CN114507129A - Refining method of organic acid in fermentation liquor - Google Patents
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- 150000007524 organic acids Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000855 fermentation Methods 0.000 title claims abstract description 29
- 230000004151 fermentation Effects 0.000 title claims abstract description 29
- 238000007670 refining Methods 0.000 title claims abstract description 27
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000047 product Substances 0.000 claims abstract description 30
- 239000004310 lactic acid Substances 0.000 claims abstract description 26
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000012046 mixed solvent Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000003463 adsorbent Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000012043 crude product Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 20
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 239000012065 filter cake Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 241001052560 Thallis Species 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 238000001471 micro-filtration Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000011549 crystallization solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 235000005985 organic acids Nutrition 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
- 238000004537 pulping Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 239000007787 solid 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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a refining method of organic acid in fermentation liquor, which is to add crude organic acid into a mixed solvent for heating reaction, wherein the mixed solvent comprises lactic acid and water; and then adding an adsorbent for treatment, filtering to remove the adsorbent after treatment, cooling and crystallizing the obtained filtrate, and filtering, washing and drying to obtain the refined organic acid. The invention uses the lactic acid which is not easy to volatilize and water as the mixed solvent to refine the organic acid, can obtain a polymer grade product, and avoids the solvent loss and the environmental pollution.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a refining method of organic acid in fermentation liquor.
Background
The organic acid of the present invention has a general molecular formula of CnH2n-2O4Wherein n is 10-18, and is metabolite obtained by fermenting microorganism with liquid wax, alkane, etc. The fermentation broth is a complex heterogeneous system containing unreacted carbon source, microbial cells and debris, unused media and metabolites, and microbial secretions, especiallyIt contains a large amount of impurities such as protein, pigment and ash, which seriously affect the purity and application of the product and bring difficulty to the extraction and purification of the organic acid.
Currently, the purification of such organic acids is mainly classified into an aqueous phase extraction method and a solvent phase recrystallization method depending on the solvent. The purity of the polymerization-grade organic acid in the market is high, the purity of the single acid is generally more than 98.5wt%, and the total nitrogen is less than 30 mug/g, and at present, the crude acid is mainly recrystallized in a solvent to obtain a polymerization-grade product meeting the requirement.
CN01142806.6 discloses a method for refining carbon 11-18 long-chain dibasic acid, which is to dissolve the long-chain dibasic acid produced by petroleum fermentation in an organic solvent, filter to remove impurities, cool the filtrate, crystallize and separate out the dibasic acid, and dry the dibasic acid to obtain the refined dibasic acid. The method for extracting the long-chain dicarboxylic acid produced by petroleum fermentation comprises the following steps: standing and layering the fermentation termination solution at the temperature of 30-90 ℃ and in an alkaline environment at the pH of 10-14, respectively taking out a fermentation clear solution and thalli, adding activated carbon to decolor at the temperature of 50-90 ℃, removing the thalli, acidifying the decolored clear solution, controlling the pH of 3-4, crystallizing at the temperature of 50-95 ℃, filtering, washing with water to obtain a dibasic acid crystal filter cake, and finally drying to obtain dibasic acid dry powder; then refining with organic solvent. The organic solvent for dissolving long-chain dicarboxylic acid is alcohol or ketone, specifically acetone, methanol, or ethanol. The method uses volatile organic solvent, which not only affects the surrounding environment, but also increases the usage amount of the solvent.
CN103772186A discloses a refining method of fermented organic acid, which comprises: I. heating and inactivating the terminated fermentation liquor; II. Acidifying to separate out organic acid crystals to obtain an organic acid crystal aqueous solution; III, directly mixing the organic acid crystallization aqueous solution with an ether solvent to dissolve the organic acid, and separating an organic phase from a water phase; IV, adding an adsorbent into the organic phase obtained in the step III, and filtering to remove solid matters; v, cooling the organic phase obtained in the step IV until organic acid crystals are separated out, filtering to obtain an organic acid crystal filter cake, and drying the filter cake to obtain a refined organic acid product. The method uses ether solvent to refine organic acid, and can obtain organic acid with purity of more than 99.5 wt%. However, the ether solvent is used in a large amount, and is particularly volatile, which adversely affects the surrounding environment.
At present, most of domestic enterprises mainly producing long-chain dibasic acid use an acetic acid method solvent refining process. Patent CN101985416A discloses a refining process for producing long carbon chain dibasic acid by biological fermentation, which comprises mixing acetic acid solvent with a weight more than 90wt% with the weight 2-3 times of the weight of crude dibasic acid dry powder obtained by pretreatment, and adding active carbon with a weight 0.05-0.2wt% of the crude product at 85-100 deg.C for decolorization; and then crystallizing and filtering the filtrate, mixing and pulping the obtained wet product with water at the temperature of 70-100 ℃, cooling, crystallizing, and then centrifugally drying to obtain the product. The method needs to use a high-concentration acetic acid solvent, the acetic acid has strong corrosivity, the investment and maintenance cost of equipment is high, the operation temperature is high, and the acetic acid is a volatile solvent, so that the solvent loss is large.
CN1570124A discloses a method for producing n-long chain dibasic acid, which comprises the steps of firstly pretreating a fermentation reaction solution to remove thalli and residual alkane or fatty acid in the fermentation reaction solution to obtain an organic acid clear solution, then carrying out acidification crystallization, and carrying out plate-and-frame filter pressing on the acidification crystallization solution to obtain an organic acid crude product; and finally, refining the obtained crude product under the high vacuum condition through wiped film evaporation and a short-path distillation device or refining by adopting an organic solvent. The organic solvent used in the method is alcohols, ketones, acids and esters, so that the acidified crystallization liquid needs to be subjected to plate-and-frame filter pressing to obtain a crude dibasic acid product, and then the crude dibasic acid product is dissolved in the organic solvent for refining. When the acetic acid is used as a solvent, the refining equipment has strict requirements on material selection, the operation and maintenance cost is high, and the acetic acid needs to be recycled and dehydrated and other complex refining processes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for refining organic acid in fermentation liquor. Compared with the existing solvent method, the invention uses the lactic acid which is not easy to volatilize and water as the mixed solvent to refine the organic acid, can obtain a polymer grade product, and avoids the solvent loss and the environmental pollution.
The refining method of the organic acid in the fermentation liquor provided by the invention comprises the following steps:
(1) adding an organic acid crude product prepared by fermentation liquor into a mixed solvent for heating reaction, wherein the mixed solvent comprises lactic acid and water, and the mass concentration of the lactic acid is not lower than 60%;
(2) and adding an adsorbent after reaction for treatment, filtering the adsorbent after treatment, cooling and crystallizing the obtained filtrate, and filtering, washing and drying to obtain the refined organic acid product.
In the present invention, the organic acid has a general molecular formula of CnH2n-2O4Wherein n is 10 to 18. The organic acid can be a single organic acid or a mixed organic acid.
In the present invention, the crude organic acid prepared from the fermentation liquid in step (1) can be obtained commercially or prepared by methods well known to those skilled in the art. The content of the monoacid in the crude organic acid is generally 96-98.5%, and the total acid content is generally 92-99%. The preparation method of the crude organic acid specifically comprises the steps of pretreating fermentation liquor and then acidifying the fermentation liquor to obtain the crude organic acid. The pretreatment can adopt a method which is conventionally used for removing thalli and pigment in the field, such as heating, filtering, decoloring and the like, and the heating temperature is generally 70-100 ℃; the filtration can adopt conventional methods and equipment such as membrane filtration and the like; active carbon is added for decolorization. Preferably, the pretreatment is to heat the fermentation liquor to 70-80 ℃, and then to carry out microfiltration and ultrafiltration. The acidification can adopt a conventional acidification mode in the field, and specifically comprises the following steps: and heating the pretreated fermentation liquor to 80-90 ℃, adding sulfuric acid to adjust the pH value to 2.0-4.0, cooling to room temperature, filtering, washing, cleaning a filter cake until the pH value of the filtrate is not less than 6.0, and drying to obtain a crude organic acid product.
In the invention, in the mixed solvent in the step (1), the mass concentration of the lactic acid is 60-92%, preferably 80-90%.
In the invention, the mass ratio of the mixed solvent in the step (1) to the crude organic acid is 3-6:1, preferably 3.5-5: 1.
In the invention, the heating reaction temperature in the step (1) is 80-105 ℃, preferably 82-102 ℃, so that the crude organic acid is dissolved in the mixed solvent.
In the present invention, the adsorbent in the step (2) may be at least one of activated carbon, diatomaceous earth, alumina, and the like.
In the invention, the adding amount of the adsorbent in the step (2) is 0.5-4% of the mass of the crude organic acid, and preferably 1-2%.
In the invention, the reaction time after the adsorbent is added in the step (2) is generally 30-60 min.
In the invention, the temperature of the filtrate in the step (2) is generally reduced to 10-50 ℃ and the cooling rate is 10-20 ℃/h.
In the invention, the filtration in the step (2) can adopt the modes of filter pressing, centrifugation and the like, and the filter cake is washed by clean water with the mass of 5-10 times of that of the crude product of the organic acid.
In the invention, the drying temperature in the step (2) is 80-105 ℃, and the drying time is 1-5 h.
Compared with the prior art, the method has the following beneficial effects:
(1) the invention uses the mixed solvent of the lactic acid and the water which are not easy to volatilize to refine the organic acid, can obtain a polymer grade product, and avoids the solvent loss and the environmental pollution.
(2) Compared with organic solvents such as acetic acid, ethers and the like, the mixed solvent has the advantages that the corrosion to equipment and the harm to the environment are obviously reduced, the investment and maintenance cost of the equipment are reduced, and particularly, the environmental protection risk is reduced.
Detailed Description
The method and effects of the present invention are further illustrated by the following examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments. In the present invention, wt% is a mass fraction.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The test materials used in the following examples were purchased from biochemical reagent stores unless otherwise specified.
In the invention, the total acid content is obtained by measuring and calculating by adopting an acid-base titration method, the single acid content is measured and calculated by adopting a gas chromatography peak area normalization method, and the total nitrogen content is detected by adopting a boat sample injection chemiluminescence method.
Example 1
(1) Taking 2L of a compound containing C12H22O4The fermentation liquor with the concentration of 160g/L is pretreated firstly, and is heated and inactivated at the temperature of 80 ℃, and then is subjected to microfiltration and ultrafiltration membrane filtration to remove thalli and partial pigment. Heating the pretreated fermentation liquor to 85 deg.C, adding 85wt% sulfuric acid to adjust pH to 3.0, cooling to room temperature, filtering, cleaning the filter cake to obtain filtrate with pH not less than 6.0, and drying at 100 deg.C for 2 hr to obtain crude organic acid product with monoacid content of 97.2% and total acid content of 98.5%.
(2) Taking 200g of crude organic acid, adding the crude organic acid into 700g of mixed solvent of lactic acid and water, wherein the mass concentration of the lactic acid is 90%, heating to 82 ℃ to dissolve the lactic acid, adding 2g of activated carbon after reaction, treating for 30min, filtering the activated carbon, introducing the filtrate into a crystallizer, cooling to room temperature at a cooling rate of 10 ℃/h, cleaning a filter cake by using 2L of water for 5 times after filtration, and drying at 100 ℃ for 2h to obtain 185.6g of refined product.
Example 2
(1) Taking 1L of C11H20O4The fermentation liquor with the concentration of 144g/L is pretreated, is heated and inactivated at the temperature of 80 ℃, and is subjected to microfiltration and ultrafiltration membrane filtration to remove thalli and partial pigment. Heating the pretreated fermentation liquor to 85 deg.C, adding 70wt% sulfuric acid to adjust pH to 3.0, cooling to room temperature, filtering, cleaning the filter cake to obtain filtrate with pH not less than 6.0, and drying at 100 deg.C for 2 hr to obtain crude organic acid product with monoacid content of 97.5% and total acid content of 98.7%.
(2) Taking 100g of crude organic acid, adding the crude organic acid into 500g of mixed solvent of lactic acid and water, wherein the mass concentration of the lactic acid is 80%, heating to 95 ℃ to dissolve the lactic acid, adding 2g of activated carbon after reaction, treating for 30min, filtering the activated carbon, introducing the filtrate into a crystallizer, cooling to room temperature at a cooling rate of 10 ℃/h, cleaning a filter cake by using 500mL of water for 5 times after filtration, and drying at 100 ℃ for 2h to obtain 92.1g of refined product.
Example 3
(1) Taking 1.5L of C13H24O4The fermentation liquor with the concentration of 152g/L is pretreated firstly, is heated and inactivated at the temperature of 80 ℃, and is subjected to microfiltration and ultrafiltration membrane filtration to remove thalli and partial pigment. Heating the pretreated fermentation liquor to 85 ℃, adding 75wt% of sulfuric acid to adjust the pH value to 3.0, naturally cooling to room temperature for filtering, cleaning a filter cake until the pH value of the filtrate is not less than 6.0, and drying the filter cake at 100 ℃ for 2h to obtain a crude organic acid product, wherein the monoacid content is 97.4%, and the total acid content is 98.6%.
(2) Adding 200g of crude acid into a mixed solvent of 800g of lactic acid and water, wherein the mass concentration of the lactic acid is 60%, heating to 102 ℃ to dissolve the lactic acid, adding 3g of activated carbon after reaction for 30min, filtering the activated carbon, introducing the filtrate into a crystallizer, cooling to room temperature at a cooling rate of 10 ℃/h, cleaning a filter cake by using 1L of water for 5 times after filtration, and drying at 100 ℃ for 2h to obtain 185.4g of a refined product.
Example 4
The difference from example 1 is that: the crude acid of the commercial dodecanedioic acid is adopted, and the content of the monoacid is 96.5 percent and the total acid content is 99.0 percent through detection. After refining, 184.5g of refined product was obtained.
Example 5
The difference from example 1 is that: the adsorbent adopts diatomite instead of activated carbon. After refining, 185.1g of refined product was obtained.
Example 6
The same as example 1, except that: the mass concentration of lactic acid in the adopted mixed solvent is 45 percent, and the adding amount is 1400 g. After refining, 162.4g of refined product was obtained.
Example 7
The difference from example 1 is that: the mass concentration of lactic acid in the adopted mixed solvent is 98%, and the addition amount is 640 g. After refining, 180.3g of refined product was obtained.
Comparative example 1
The difference from example 1 is that: the mixed solvent is prepared by replacing lactic acid with the same amount of acetic acid. After refining, 174.2g of refined product was obtained.
Comparative example 2
The same as example 1, except that: the mixed solvent is prepared by replacing lactic acid with the same amount of butyl ether. After refining, 180.6g of refined product was obtained.
Comparative example 3
The difference from example 1 is that: the refining solvent adopts the same amount of lactic acid and does not contain water. After refining, 175.0g of refined product was obtained.
Comparative example 4
The difference from example 1 is that: the refining solvent adopts equal amount of water and does not contain lactic acid. After refining 194.4g of refined product were obtained.
TABLE 1 test results of examples and comparative examples
As can be seen from Table 1, the mixed solvent of lactic acid and water is adopted to refine organic acid, the product quality meets the requirements of polymer-grade products, and the mixed solvent does not volatilize in the using process to cause solvent loss and environmental pollution.
Claims (13)
1. A refining method of organic acid in fermentation liquor is characterized by comprising the following steps:
(1) adding an organic acid crude product prepared by fermentation liquor into a mixed solvent for heating reaction, wherein the mixed solvent comprises lactic acid and water, and the mass concentration of the lactic acid is not lower than 60%;
(2) and adding an adsorbent to treat after the reaction, filtering the adsorbent after the treatment, cooling and crystallizing the obtained filtrate, and filtering, washing and drying to obtain the organic acid refined product.
2. The method of claim 1, wherein: the organic acid has a molecular formula of CnH2n-2O4Wherein n is 10 to 18.
3. The method according to claim 1 or 2, characterized in that: the organic acid is a single organic acid or a mixed organic acid.
4. The method of claim 1, wherein: in the crude organic acid product in the step (1), the content of the monoacid is generally 96-98.5%, and the total acid content is generally 92-99%.
5. The method of claim 1, wherein: in the mixed solvent in the step (1), the mass concentration of the lactic acid is 60-92%, preferably 80-90%.
6. The method according to claim 1 or 5, characterized in that: the mass ratio of the mixed solvent in the step (1) to the crude organic acid is 3-6:1, preferably 3.5-5: 1.
7. The method of claim 1, wherein: the heating reaction temperature in the step (1) is 80-105 ℃, and preferably 82-102 ℃.
8. The method of claim 1, wherein: the adsorbent in the step (2) is at least one of activated carbon, diatomite and alumina.
9. The method according to claim 1 or 8, characterized in that: the adding amount of the adsorbent in the step (2) is 0.5-4% of the mass of the crude organic acid, and preferably 1-2%.
10. The method of claim 1, wherein: the reaction time is 30-60min after the adsorbent is added in the step (2).
11. The method of claim 1, wherein: and (3) cooling the filtrate in the step (2) to crystallize, wherein the temperature is reduced to 10-50 ℃, and the cooling rate is 10-20 ℃/h.
12. The method of claim 1, wherein: and (3) filtering in the step (2) by adopting a filter pressing and centrifuging mode, and washing with water with the mass of 5-10 times of that of the crude organic acid.
13. The method of claim 1, wherein: the drying temperature in the step (2) is 80-105 ℃, and the drying time is 1-5 h.
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Citations (11)
| 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 |
| CN102329211A (en) * | 2011-09-13 | 2012-01-25 | 淮安清江石油化工有限责任公司 | C12-C13 long-chain binary acid refining method |
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