6, and the mixture was acidified at 90℃for 2 hours. Naturally cooling to 35 ℃, conveying to a plate-frame filter, then using desalted water to wash a filter cake, stopping washing when the pH value of the washing liquid is raised to 5.5, discharging the filter cake after purging, conveying to a hot air dryer for drying, wherein the drying temperature is 95 ℃, and the drying time is 2 hours, thus obtaining the product. The results are shown in Table 1.
Example 3
(1) 2000mL of C with the concentration of 140g/L is taken 16 H 30 O 4 Fermentation broth, pretreatment: heating the fermentation liquor to 80 ℃ for inactivation, then carrying out microfiltration and ultrafiltration membrane filtration, and then decolorizing and filtering by activated carbon.
(2) And (3) adding the fermentation liquor obtained in the step (1) into a NaOH solution with the mass concentration of 40% until the pH value reaches 11, and reacting for 10min.
(3) 100mL of n-amyl ether is added, the reaction is stopped after stirring at 93 ℃ for 30min, the reaction is kept stand for 75min, and the lower water phase is cut out and then is conveyed to an acidifier in a heat preservation way.
(4) After the cut aqueous phase was collected, 95% sulfuric acid was slowly added and stirring was started, and the addition was stopped when the pH was lowered to 3.0, and the mixture was acidified at 90℃for 1.5 hours. Naturally cooling to 30 ℃, conveying to a plate-frame filter, then using desalted water to wash a filter cake, stopping washing when the pH value of the washing liquid is raised to 6.5, discharging the filter cake after purging, conveying to a hot air dryer for drying, wherein the drying temperature is 100 ℃, and the drying time is 1.5h, thus obtaining the product. The results are shown in Table 1.
Example 4
The refining process and operating conditions were the same as in example 1, except that: and (2) replacing sodium hydroxide with potassium hydroxide with the mass concentration of 32%, and adjusting the pH to 9.5.
Example 5
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting a mixed solvent of n-butyl ether and n-heptyl ether (volume ratio is 1:1) to replace n-amyl ether.
Example 6
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting diethyl ether to replace n-amyl ether.
Example 7
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting n-propyl ether to replace n-amyl ether.
Example 8
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting n-butyl ether to replace n-amyl ether.
Example 9
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting n-hexyl ether to replace n-amyl ether.
Example 10
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting n-heptyl ether to replace n-amyl ether.
Example 11
The refining process and operating conditions were the same as in example 1, except that: and (4) acidifying, namely replacing sulfuric acid with nitric acid.
Example 12
The refining process and operating conditions were the same as in example 1, except that: and (4) acidizing by adopting hydrochloric acid to replace sulfuric acid.
Comparative example 1
The refining process and operating conditions were the same as in example 1, except that: and (3) regulating the pH value to 7.8 in the step (2).
Comparative example 2
The refining process and operating conditions were the same as in example 1, except that: the reaction temperature in the step (3) is 75 ℃.
Comparative example 3
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting n-butanol to replace n-amyl ether.
Comparative example 4
The refining process and operating conditions were the same as in example 1, except that: and (3) adopting ethyl acetate to replace n-amyl ether.
The residual water phase and solvent phase in each example and comparative example are naturally cooled and then are conveyed to a storage tank for storage, 6 batches are accumulated, and the treatment and the recycling are carried out uniformly. The specific method comprises the following steps: heating the mixed solution to 85 ℃, standing for 45min, cutting off a lower water phase, naturally cooling the rest solvent phase after the water phase is treated in the step (4), and centrifuging at a low temperature of 0 ℃ usually at a high-speed centrifuge with a centrifugal speed of 12000rpm for 10min to ensure the separation effect.
Table 1 effects of the products of examples and comparative examples
As can be seen from Table 1, the total nitrogen content in the product obtained by the technical scheme of the present application is significantly reduced, while the total nitrogen content of comparative examples 1-4 lacking the technical features of the present application is relatively high.
Claims (16)
1. A method for refining long-chain dicarboxylic acid in fermentation liquor in an aqueous phase, which is characterized by comprising the following steps:
(1) Pretreating long-chain dicarboxylic acid fermentation liquor to remove thalli and partial pigment;
(2) Adding alkali to regulate pH to not less than 8 and reacting for certain time;
(3) Adding a small amount of ether solvent, fully back mixing at 80-95 ℃, and standing for layering; the ether solvent is at least one of propyl ether, butyl ether, amyl ether, hexyl ether or heptyl ether, and the adding amount is added according to the volume ratio of the solvent to the volume ratio of the fermentation liquor of 2% -5%;
(4) Cutting out the lower water phase, acidifying at 80-95 deg.c, cooling, filtering, washing filter cake and stoving to obtain the product.
2. The method according to claim 1, characterized in that: the long-chain dicarboxylic acid fermentation broth in the step (1) is fermentation broth prepared by fermenting microorganisms by utilizing alkane, wherein the molecular general formula of the contained long-chain dicarboxylic acid is C n H 2n-2 O 4 Wherein n is 10 to 18.
3. The method according to claim 1 or 2, characterized in that: the pretreatment method of the fermentation liquor in the step (1) comprises the following steps: heating the long-chain dicarboxylic acid fermentation liquor to 70-80 ℃, carrying out microfiltration and ultrafiltration, and then decolorizing and filtering by using activated carbon to remove thalli and partial pigment.
4. The method according to claim 1, characterized in that: and (3) adding alkali in the step (2) to adjust the pH value to 9-11.
5. The method according to claim 1 or 4, characterized in that: the alkali in the step (2) is at least one of potassium hydroxide and sodium hydroxide.
6. The method according to claim 1 or 4, characterized in that: and (3) adding alkali to adjust the pH value in the step (2), and reacting for 10-60 min.
7. The method according to claim 1, characterized in that: the ether solvent in the step (3) is at least one of butyl ether, amyl ether and hexyl ether.
8. The method according to claim 1, characterized in that: step (3) adding an ether solvent, and then carrying out back mixing at 80-95 ℃ for not less than 45min; the standing delamination does not need to preserve heat, and the standing time is 60-90 min.
9. The method according to claim 1, characterized in that: the acid added in the step (4) is any one or more of inorganic acid.
10. The method according to claim 9, wherein: the acid added in the step (4) is at least one of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.
11. The method according to claim 10, wherein: the acid added in the step (4) is sulfuric acid.
12. The method according to claim 1, characterized in that: in the step (4), the pH value of acidification is 2-4, the acidification temperature is 80-95 ℃, and the acidification time is 1.5-2.5 h.
13. The method according to claim 1, characterized in that: cooling to not higher than 40 ℃ in the step (4), and filtering; the filtration adopts plate frame filtration.
14. The method according to claim 1, characterized in that: the cleaning solution in the step (4) is desalted water, and the cleaning is stopped when the pH value of the filtrate is more than 5.5.
15. The method according to claim 1, characterized in that: and (4) drying at 95-100 ℃ for 1.5-2 h by hot air.
16. The method according to claim 1, characterized in that: and (3) naturally cooling the residual water phase and the solvent phase, then conveying the residual water phase and the solvent phase to a storage tank for storage, heating the mixed solution after multiple batches of accumulation to 85-90 ℃, standing for 30-60 min, cutting off the lower water phase, naturally cooling the residual solvent phase after the water phase is treated in the step (4), centrifuging at the low temperature of-15-5 ℃, and directly returning the centrifuged clear liquid component to the solvent storage tank for continuous use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910702770.3A CN112299985B (en) | 2019-07-31 | 2019-07-31 | Method for refining long-chain dicarboxylic acid in fermentation liquor by using aqueous phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910702770.3A CN112299985B (en) | 2019-07-31 | 2019-07-31 | Method for refining long-chain dicarboxylic acid in fermentation liquor by using aqueous phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112299985A CN112299985A (en) | 2021-02-02 |
| CN112299985B true CN112299985B (en) | 2023-05-30 |
Family
ID=74485324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910702770.3A Active CN112299985B (en) | 2019-07-31 | 2019-07-31 | Method for refining long-chain dicarboxylic acid in fermentation liquor by using aqueous phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112299985B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1255483A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for refining long-chain biatomic acid |
| CN103772186A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Refining method of fermented organic acid |
| CN103804173A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Fermentation organic acid refining method |
| CN108947809A (en) * | 2017-05-18 | 2018-12-07 | 中国石油化工股份有限公司 | A method of extracting simultaneously refining long-chain dicarboxylic acids from fermentation liquid |
| CN109485558A (en) * | 2017-09-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of method of purification of long-chain biatomic acid |
-
2019
- 2019-07-31 CN CN201910702770.3A patent/CN112299985B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1255483A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for refining long-chain biatomic acid |
| CN103772186A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Refining method of fermented organic acid |
| CN103804173A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Fermentation organic acid refining method |
| CN108947809A (en) * | 2017-05-18 | 2018-12-07 | 中国石油化工股份有限公司 | A method of extracting simultaneously refining long-chain dicarboxylic acids from fermentation liquid |
| CN109485558A (en) * | 2017-09-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of method of purification of long-chain biatomic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112299985A (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108017535B (en) | Method for extracting long-chain dicarboxylic acid from fermentation liquor | |
| CN102976923B (en) | New process for extracting lactic acid from lactic acid fermentation liquid | |
| CN104591994B (en) | A kind of method of refining long-chain biatomic acid | |
| CN104591998A (en) | Purification method for long-chain dicarboxylic acid | |
| CN109516913B (en) | Aqueous phase melting crystallization process of long-chain dicarboxylic acid | |
| CN102911036A (en) | Method for obtaining high pure dicarboxylic acid | |
| CN108947809B (en) | Method for extracting and refining long-chain dicarboxylic acid from fermentation liquor | |
| CN111349006B (en) | Method for refining long-chain dicarboxylic acid | |
| CN103804173B (en) | A kind of process for purification of fermentation organic acid | |
| CN1221510C (en) | Refining method for long-chain biatomic acid | |
| CN103804174B (en) | A kind of organic acid process for purification | |
| CA3119841A1 (en) | Purification of magnesium lactate from fermentation broths having high amounts of impurities | |
| CN112299985B (en) | Method for refining long-chain dicarboxylic acid in fermentation liquor by using aqueous phase | |
| CN104592004B (en) | A kind of method of refining long-chain organic acid | |
| CN103772186A (en) | Refining method of fermented organic acid | |
| CN109485558B (en) | Purification method of long-chain dibasic acid | |
| CN106554273B (en) | Method for purifying long-chain dicarboxylic acid in fermentation liquor | |
| CN110683947B (en) | Long-chain dibasic acid with low content of hydroxy acid impurities and method for reducing content of hydroxy acid impurities | |
| CN112794799B (en) | Method for reducing solvent evaporation amount in binary acid refining process | |
| CN112724012B (en) | Method for refining long-chain dibasic acid | |
| CN109809982B (en) | Long-chain dicarboxylic acid industrialized refining system and refining process | |
| CN114478235B (en) | Method for purifying organic acid in fermentation liquor | |
| CN1216026C (en) | Refining method for decanedioic acid | |
| CN114685269B (en) | Purification method of long-chain dibasic acid and long-chain dibasic acid product | |
| CN114524722A (en) | Method for extracting long-chain dicarboxylic acid |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231123 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |