CN114380683A - Method for extracting lactic acid from fermentation liquor containing calcium lactate - Google Patents
Method for extracting lactic acid from fermentation liquor containing calcium lactate Download PDFInfo
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- CN114380683A CN114380683A CN202111575700.XA CN202111575700A CN114380683A CN 114380683 A CN114380683 A CN 114380683A CN 202111575700 A CN202111575700 A CN 202111575700A CN 114380683 A CN114380683 A CN 114380683A
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- lactic acid
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 278
- 239000004310 lactic acid Substances 0.000 title claims abstract description 137
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000000855 fermentation Methods 0.000 title claims abstract description 25
- 230000004151 fermentation Effects 0.000 title claims abstract description 25
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 title claims abstract description 23
- 239000001527 calcium lactate Substances 0.000 title claims abstract description 23
- 229960002401 calcium lactate Drugs 0.000 title claims abstract description 23
- 235000011086 calcium lactate Nutrition 0.000 title claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 65
- 238000005342 ion exchange Methods 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 230000001954 sterilising effect Effects 0.000 claims abstract description 9
- 238000011033 desalting Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003599 detergent Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008234 soft water Substances 0.000 claims description 8
- -1 alcohol compound Chemical class 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000004659 sterilization and disinfection Methods 0.000 claims description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical group CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 claims description 3
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- SNAMIIGIIUQQSP-UHFFFAOYSA-N bis(6-methylheptyl) hydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(=O)OCCCCCC(C)C SNAMIIGIIUQQSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- MEXKFCWMWJZDMF-UHFFFAOYSA-N n,n-dibutylacetamide Chemical compound CCCCN(C(C)=O)CCCC MEXKFCWMWJZDMF-UHFFFAOYSA-N 0.000 claims description 2
- SILWLTRTLXQJSO-UHFFFAOYSA-N n,n-dipentylacetamide Chemical compound CCCCCN(C(C)=O)CCCCC SILWLTRTLXQJSO-UHFFFAOYSA-N 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 18
- 239000012528 membrane Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 3
- 229960000448 lactic acid Drugs 0.000 description 110
- 239000000243 solution Substances 0.000 description 35
- 239000012071 phase Substances 0.000 description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000003957 anion exchange resin Substances 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000186660 Lactobacillus Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 238000005303 weighing 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
-
- 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
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Abstract
The invention provides a method for extracting lactic acid from a calcium lactate-containing fermentation broth. The method comprises the following steps: (1) sterilizing a fermentation liquor containing calcium lactate, carrying out acidolysis with sulfuric acid, and filtering to obtain acidolysis liquor containing lactic acid; (2) desalting and decoloring acidolysis solution containing lactic acid by ion exchange to obtain ion exchange decolored solution containing lactic acid; (3) extracting, washing and back-extracting the ion exchange decolorized solution containing lactic acid to obtain back-extraction solution containing lactic acid; (4) extracting the lactic acid from the stripping solution. The method for extracting lactic acid provided by the invention is simple to operate, the obtained lactic acid is high in yield and quality, and the consumption of auxiliary materials and energy can be reduced.
Description
Technical Field
The invention belongs to the technical field of lactic acid fermentation, relates to a method for extracting lactic acid from calcium lactate-containing fermentation liquor, and particularly relates to a method for extracting high-purity lactic acid from calcium lactate-containing fermentation liquor.
Background
Lactic acid (lactic acid) with the chemical name of alpha-hydroxypropionic acid and the molecular formula of C3H6O3Molecular weight 90.08, a naturally occurring organic acid, is widely found in humans, animals, plants and microorganisms. Is easily soluble in water, ethanol and glycerol, slightly soluble in diethyl ether, and insoluble in chloroform, benzene, gasoline, carbon dioxide, etc. Lactic acid contains an asymmetric C atom in its molecule, and thus has optical activity, and thus has two configurations, D-type and L-type. L-lactic acid is dextrorotatory, D-lactic acid is levorotatory, and DL-lactic acid is racemization. Since lactic acid contains one hydroxyl group and one carboxyl group, lactic acid can participate in oxidation reaction, reduction reaction, condensation reaction, esterification reaction, and the like. Lactic acid is an important organic acid and is widely applied to the fields of food, medicine, chemical industry and the like. Lactic acid is widely used in the food industry as an acidulant, preservative and reducing agent because it is mildly acidic and stable, and contributes to the flavor of food. Lactic acid has a strong bactericidal effect and can be used as a disinfectant in places such as operating rooms, wards, laboratories, workshops and the like. In cosmetics and sanitary products, lactic acid, sodium lactate, calcium lactate may provide moisturizing properties. With the increase of the demand of industries such as food, medicine, chemical industry and the like on lactic acid and derivatives thereof, the market competitiveness is more and more strong, and therefore higher requirements are also put forward on the extraction process of the lactic acid. The heat-resistant grade lactic acid is high-purity lactic acid, and the color value of the lactic acid is lower than 50 without color change when the lactic acid is heated for 2 hours at 180 ℃.
In the traditional process, the lactic acid is extracted from the lactic acid fermentation liquor, and an ion exchange method is generally adopted to purify the lactic acid. However, the product obtained by the process has low purity and cannot be suitable for some applications with high requirements on lactic acid. Further, there is a method of purifying lactic acid by esterification or distillation, but these two methods increase the purity of lactic acid, but have high energy consumption and low yield.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for extracting lactic acid from a calcium lactate-containing fermentation broth. The method for extracting lactic acid provided by the invention is simple to operate, and the obtained lactic acid is high in yield, high in purity and low in energy consumption.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for extracting lactic acid from a calcium lactate-containing fermentation broth, which comprises the following steps:
(1) sterilizing a fermentation liquor containing calcium lactate, carrying out acidolysis with sulfuric acid, and filtering to obtain acidolysis liquor containing lactic acid;
(2) desalting and decoloring acidolysis solution containing lactic acid by ion exchange to obtain decolored ion exchange solution containing lactic acid;
(3) extracting, washing and back-extracting the decolorized ion exchange liquid to obtain a back-extraction liquid containing lactic acid;
(4) and (4) carrying out ion exchange, decoloration, concentration and the like on the back extraction solution to obtain the finished product lactic acid.
The lactic acid obtained by the method for extracting lactic acid provided by the invention has high purity and high yield, and can reduce the consumption of auxiliary materials and energy.
The decolorized ion exchange liquid containing lactic acid is mixed with an extracting agent according to a certain ratio for extraction, and an extraction load phase and a raffinate phase containing lactic acid can be obtained.
In a preferred embodiment of the present invention, a phase modifier and/or a diluent is further added to the extractant used in the extraction.
The extractant is selected from one or the combination of at least two of phosphorus oxide extractant, amide extractant and amine extractant.
Preferably, the phosphorus-oxygen extractant is selected from one or a combination of at least two of diisooctyl phosphate, tributyl phosphate, trialkyl phosphine oxide and trioctyl phosphine oxide.
Preferably, the amide extractant is selected from one or a combination of at least two of N, N-dibutylacetamide and N, N-diamylacetamide.
Preferably, the amine extractant is trilaurylamine.
The phase regulator is selected from a single alcohol compound or a mixture of several alcohol compounds.
Preferably, the phase modifier is C6-C20One or a mixture of at least two of alcohol compounds, preferably, the phase regulator is C8-C18Alcohol compounds such as n-octanol, n-decanol, isomeric octadecanol, etc.;
the diluent is C12-C31An alkane compound or an aromatic compound, or a mixture thereof.
Preferably, the diluent is C16-C28One or a mixture of at least two of alkane compounds, such as No. 260 solvent oil, white oil, isoparaffin (IP80), etc.
The volume of the extractant, the phase regulator and the diluent in the extraction system is respectively 20-80%, 0-30% and 75-20%.
In a preferred embodiment of the present invention, the extraction temperature is 20 to 60 ℃ and may be, for example, 25 ℃, 30 ℃, 35 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 45 ℃, 50 ℃, 55 ℃, preferably 25 to 45 ℃.
As a preferable technical scheme of the invention, the volume ratio of the extracting agent to the ion-exchange decolorization solution containing lactic acid in the extracted extraction phase is (0.5-5.5): 1, for example, may be 0.5: 1. 0.8: 1. 1:1, 1.2: 1. 1.5: 1. 1.8: 1. 2: 1. 2.2: 1. 2.5: 1. 2.8: 1. 3: 1. 3.5: 1. 4: 1. 4.5: 1.5: 1 or 5.5: 1, etc., preferably (1-2.5): 1.
in a preferred embodiment of the present invention, the number of extraction stages is 2 to 10, and may be, for example, 3, 4, 5, 6, 7, 8, 9, or preferably 4 to 9.
And the organic phase obtained after back extraction can be returned to the extraction step to be used as the extractant for the next extraction, so that the recycling of the extractant is realized.
In a preferred embodiment of the present invention, the detergent for washing is soft water and/or a lactic acid solution, preferably a lactic acid solution.
In a preferred embodiment of the present invention, the washing temperature is 20 to 60 ℃ and may be, for example, 20 ℃, 25 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 55 ℃, or the like, preferably 25 to 45 ℃.
In a preferred embodiment of the present invention, the volume ratio of the lactic acid-containing extraction load phase to the detergent is (10-50): 1, for example, may be 10: 1. 15: 1. 20: 1. 25: 1. 30: 1. 35: 1. 40: 1. 45, and (2) 45: 1 or 50: 1, etc. Preferably (20-30): 1. the volume ratio of the extraction load phase containing lactic acid to the detergent is optimized, so that the washing effect is further improved.
In a preferred embodiment of the present invention, the number of washing stages is 2 to 10, and may be, for example, 3, 4, 5, 6, 7, 8, 9, or preferably 4 to 8.
In a preferred embodiment of the present invention, the temperature of the stripping is 60 to 100 ℃, for example, 70 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 97 ℃, preferably 75 to 95 ℃.
In a preferred embodiment of the present invention, the volume ratio of the washing load phase containing lactic acid to the soft water is (0.5-10): 1, for example, may be 0.5: 1. 1:1, 1.2: 1. 1.5: 1. 1.8: 1. 2: 1. 2.2: 1. 2.5: 1. 2.8: 1. 3: 1. 3.5: 1. 4: 1. 4.5: 1.5: 1. 6: 1. 7: 1. 8: 1. 9: 1 or 10: 1, etc. Preferably (2-3): 1.
in a preferred embodiment of the present invention, the number of stages of the stripping process is 2 to 10, and may be, for example, 3, 4, 5, 6, 7, 8, 9, or the like, preferably 4 to 9.
The acidolysis solution containing lactic acid is obtained by the following method: filtering and sterilizing the fermentation liquor containing calcium lactate, adding sulfuric acid for acidolysis, and filtering to obtain acidolysis liquor containing lactic acid.
In a preferred embodiment of the present invention, the temperature of the acid hydrolysis is 40 to 90 ℃, for example, 50 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, preferably 60 to 85 ℃.
In a preferred embodiment of the present invention, the final pH of the acid hydrolysis is 1.0 to 3.0, for example, 1.2, 1.5, 1.7, 1.9, 2.0, 2.5, 2.8, etc., preferably 1.5 to 2.0.
As a preferred technical scheme of the present invention, the filtration is performed by using a centrifuge, a plate and frame filter press, a belt conveyor or a horizontal screw separator, preferably a belt conveyor or a horizontal screw separator.
As a preferable technical scheme of the invention, the ion exchange desalination of the step (2) of the invention adopts cation exchange resin and anion exchange resin to remove cations and anions, and Ca in the obtained ion exchange liquid is controlled2+200ppm or less, preferably Ca2+≤50ppm，SO4 2-500ppm or less, preferably SO4 2-≤200ppm。
As a preferred technical solution of the present invention, the decoloring in the step (2) is performed by using activated carbon, resin or an organic film, preferably by using an organic film; the color of the decolorized liquor is controlled to be 20-500Hazen, preferably 50-200 Hazen.
As a preferable technical scheme of the invention, the step (4) comprises the following steps: and (4) concentrating the back extraction solution obtained in the step (3), desalting by ion exchange, and decoloring to obtain the lactic acid.
The lactic acid with high purity can be obtained by the method for extracting lactic acid, and the purity of the lactic acid is more than or equal to 98.5%.
Compared with the prior art, the invention has the following beneficial effects:
the method for extracting the lactic acid provided by the invention is simple to operate, the obtained lactic acid is high in yield and purity, and the consumption of auxiliary materials and energy can be reduced. The method provided by the invention can effectively solve the problem that emulsification is easy to occur in the lactic acid extraction process, so that phase separation is easy to occur during extraction, specifically, the phase separation is faster, the phase interface is clearer, and the pollution to the extractant is reduced, so that the extractant is conveniently recycled, and thus, high-purity lactic acid is obtained.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. And (3) measuring the content of lactic acid: accurately weighing 1g (accurate to 0.001g) of sample in a clean triangular flask, adding a proper amount of neutral carbon dioxide-free distilled water to dissolve the sample, adding 2-3 drops of phenolphthalein indicator, titrating the solution to pink (no fading in 30 seconds) by using 0.5mol/L sodium hydroxide standard solution, and calculating the content of lactic acid according to the consumed sodium hydroxide and the sample.
Ca2+And (3) determination of mass content: adding 1mL of ion exchange liquid sample into a colorimetric tube, adding 2mL of 4 wt% ammonium oxalate and 1mL of 95 wt% ethanol, adding water to a constant volume of 10mL, and standing for 10 minutes; the other cuvette was taken and added with a calcium standard solution (1mL, 10ppm) and subjected to the same procedure as the sample to compare the turbidity of the sample tube with that of the standard tube.
SO4 2-And (3) determination of mass content: 1mL of the sample was placed in a 50mL cuvette, 1mL of a 24 wt% hydrochloric acid solution was added, and 3mL of 25 wt% BaCl was added2Shaking the solution evenly, adding distilled water to a constant volume of 25mL, shaking evenly, and standing for 10 minutes; the turbidity of the sample tube was compared to that of the standard tube by adding a standard solution of sulfate (1mL, 10ppm) to the other cuvette and performing the same operation as the sample.
The method for measuring the chromaticity comprises the following steps: the zero point of the colorimeter was first calibrated with distilled water and the sample was then poured directly into a 5ml cuvette, and the colorimeter would automatically give the colorimetric values in Hazen units. When the chroma is more than 500Hazen, the sample is diluted by the smallest multiple step by step, and the result is multiplied by the dilution multiple.
The lactic acid fermentation liquor used in the embodiment of the invention is prepared by fermenting corn, cassava, cane sugar and the like serving as main raw materials for 30-60 hours at the temperature of 20-55 ℃ by using lactobacillus.
Example 1
This example provides a method for extracting lactic acid from a calcium lactate-containing fermentation broth.
(1) 100kg of fermentation liquor containing calcium lactate is heated to 80 ℃ for filtration and sterilization, the sterilization liquid is slowly added with sulfuric acid for acidolysis until the pH value is 1.72, and an adhesive tape machine is used for separation to obtain 83.7kg of acidolysis liquid (the acidity is 15.96% (m/m)) containing lactic acid.
(2) Introducing the acidolysis solution containing lactic acid obtained in step (1) into cation exchange column (styrene gel type strongly acidic cation exchange resin 001 × 7) and anion exchange column (styrene macroporous type weakly basic anion exchange resin D319), and collecting to obtain 91.2kg (acidity of 14.43% (m/m), Ca2+40ppm、SO4 2-100ppm) of an ion exchange liquid containing lactic acid, and then decolorizing the ion exchange liquid with activated carbon to obtain 95.8kg of ion exchange decolorized liquid containing lactic acid (acidity of 13.60% (m/m) and chroma of 100 Hazen).
(3) Extracting with extractant (trilaurylamine: n-decanol: No. 260 solvent oil ═ 6.5:1.5:2.0) and the lactic acid-containing ion-exchange decolorized solution obtained in step (2) at 30 ℃ in a volume ratio of 1:1, performing 8-stage countercurrent extraction, wherein no emulsification phenomenon occurs in the extraction process, the phase separation time is 0.6min, 108kg (acidity: 11.88% (m/m)) of lactic acid-containing extraction load phase and 83.6kg (acidity: 0.24% (m/m)) of raffinate phase are obtained, and the extraction yield is 98.48%.
(4) Adding a lactic acid solution with acidity of 12.43% (m/m) into the lactic acid extraction load phase obtained in the step (3) and a detergent according to the volume ratio of 25:1, and carrying out 6-stage washing at 35 ℃ to obtain 106.92kg of a washing load phase containing lactic acid (with acidity of 11.82% (m/m)); then carrying out 8-stage counter-current back extraction on the washing load phase containing lactic acid and soft water at the temperature of 95 ℃ according to the volume ratio of 2:1 to obtain 65.94kg of back extraction solution containing lactic acid (the acidity is 19.16 percent (m/m)) and 94.44kg of organic phase after back extraction (the acidity is 0.20 percent (m/m)), wherein the total back extraction rate is 98.49 percent; and (4) directly returning the solvent phase after back extraction to the step (3) to perform countercurrent extraction with the ion exchange decolorized solution containing lactic acid.
(5) Will be provided withSubjecting the lactic acid-containing back extraction solution obtained in step (4) to ion exchange (cation exchange resin 001 x 8 and anion exchange resin LX-67) to control Fe in the ion exchange solution3+≤4ppm、SO4 2-Less than or equal to 4ppm), decolorization (special carbon for decolorizing lactic acid, controlling the chroma of the ion exchange decolorized solution to be less than or equal to 30Hazen), concentration (concentration at 65-80 ℃) to obtain the finished product of lactic acid (the content is 93.17 percent, and the purity is 98.58 percent).
Example 2
This example provides a method for extracting lactic acid from a calcium lactate-containing fermentation broth.
(1) 100kg of fermentation liquor containing calcium lactate is heated to 85 ℃ for filtration and sterilization, the sterilization liquid is slowly added with sulfuric acid for acidolysis until the pH value is 1.65, and 86.7kg of acidolysis liquid containing lactic acid (the acidity is 15.56% (m/m)) is obtained by separation with a horizontal spiral separator.
(2) Introducing the acidolysis solution containing lactic acid obtained in step (1) into cation exchange column (styrene gel type strongly acidic cation exchange resin 001 × 7) and anion exchange column (styrene macroporous type weakly basic anion exchange resin D319), and collecting to obtain 91.1kg (acidity of 14.58% (m/m), Ca2+50ppm、SO4 2-160ppm) of an ion exchange liquid containing lactic acid, and then decolorizing the ion exchange liquid by activated carbon to obtain 95.6kg of ion exchange decolorized liquid containing lactic acid (acidity of 13.69% (m/m) and chroma of 150 Hazen).
(3) Extracting the lactic acid-containing ion-exchange decolorized solution obtained in the step (2) by 8 stages of countercurrent extraction with an extractant (trioctylamine: n-octanol: white oil: 6.0:1.5:2.5) according to a volume ratio of 1:1 at 35 ℃, wherein no emulsification phenomenon occurs in the extraction process, the phase separation time is 0.7min, 108.4kg (acidity is 11.83% (m/m)) of an extraction load phase containing lactic acid and 82.7kg (acidity is 0.316% (m/m)) of a raffinate phase are obtained, and the extraction yield is 98.01%.
(4) Adding a lactic acid solution with acidity of 12.15% (m/m) into the lactic acid extraction load phase obtained in the step (3) and a detergent according to the volume ratio of 25:1, and washing at 30 ℃ for 6 stages to obtain 108.2kg of a washing load phase containing lactic acid (with acidity of 11.56% (m/m)); then, the washing load phase containing lactic acid and soft water are subjected to 8-stage countercurrent back extraction at 95 ℃ according to the volume ratio of 2:1 to obtain 66.37kg (acidity of 18.49% (m/m)) of back extraction solution containing lactic acid and 95.9kg (acidity of 0.247% (m/m)) of organic phase after back extraction, wherein the total back extraction rate is 98.17%; and (4) directly returning the solvent phase after back extraction to the step (3) to perform countercurrent extraction with the ion exchange decolorized solution containing lactic acid.
(5) Subjecting the lactic acid-containing back extraction solution obtained in step (4) to ion exchange (cation exchange resin 001 x 8 and anion exchange resin LX-67) to control Fe in the ion exchange solution3+≤4ppm、SO4 2-Less than or equal to 4ppm), decolorization (special carbon for decolorizing lactic acid, controlling the chroma of the ion exchange decolorized solution to be less than or equal to 35Hazen), concentration (concentration at 65-80 ℃) to obtain the finished product of lactic acid (the content is 94.20%, the purity is 98.37%).
Example 3
This example provides a method for extracting lactic acid from a calcium lactate-containing fermentation broth.
The difference from the embodiment 2 is that the step (3) in this embodiment is: extracting the lactic acid-containing ion-exchange decolorized solution obtained in the step (2) by 9 stages of countercurrent extraction at 25 ℃ by using an extracting agent (tributyl phosphate: n-decanol: isoparaffin IP80 is 6.5:1.5:2.0) and the volume ratio of 1:1, wherein no emulsification phenomenon occurs in the extraction process, the phase separation time is 0.6min, 108.43kg (acidity is 11.73% (m/m)) of lactic acid-containing extraction load phase and 82.77kg (acidity is 0.44% (m/m)) of raffinate phase are obtained, and the extraction yield is 97.19%.
108.1kg (acidity of 11.59% (m/m)) of the washed load phase containing lactic acid obtained in step (4), 66.30kg (acidity of 18.48% (m/m)) of a stripping solution containing lactic acid and 95.85kg (acidity of 0.287% (m/m)) of the solvent phase after stripping, the total stripping rate being 97.8%.
And (4) obtaining the finished product lactic acid (with the content of 92.1 percent and the purity of 98.56 percent) in the step (5).
Example 4
This example provides a method for extracting lactic acid from a calcium lactate-containing fermentation broth.
The difference from the embodiment 2 is that the step (4) in this embodiment is: adding soft water into the lactic acid extraction load phase obtained in the step (3) and a detergent according to the volume ratio of 40:1, and washing at 40 ℃ for 4 stages to obtain 108.2kg of a washing load phase containing lactic acid (the acidity is 11.67% (m/m)); then, the washing load phase containing lactic acid and soft water are subjected to 5-stage countercurrent back extraction at 70 ℃ according to the volume ratio of 5:1 to obtain 33.07kg (acidity of 34.55 percent (m/m)) of back extraction solution containing lactic acid and 96.78kg (acidity of 1.24 percent (m/m)) of solvent phase after back extraction, wherein the total back extraction rate is 90.48 percent; directly returning the organic phase after back extraction to the step (3) to perform countercurrent extraction with the decolored solution containing lactic acid;
and (4) obtaining the finished product lactic acid (the content is 90.15 percent, and the purity is 98.52 percent) in the step (5).
Comparative example 1
The present comparative example provides a method for extracting lactic acid from a calcium lactate-containing fermentation broth.
The difference from example 2 is that this comparative example does not perform steps (3) and (4) to obtain the final lactic acid (content 88.6%, purity 97.55%).
Comparative example 2
The comparative example provides a method for extracting lactic acid from a calcium lactate fermentation broth.
The only difference from example 2 is that step (2) is not performed, and the lactic acid-containing acid hydrolysis solution obtained in step (1) is directly subjected to the operations of the subsequent steps (3), (4) and (5).
The method of comparative example 1 produced emulsification during the extraction process, resulting in finished lactic acid (91.2% content, 98.06% purity).
Comparative example 3
The comparative example provides a method for extracting lactic acid from a calcium lactate fermentation broth.
The only difference from example 2 is that, without carrying out the operations of steps (3) and (4), 2kg (acidity 13.69% w/w) of the lactic acid-containing ion-exchange decolorized solution obtained in step (2) was subjected to concentration and molecular distillation to obtain 223.0g (content 98.3%, purity 98.46%) of lactic acid, and the distillation yield of lactic acid was calculated to be 80.06%.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for extracting lactic acid from a calcium lactate-containing fermentation broth, comprising:
(1) sterilizing a fermentation liquor containing calcium lactate, carrying out acidolysis with sulfuric acid, and filtering to obtain acidolysis liquor containing lactic acid;
(2) desalting and decoloring acidolysis solution containing lactic acid by ion exchange to obtain ion exchange decolored solution containing lactic acid;
(3) extracting, washing and back-extracting the ion exchange decolorized solution containing lactic acid to obtain back-extraction solution containing lactic acid;
(4) and (3) carrying out ion exchange, decoloring and concentrating on the back extraction solution containing the lactic acid to obtain a lactic acid product.
2. The method according to claim 1, characterized in that the extractant used in the extraction in step (3) is further added with a phase modifier and/or a diluent,
wherein the extractant is selected from one or the combination of at least two of phosphorus oxide extractant, amide extractant and amine extractant;
preferably, the phosphorus-oxygen extractant is selected from one or a combination of at least two of diisooctyl phosphate, tributyl phosphate, trialkyl phosphine oxide and trioctyl phosphine oxide;
preferably, the amide extractant is selected from one or a combination of at least two of N, N-dibutylacetamide and N, N-diamylacetamide;
preferably, the amine extractant is trilaurylamine;
wherein, the phase regulator is selected from a single alcohol compound or a mixture of several alcohol compounds;
preferably, the phase modifier is C6-C20One or a mixture of at least two of alcohol compounds, preferably, the phase regulator is C8-C18An alcohol compound;
wherein the diluent is selected from C12-C31An alkane compound or an aromatic compound or a mixture thereof;
preferably, theThe diluent is C14-C28One or a mixture of at least two of alkane-like compounds;
preferably, the volume percentage of the extractant, the phase regulator and the diluent in the extraction in the step (3) is respectively 20-80%, 0-30% and 75-20%.
3. The method according to claim 1 or 2, characterized in that the temperature of the extraction is 20-60 ℃, preferably 25-45 ℃; and/or the presence of a gas in the gas,
the volume ratio of the extracting agent to the ion-exchange decolorizing liquid containing lactic acid is (0.5-5.5): 1, preferably (1-2.5): 1; and/or the presence of a gas in the gas,
the number of stages of extraction is 2-10 stages, preferably 4-9 stages.
4. A method according to any of claims 1-3, characterized in that the detergent for washing is a soft water and/or lactic acid solution, preferably a lactic acid solution; and/or the presence of a gas in the gas,
the washing temperature is 20-60 ℃, preferably 25-45 ℃; and/or the presence of a gas in the gas,
in the washing, the volume ratio of the extraction load phase containing lactic acid to the detergent is (10-50): 1, preferably (20-30): 1; and/or the presence of a gas in the gas,
the number of washing stages is 2 to 10 stages, preferably 4 to 8 stages.
5. The process according to any one of claims 1 to 4, wherein the stripping temperature is 60 to 100 ℃, preferably 75 to 95 ℃; and/or the presence of a gas in the gas,
the volume ratio of the washing load phase containing lactic acid to the soft water in the back extraction is (0.5-10): 1, preferably (2-3): 1; and/or the presence of a gas in the gas,
the stage number of the back extraction is 2-10 stages, and preferably 4-9 stages.
6. The method as claimed in any one of claims 1 to 5, wherein the lactic acid containing acidolysis solution is obtained by: and (3) carrying out sterilization, acidolysis and filtration on the fermentation liquor containing calcium lactate to obtain the acidolysis liquor containing lactic acid.
7. The process according to claim 6, characterized in that the temperature of the acid hydrolysis is 40-95 ℃, preferably 60-85 ℃; and/or the presence of a gas in the gas,
the final pH value of the acidolysis is 1.0-3.0, preferably 1.5-2.0; and/or the presence of a gas in the gas,
the filtration adopts a centrifuge, a plate-and-frame filter press, a belt conveyor or a horizontal screw separator, preferably a belt conveyor or a horizontal screw separator.
8. The process according to any one of claims 1 to 7, wherein the decolorization in step (2) is carried out using activated carbon, a resin or an organic membrane, preferably an organic membrane.
9. The method according to any one of claims 1-8, wherein step (4) comprises: and (4) desalting the back extraction solution obtained in the step (3) by ion exchange, decoloring and concentrating to obtain the lactic acid.
10. The method according to any one of claims 1 to 9, wherein the lactic acid product has a lactic acid content of 80 to 95% and a purity of 98.5% or more.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377335A (en) * | 1999-10-04 | 2002-10-30 | 卡吉尔道有限责任公司 | Process for producing a purified lactic acid solution |
| WO2002090312A1 (en) * | 2001-05-07 | 2002-11-14 | Cargill, Incorporated | Process for preparing carboxylic acids and derivatives thereof |
| CN104487583A (en) * | 2012-07-23 | 2015-04-01 | 旭硝子株式会社 | Method for producing organic acid |
| CN105367412A (en) * | 2015-12-14 | 2016-03-02 | 淮北中润生物能源技术开发有限公司 | Method for separation and extraction of glycollic acid and lactic acid in hydrothermal liquefied liquid by solvent extraction method |
| CN106431895A (en) * | 2016-09-18 | 2017-02-22 | 宁波工程学院 | Method for extracting lactic acid from fermentation liquor through combination of molecular distillation and extraction |
| CN106431893A (en) * | 2016-09-18 | 2017-02-22 | 宁波工程学院 | Technology for preparing sodium lactate from lactic acid fermentation broth |
| CN107324989A (en) * | 2017-06-09 | 2017-11-07 | 安徽丰原发酵技术工程研究有限公司 | It is a kind of by being dehydrated the method that extraction prepares lactic acid and lactide |
-
2021
- 2021-12-21 CN CN202111575700.XA patent/CN114380683A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377335A (en) * | 1999-10-04 | 2002-10-30 | 卡吉尔道有限责任公司 | Process for producing a purified lactic acid solution |
| WO2002090312A1 (en) * | 2001-05-07 | 2002-11-14 | Cargill, Incorporated | Process for preparing carboxylic acids and derivatives thereof |
| CN104487583A (en) * | 2012-07-23 | 2015-04-01 | 旭硝子株式会社 | Method for producing organic acid |
| CN105367412A (en) * | 2015-12-14 | 2016-03-02 | 淮北中润生物能源技术开发有限公司 | Method for separation and extraction of glycollic acid and lactic acid in hydrothermal liquefied liquid by solvent extraction method |
| CN106431895A (en) * | 2016-09-18 | 2017-02-22 | 宁波工程学院 | Method for extracting lactic acid from fermentation liquor through combination of molecular distillation and extraction |
| CN106431893A (en) * | 2016-09-18 | 2017-02-22 | 宁波工程学院 | Technology for preparing sodium lactate from lactic acid fermentation broth |
| CN107324989A (en) * | 2017-06-09 | 2017-11-07 | 安徽丰原发酵技术工程研究有限公司 | It is a kind of by being dehydrated the method that extraction prepares lactic acid and lactide |
Non-Patent Citations (1)
| Title |
|---|
| 程丽娟主编: "《发酵食品工艺学》", 西北农林科技大学出版社, pages: 425 * |
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