CN114181073A - Long-chain dibasic acid oxidation decoloring process - Google Patents
Long-chain dibasic acid oxidation decoloring process Download PDFInfo
- Publication number
- CN114181073A CN114181073A CN202111437184.4A CN202111437184A CN114181073A CN 114181073 A CN114181073 A CN 114181073A CN 202111437184 A CN202111437184 A CN 202111437184A CN 114181073 A CN114181073 A CN 114181073A
- Authority
- CN
- China
- Prior art keywords
- long
- acid
- oxidation
- chain
- dibasic acid
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000003647 oxidation Effects 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 45
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 238000004042 decolorization Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 claims description 4
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 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
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 4
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 abstract description 46
- 230000004151 fermentation Effects 0.000 abstract description 46
- 239000012535 impurity Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 150000007513 acids Chemical class 0.000 abstract description 4
- 239000000049 pigment Substances 0.000 abstract description 4
- 230000004060 metabolic process Effects 0.000 abstract description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000005374 membrane filtration Methods 0.000 description 8
- 230000001954 sterilising effect Effects 0.000 description 8
- 238000004659 sterilization and disinfection Methods 0.000 description 8
- 238000002203 pretreatment Methods 0.000 description 7
- 238000010170 biological method Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 102100028175 Abasic site processing protein HMCES Human genes 0.000 description 2
- 102100022210 COX assembly mitochondrial protein 2 homolog Human genes 0.000 description 2
- 101001006387 Homo sapiens Abasic site processing protein HMCES Proteins 0.000 description 2
- 101000900446 Homo sapiens COX assembly mitochondrial protein 2 homolog Proteins 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000008452 baby food Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013350 formula milk Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001953 recrystallisation Methods 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
- 239000010865 sewage Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil 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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention provides an oxidation decoloration process under strong alkaline conditions, aiming at impurities such as pigments, unsaturated acids and the like generated by metabolism of long-chain dibasic acids prepared by a biological fermentation method, and better decoloration effect can be obtained by oxidation under strong alkaline conditions.
Description
Technical Field
The invention relates to a refining method of long-chain dibasic acid prepared by a biological fermentation method, in particular to an oxidation decoloration process of long-chain dibasic acid.
Background
Long chain dicarboxylic acids (Long chain dicarboxylic acids) refer to aliphatic dicarboxylic acids (DCn for short) with more than 10 carbon atoms in the carbon chain, including saturated and unsaturated dicarboxylic acids, are a class of fine chemical products with important and wide industrial application, and are important basic raw materials for synthesizing high-grade spices, 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. Due to the wide development potential of downstream products of the long-chain dibasic acid, the demand of the long-chain dibasic acid is continuously increased at home and abroad, and the market potential is extremely high.
The production of long-chain dicarboxylic acid by biological method (fermentation method) is the application of microbial technology in petrochemical industry, which has emerged in the last 70 th century. The method is characterized in that abundant petroleum resources are used as raw materials, two methyl groups at two ends of long-chain n-alkane are respectively oxidized under normal temperature and normal pressure by utilizing the specific oxidizing capacity of microorganisms and the action of intracellular enzymes of the microorganisms, and four oxygen atoms are added in one step to generate various long-chain dibasic acids with corresponding chain lengths; the biological method for producing the long-chain dibasic acid overcomes various defects of a simple chemical synthesis method and a vegetable oil cracking preparation method, and opens up a new way for the mass production of the long-chain dibasic acid. Compared with chemical synthesis methods, biological methods for producing long carbon chain dibasic acids have undoubted advantages and are generally regarded at home and abroad. The biological method can not only provide the series of long carbon chain dibasic acid monomers from C9 to C18, even C22, but also can produce long chain dibasic acid (such as long chain dibasic acid with the length of more than C13) which can not be produced by the chemical synthesis method, thereby greatly expanding the application of the dibasic acid in the industrial field.
The biological method for preparing the long-chain dicarboxylic acid has mild conditions and simple and convenient process. However, the fermentation broth is a mixture containing dibasic acid, residual alkane, emulsion, cells, medium and various metabolites. Some pigments and nitrogen compounds remained in the purification are extracted, and the late polymerization is influenced. In industrial production, the extraction of the long-chain dicarboxylic acid mainly uses solvent treatment and water treatment. The decolorization process is mainly carried out in water and solvent.
In patent CN1351006A (published Japanese 2002-05-29), the contents of impurities such as protein and organic pigment in the product are reduced by using a primary acidification and primary melting decolorization process. The adsorbent used is activated carbon, activated clay, etc. The method needs to melt the crude product of the dibasic acid, is easy to generate Maillard reaction at high temperature, enables the reductive group to react, influences the product, has low product yield and high melting energy consumption, and is not suitable for industrial production.
Patent CN102010318A (published japanese 2011-04-13) uses two or more decolorization and then acidification methods in the water phase to remove some pigments and improve the purity of the mixed dibasic acid. The disadvantages are that: the process needs two or more times of activated carbon decolorization, which causes great loss of the dibasic acid, low yield and high cost.
The oxidation process is a common long-chain dibasic acid decoloring process in the prior art, and a long-chain dibasic acid water phase two-stage purification method is provided in patent CN103497100A (published as 2014-01-08), wherein an oxidant is added after heating at the pH of 5-9, the dicarboxylic acid carboxyl is shielded from reacting with reductive impurities, the heating temperature is controlled at 80-100 ℃, the oxidant is sodium hypochlorite or ozone, and the long-chain dibasic acid is obtained by acidification after oxidation.
Patent CN104844441A (published japanese 2015-08-19) provides a method for extracting a long-chain mixed dibasic acid (also referred to as a mixed dibasic acid for short) which is a waste in the production of long-chain dibasic acid. The method comprises the steps of firstly adjusting the pH value to be between 5.6 and 7.2 by adding alkali, cooling and precipitating after dissolving to obtain an intermediate, then adding an oxidant for oxidation after dissolving, wherein the oxidant is ozone and/or hydrogen peroxide. Finally, the long-chain dicarboxylic acid is obtained by acidification. The invention combines the secondary precipitation and the oxidation process in the water phase to obtain the high-quality mixed dibasic acid finished product which has white color, good quality and low content of high-carbon number dibasic acid (dibasic acid with more than C16).
In the prior art, the oxidation of the dibasic acid is carried out in an acidic or weakly alkaline range, and the pH value is concentrated in a range of 5-9. Under acidic and weakly alkaline conditions, some impurities are not completely dissolved, and are in a molecular state rather than a salt state, and oxidation is insufficient, so that the decoloring effect is not good.
Disclosure of Invention
The invention provides an oxidation decoloring process under a strong alkaline condition aiming at the defects of a decoloring process of long-chain dibasic acid in the prior art. The inventor finds that better decolorization effect can be obtained by oxidizing impurities such as pigment, unsaturated acid and the like generated by metabolism of long-chain dibasic acid prepared by a biological fermentation method under strong alkaline conditions.
Specifically, the oxidation decoloring process of the long-chain dibasic acid comprises the following steps:
diluting the material containing long-chain dibasic acid with water, adding alkali to adjust the pH value, adding an oxidant to oxidize, and filtering insoluble substances to obtain an oxidized clear solution.
The long-chain dibasic acid is one or a mixture of more of azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid or 9-ene-octadecanedioic acid. The material containing the long-chain dibasic acid can be obtained by carrying out certain treatment, such as centrifugation, membrane filtration sterilization and the like, on long-chain dibasic acid fermentation liquor prepared by a biological method to obtain filtrate.
The long-chain dibasic acid fermentation liquor is a multiphase mixture obtained after the production of long-chain dibasic acid by microbial fermentation is finished, contains water, fermentation substrate residues, long-chain dibasic acid salts, thalli and other impurities, and can also be a multiphase mixture (namely the treatment liquor of the fermentation liquor) obtained by treating the fermentation liquor after the fermentation of the long-chain dibasic acid is finished and removing one or more other components except the long-chain dibasic acid salts in the fermentation liquor or reducing the content of the components.
The material containing the long-chain dicarboxylic acid can also be from waste liquid which is discharged in the fermentation and refining processes and is rich in the long-chain dicarboxylic acid, such as a long-chain dicarboxylic acid mixture which is obtained in the extraction process of a long-chain dicarboxylic acid product and is obtained by drying a recrystallization mother liquor of the long-chain dicarboxylic acid, and long-chain dicarboxylic acid precipitates (called heavy components for short) which are obtained by long-term precipitation and accumulation in a long-chain dicarboxylic acid sewage treatment workshop.
In the invention, the pH value is adjusted by adding alkali to 9.2-12.5, preferably 10-12.
In the invention, the mass concentration of the long-chain dicarboxylic acid in the material containing the long-chain dicarboxylic acid is adjusted to 3-15%, preferably 3-10%, and more preferably 4-8% after water is added.
The oxidation process can be controlled by continuously adjusting pH, and the oxidation process maintains pH at 9.2-12.5, preferably 10-12.
The oxidation temperature in the oxidation process of the present invention is 10-95 deg.C, preferably 20-80 deg.C. The oxidation time is 0.5 to 6 hours, preferably 0.5 to 3 hours, and more preferably 0.5 to 2 hours.
The oxidant is one or more of potassium permanganate, ozone, hydrogen peroxide or sodium hypochlorite.
The addition amount of the oxidant is 0.02-8% of the mass of the long-chain dicarboxylic acid, preferably 0.05-5%, and more preferably 0.1-4%.
In the invention, a small amount of active carbon can be added during oxidation, so that an oxidation adsorption center is increased. The adding amount of the active carbon needs to be adjusted according to the quality requirement of the product, and is generally 0.05-3 percent of the mass of the long-chain dicarboxylic acid, and preferably 0.1-1 percent.
In the invention, insoluble substances can be filtered by adding any one or more of active carbon, diatomite and activated clay after oxidation, and the addition amount of any one or more of active carbon, diatomite and activated clay is 0.5-10% of the weight of the long-chain dibasic acid, preferably 1-5%.
The oxidizing clear liquid obtained in the invention is acidified and precipitated to obtain the long-chain dicarboxylic acid finished product.
The invention has the advantages of simple operation; the dibasic acid and the impurities are dissolved in the solvent, and the oxidation effect under the alkaline condition is good, thereby having unexpected effect. Under the condition of strong alkalinity, all components are in a state of completely dissolved salts, can be fully oxidized, and after oxidation, some acidic components are generated and continuously react with alkali to form salts, so that the condition that the pH value is reduced too much to influence the unoxidized part is avoided.
Detailed Description
1. And (3) detecting by using a binary acid gas chromatography:
reference is made to the determination of fatty acids in infant food and milk of GB5413.27-2010, using standard diacid samples as controls.
2. And (3) light transmittance measurement:
the dibasic acid sample was dissolved in an aqueous solution of sodium salt at a concentration of 5% by weight, and then the light transmittance at 430nm was measured by UV.
Comparative example 1
Sodium hypochlorite oxidation at pH 7 of DC12
A dodecanedioic acid fermentation liquid is obtained according to a fermentation method of example 4 of patent document CN1570124A, and a filtrate is obtained after a membrane filtration sterilization method is adopted according to a fermentation liquid pretreatment method. Adjusting the concentration of the fermentation liquor to 6.3 percent and the pH value to 7.0, taking 1000g of filtrate, adding 2.5g of 13 percent sodium hypochlorite solution into the fermentation liquor at 60 ℃, and oxidizing for 1h under stirring. Acidifying, precipitating, filtering and drying to obtain the dodecanedioic acid.
Comparative example 2
Heavy component pH 7 ozone oxidation
According to the fermentation method of the embodiment 4 of the patent document CN1570124A, the fermentation liquid of the dodecanedioic acid is obtained, according to the pretreatment method of the fermentation liquid, firstly, the membrane filtration sterilization method is adopted to obtain filtrate, then, 3% of activated carbon is added for decolorization, and the acidified precipitate is filtered and dried to obtain the acidified crude product of the dodecanedioic acid. And refined with solvent as in example 30. And evaporating the mother liquor obtained after crystal separation in the refining process to obtain a heavy component rich in long-chain dicarboxylic acid. Diluting the heavy component with water, adding caustic soda flakes to fully dissolve, adding water to adjust the concentration to 5%, and adjusting the pH to 7. Ozone is introduced into the fermentation liquor for 2 hours at 40 ℃ by adopting an ozone generator. Adding diatomite with the mass of 0.5 percent of the weight of the heavy component, filtering, acidifying, precipitating, filtering and drying to obtain a heavy component oxidation product.
Comparative example 3
Oxidation of DC13 with pH 9 potassium permanganate
A tridecanoic acid fermentation broth is obtained according to the fermentation method of example 5 of patent document CN1570124A, and a filtrate is obtained after membrane filtration sterilization according to the pretreatment method of the fermentation broth. Adjusting the concentration of the fermentation liquor to 6.1 percent, adjusting the pH value to 9, taking 1000g of filtrate, adding 1.2g of potassium permanganate into the fermentation liquor at 60 ℃, and oxidizing for 1h under stirring. Adding diatomite with the weight of 0.5 percent of that of the dibasic acid, filtering, acidifying the precipitate, filtering and drying to obtain the tridecanedioic acid.
Example 1
Sodium hypochlorite oxidation at pH 11 of DC12
A dodecanedioic acid fermentation liquid is obtained according to a fermentation method of example 4 of patent document CN1570124A, and a filtrate is obtained after a membrane filtration sterilization method is adopted according to a fermentation liquid pretreatment method. Adjusting the concentration of the fermentation liquor to 6.3 percent, adjusting the pH value to 11.0, taking 1000g of filtrate, adding 2.5g of 13 percent sodium hypochlorite solution into the fermentation liquor at 60 ℃, and oxidizing for 1h under stirring. Acidifying, precipitating, filtering and drying to obtain the dodecanedioic acid.
Example 2
Heavy ends pH 12 ozone oxidation
According to the fermentation method of the embodiment 4 of the patent document CN1570124A, the fermentation liquid of the dodecanedioic acid is obtained, according to the pretreatment method of the fermentation liquid, firstly, the membrane filtration sterilization method is adopted to obtain filtrate, then, 3% of activated carbon is added for decolorization, and the acidified precipitate is filtered and dried to obtain the acidified crude product of the dodecanedioic acid. And refined with solvent as in example 30. And evaporating the mother liquor obtained after crystal separation in the refining process to obtain a heavy component rich in long-chain dicarboxylic acid. Adding water to the heavy component to adjust the concentration to 5%, adding caustic soda flakes to fully dissolve, and adjusting the pH to 12. Introducing ozone into the fermentation liquor for 2h at 40 ℃ by adopting an ozone generator, adding diatomite with the mass of 0.5 percent of the weight of the heavy component, filtering, acidifying, precipitating, filtering and drying to obtain a heavy component oxidation product.
Example 3
Heavy component pH 10 ozone oxidation
According to the fermentation method of the embodiment 4 of the patent document CN1570124A, the fermentation liquid of the dodecanedioic acid is obtained, according to the pretreatment method of the fermentation liquid, firstly, the membrane filtration sterilization method is adopted to obtain filtrate, then, 3% of activated carbon is added for decolorization, and the acidified precipitate is filtered and dried to obtain the acidified crude product of the dodecanedioic acid. And refined with solvent as in example 30. And evaporating the mother liquor obtained after crystal separation in the refining process to obtain a heavy component rich in long-chain dicarboxylic acid. Adding water to the heavy component to adjust the concentration to 7%, adding caustic soda flakes to fully dissolve, and adjusting the pH to 10. Introducing ozone into the fermentation liquor for 2h at 60 ℃ by adopting an ozone generator, adding activated clay with the mass of 4% of the heavy component, filtering, acidifying, precipitating, filtering and drying to obtain a heavy component oxidation product.
Example 4
Oxidation of DC13 with pH 11 potassium permanganate
A dodecanedioic acid fermentation liquid is obtained according to a fermentation method of example 5 of patent document CN1570124A, and a filtrate is obtained after a membrane filtration sterilization method is adopted according to a fermentation liquid pretreatment method. Adjusting the concentration of the fermentation liquor to 6.1 percent, adjusting the pH value to 11.0, taking 1000g of filtrate, adding 1.2g of potassium permanganate into the fermentation liquor at 60 ℃, and oxidizing for 1h under stirring. Adding diatomite with the weight of 0.5 percent of that of the dibasic acid, filtering, acidifying the precipitate, filtering and drying to obtain the tridecanedioic acid.
TABLE 1 comparison of the quality of the products of different processes
Sample (I) | Purity in gas phase | Light transmittance |
Comparative example 1 | 98.67% | 98.14% |
Comparative example 2 | 62.47% (note: total content of DC11-DC14 dibasic acid) | 83.96% |
Comparative example 3 | 97.30% | 95.22% |
Example 1 | 98.77% | 99.01% |
Example 2 | 70.11% (note: total content of DC11-DC14 dibasic acid) | 95.23% |
Example 3 | 66.43% (note: total content of DC11-DC14 dibasic acid) | 90.31% |
Example 4 | 98.12% | 98.04% |
In table 1, comparing example 1 with comparative example 1, comparing examples 2 and 3 with comparative example 2, and comparing example 4 with comparative example 3, it can be seen that oxidation under strongly alkaline condition can significantly improve the light transmittance of the obtained product and improve the decoloring effect. Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (7)
1. The oxidation decoloration process of the long-chain dibasic acid is characterized by comprising the following steps: diluting the material containing the long-chain dibasic acid with water, adjusting the mass concentration of the long-chain dibasic acid to be 3% -15% after diluting with water, adjusting the pH value by adding alkali, adding an oxidant, oxidizing, and filtering insoluble substances to obtain an oxidized clear liquid, wherein the pH value is 10-12.
2. The process for oxidative decolorization of long chain dibasic acid according to claim 1, wherein the long chain dibasic acid is one or more of azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid or 9-ene-octadecanedioic acid.
3. The oxidation decoloring process of the long-chain dicarboxylic acid according to claim 1, wherein the mass concentration of the long-chain dicarboxylic acid is adjusted to 3% -10%, and more preferably 4% -8% after the long-chain dicarboxylic acid is diluted by water.
4. The oxidation decoloring process of the long-chain dicarboxylic acid according to claim 1, wherein the oxidation temperature in the oxidation process is 10-95 ℃, preferably 20-80 ℃, and the oxidation time is 0.5-6h, preferably 0.5-3h, and further preferably 0.5-2 h.
5. The oxidation decoloration process of long-chain dibasic acid according to claim 1, wherein the oxidant is one or more of potassium permanganate, ozone, hydrogen peroxide or sodium hypochlorite; the addition amount of the oxidant is 0.02-8% of the mass of the long-chain dicarboxylic acid, preferably 0.05-5%, and more preferably 0.1-4%.
6. The oxidation decoloration process of long-chain dibasic acid according to claim 1, further comprising a step of adding activated carbon during oxidation, wherein the adding amount of the activated carbon is 0.05-3% of the mass of the long-chain dibasic acid, and is preferably 0.1-1%.
7. The oxidation decoloring process of the long-chain dicarboxylic acid according to claim 1, further comprising filtering insoluble substances by adding any one or more of activated carbon, diatomite and activated clay after oxidation, wherein the addition amount of any one or more of the activated carbon, the diatomite and the activated clay is 0.5-10% of the weight of the long-chain dicarboxylic acid, and is preferably 1-5%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111437184.4A CN114181073B (en) | 2017-12-28 | 2017-12-28 | Long-chain binary acid oxidation decoloring technology |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111437184.4A CN114181073B (en) | 2017-12-28 | 2017-12-28 | Long-chain binary acid oxidation decoloring technology |
CN201711464080.6A CN109970548B (en) | 2017-12-28 | 2017-12-28 | Long-chain dibasic acid oxidation decoloring process |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711464080.6A Division CN109970548B (en) | 2017-12-28 | 2017-12-28 | Long-chain dibasic acid oxidation decoloring process |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114181073A true CN114181073A (en) | 2022-03-15 |
CN114181073B CN114181073B (en) | 2024-08-09 |
Family
ID=67075054
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111437184.4A Active CN114181073B (en) | 2017-12-28 | 2017-12-28 | Long-chain binary acid oxidation decoloring technology |
CN201711464080.6A Active CN109970548B (en) | 2017-12-28 | 2017-12-28 | Long-chain dibasic acid oxidation decoloring process |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711464080.6A Active CN109970548B (en) | 2017-12-28 | 2017-12-28 | Long-chain dibasic acid oxidation decoloring process |
Country Status (1)
Country | Link |
---|---|
CN (2) | CN114181073B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114426476A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Refining method and device for long-chain dibasic acid |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1219530A (en) * | 1997-12-08 | 1999-06-16 | 中国石油化工总公司抚顺石油化工研究院 | Method for refining long-chain bibasic acid |
CN101108928A (en) * | 2006-07-20 | 2008-01-23 | 上海凯赛生物技术研发中心有限公司 | Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride |
CN102976917A (en) * | 2012-11-29 | 2013-03-20 | 中国石油化工股份有限公司 | Aqueous-phase refining method of long-chain dibasic acid |
CN103497100A (en) * | 2013-09-23 | 2014-01-08 | 中国石油化工股份有限公司 | Double-stage purification method of long chain dicarboxylic acid aqueous phase |
CN104693018A (en) * | 2013-12-10 | 2015-06-10 | 上海凯赛生物技术研发中心有限公司 | Method for demulsifying and refining long-chain diacid fermentation broth |
CN104844441A (en) * | 2014-02-17 | 2015-08-19 | 上海凯赛生物技术研发中心有限公司 | Long-chain mixed dicarboxylic acid purification method |
-
2017
- 2017-12-28 CN CN202111437184.4A patent/CN114181073B/en active Active
- 2017-12-28 CN CN201711464080.6A patent/CN109970548B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1219530A (en) * | 1997-12-08 | 1999-06-16 | 中国石油化工总公司抚顺石油化工研究院 | Method for refining long-chain bibasic acid |
CN101108928A (en) * | 2006-07-20 | 2008-01-23 | 上海凯赛生物技术研发中心有限公司 | Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride |
CN102976917A (en) * | 2012-11-29 | 2013-03-20 | 中国石油化工股份有限公司 | Aqueous-phase refining method of long-chain dibasic acid |
CN103497100A (en) * | 2013-09-23 | 2014-01-08 | 中国石油化工股份有限公司 | Double-stage purification method of long chain dicarboxylic acid aqueous phase |
CN104693018A (en) * | 2013-12-10 | 2015-06-10 | 上海凯赛生物技术研发中心有限公司 | Method for demulsifying and refining long-chain diacid fermentation broth |
CN104844441A (en) * | 2014-02-17 | 2015-08-19 | 上海凯赛生物技术研发中心有限公司 | Long-chain mixed dicarboxylic acid purification method |
Also Published As
Publication number | Publication date |
---|---|
CN109970548A (en) | 2019-07-05 |
CN109970548B (en) | 2022-01-04 |
CN114181073B (en) | 2024-08-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3842409A1 (en) | Method and system for refining long chain dicarboxylic acid | |
CN104693018A (en) | Method for demulsifying and refining long-chain diacid fermentation broth | |
CN108947809B (en) | Method for extracting and refining long-chain dicarboxylic acid from fermentation liquor | |
CN109970548B (en) | Long-chain dibasic acid oxidation decoloring process | |
CN111349006B (en) | Method for refining long-chain dicarboxylic acid | |
CN110256238B (en) | Refining method of long-chain mixed dibasic acid | |
CN110054561A (en) | A kind of oxidative decoloration technique of long-chain biatomic acid | |
CN110512213B (en) | Purification method of long-chain mixed dibasic acid | |
CN111777504B (en) | Method for purifying L-lactic acid extracted from fermentation liquor | |
CN111704537A (en) | Preparation method of refined long-chain dicarboxylic acid | |
US12017182B2 (en) | Method and system for refining long chain dicarboxylic acid | |
CN111533651A (en) | Method for preparing long-chain dicarboxylic acid by aqueous phase method | |
CN114716311B (en) | Two-aqueous phase extraction process, product and application of long-chain dibasic acid | |
CN104513151B (en) | A kind of method extracting high purity butylene diacid from succinate fermentation liquid | |
CN111960942B (en) | Refining method and product of long-chain mixed dibasic acid | |
CN110683946B (en) | Odd-carbon long-chain dibasic acid with low content of monoacid impurities and method for reducing content of monoacid impurities | |
CN115947662A (en) | Separation and purification method of L-tyrosine and preparation method thereof | |
CN114685269B (en) | Purification method of long-chain dibasic acid and long-chain dibasic acid product | |
CN112794799B (en) | Method for reducing solvent evaporation amount in binary acid refining process | |
CN114478235B (en) | Method for purifying organic acid in fermentation liquor | |
CN111099987B (en) | Refining method of long-chain dicarboxylic acid in fermentation liquor | |
JP2023533798A (en) | Purification of aliphatic dicarboxylic acids produced by biotechnological methods | |
CN116550283A (en) | Compound decolorizing agent for decolorizing dicarboxylic acid fermentation liquor and method for decolorizing and refining dicarboxylic acid fermentation liquor | |
CN117342947A (en) | Extraction and refining method of long-chain dibasic acid and product | |
CN111592456A (en) | Extraction method of mixed long-chain dibasic acid and mixed long-chain dibasic 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 |