CN112481345A - Method for preparing D-pantoic acid by continuous catalysis - Google Patents
Method for preparing D-pantoic acid by continuous catalysis Download PDFInfo
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- OTOIIPJYVQJATP-BYPYZUCNSA-N (R)-pantoic acid Chemical compound OCC(C)(C)[C@@H](O)C(O)=O OTOIIPJYVQJATP-BYPYZUCNSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001728 nano-filtration Methods 0.000 claims abstract description 32
- -1 DL-pantoic acid lactone Chemical class 0.000 claims abstract description 31
- 239000000413 hydrolysate Substances 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 238000000605 extraction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000005086 pumping Methods 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 230000003311 flocculating effect Effects 0.000 claims abstract description 12
- 239000008055 phosphate buffer solution Substances 0.000 claims abstract description 11
- 239000008394 flocculating agent Substances 0.000 claims abstract description 7
- 108010093096 Immobilized Enzymes Proteins 0.000 claims abstract description 6
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- SERHXTVXHNVDKA-UHFFFAOYSA-N pantolactone Chemical compound CC1(C)COC(=O)C1O SERHXTVXHNVDKA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000000706 filtrate Substances 0.000 abstract 1
- 108090000790 Enzymes Proteins 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 9
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- FAPWYRCQGJNNSJ-UBKPKTQASA-L calcium D-pantothenic acid Chemical compound [Ca+2].OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O.OCC(C)(C)[C@@H](O)C(=O)NCCC([O-])=O FAPWYRCQGJNNSJ-UBKPKTQASA-L 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- GHOKWGTUZJEAQD-UHFFFAOYSA-N pantothenic acid Chemical compound OCC(C)(C)C(O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011703 D-panthenol Substances 0.000 description 1
- SNPLKNRPJHDVJA-ZETCQYMHSA-N D-panthenol Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCCO SNPLKNRPJHDVJA-ZETCQYMHSA-N 0.000 description 1
- 235000004866 D-panthenol Nutrition 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical class C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960003949 dexpanthenol Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
- C12P41/003—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- 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
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/42—Hydroxy-carboxylic acids
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Abstract
The invention discloses a method for preparing D-pantoic acid by continuous catalysis, which comprises the following steps: filling the immobilized enzyme into a group of resin columns connected in series, connecting a storage tank between two adjacent resin columns, and washing with deionized water until the effluent liquid is colorless; dissolving DL-pantoic acid lactone in deionized water, and adjusting the pH value of a DL-pantoic acid lactone solution to 6.5-7.5 by using a phosphate buffer solution; adding activated carbon and a flocculating agent into the DL-pantoic acid lactone solution for decoloring and flocculating to obtain a decoloring solution; pumping the decolorized solution into a resin column to perform an enzymatic hydrolysis reaction to obtain a hydrolysate; pumping the hydrolysate into a nanofiltration system, and concentrating and removing water to obtain nano filtrate; pumping the nanofiltration liquid into a group of extraction columns connected in series, performing multi-stage countercurrent extraction, and recycling the extract liquid; concentrating the raffinate in vacuum to obtain D-pantoic acid; the method can improve the production efficiency of the D-pantoic acid, reduce the production cost and solve the problem of odor of a production field.
Description
Technical Field
The invention relates to the technical field of enzyme engineering, in particular to a method for preparing D-pantoic acid by continuous catalysis.
Background
The D-calcium pantothenate is widely applied to food, feed and medicine industries, and has large market demand. The prior production process comprises the steps of firstly synthesizing DL-pantoic acid lactone by isobutyraldehyde, formaldehyde and sodium cyanide, then obtaining D-pantoic acid by chemical resolution or biological enzyme resolution, generating D-pantoic acid lactone by cyclization reaction, and finally generating D-calcium pantothenate by condensing beta-calcium alanine and the D-pantoic acid lactone.
In the prior art, the chemical method for splitting DL-pantoic acid lactone has the following defects: chemical resolving agents such as quinine compounds, chiral amines and the like have high cost and are not beneficial to environmental protection; the DL-pantoic acid lactone is separated by a biological enzyme method, firstly D-pantoic acid lactone hydrolase selectively hydrolyzes racemic DL-pantoic acid lactone to generate D-pantoic acid, then the D-pantoic acid is separated from the DL-pantoic acid lactone by utilizing different solubilities (part of the D-pantoic acid lactone is not hydrolyzed), and the D-pantoic acid is lactonized to form the D-pantoic acid lactone. And recovering and utilizing DL-pantoic acid lactone, and using for resolution again after racemization. The enzymatic resolution is more environment-friendly than the chemical resolution, and the industrial production of D-calcium pantothenate, D-pantothenic acid, D-panthenol and the like is realized at present.
The existing biological enzyme method is mainly carried out in a reaction kettle, and because mechanical stirring is adopted for hydrolysis and plate-frame filter pressing is adopted for post-treatment, the enzyme is gradually inactivated, and the enzyme is crushed or crushed in the using process, so that the loss is large; in addition, hydrolysis in a reaction kettle is intermittent production, post-treatment processes are complicated and comprise filter pressing, water washing, material mixing, weighing, diluting and feeding, and the like, and the problems of large smell in a production field, high labor intensity of operators, low production efficiency compared with continuous production efficiency and the like exist; the D-pantoic acid lactone series products are bulk products, so that the operation is urgently required to be simplified, the production efficiency is improved, the cost is reduced, and the environmental protection problem is solved.
Disclosure of Invention
The invention aims to provide a method for continuously catalytically preparing D-pantoic acid, which can improve the production efficiency of the D-pantoic acid, reduce the production cost and solve the problem of odor of a production field.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing D-pantoic acid by continuous catalysis, which comprises the following steps:
s1, filling the immobilized enzyme into a group of resin columns connected in series, connecting a storage tank between two adjacent resin columns, and washing with deionized water until the effluent liquid is colorless;
s2, dissolving DL-pantolactone in deionized water, and adjusting the pH value of the DL-pantolactone solution to 6.5-7.5 by using a phosphate buffer solution;
s3, adding activated carbon and a flocculating agent into the DL-pantoic acid lactone solution for decoloring and flocculating to obtain a decoloring solution;
s4, pumping the decolorized solution into a resin column to perform enzymatic hydrolysis reaction to obtain a hydrolysate; adjusting the temperature of the hydrolysate to be 30 +/-2 ℃ on line through a storage tank, wherein the pH value of the hydrolysate is 6.5-7.5;
s5, pumping the hydrolysate into a nanofiltration system, and concentrating and dewatering to obtain nanofiltration solution;
s6, pumping the nanofiltration liquid into a group of extraction columns connected in series, performing multi-stage countercurrent extraction, and recycling the extraction liquid;
s7, and concentrating the raffinate in vacuum to obtain D-pantoic acid.
Further, in the step S1, the diameter of the resin column is 40-100 cm, the ratio of the height to the diameter of the resin column is 8: 1-3: 1, and the number of the resin columns connected in series is 3-5; the volume of the storage tank is 250-1000L.
Further, the concentration of the DL-pantoic acid lactone solution in the step S2 is 20-40%; the phosphate buffer solution is a mixed solution of disodium hydrogen phosphate and sodium dihydrogen phosphate in any proportion.
Further, in the step S3, the activated carbon is needle activated carbon or powdered activated carbon, the flocculating agent is polyaluminium chloride, the dosage of the activated carbon is 1-3% of the weight of the DL-pantoic acid lactone, the dosage of the flocculating agent is 0.5-1.5% of the weight of the DL-pantoic acid lactone, and the decoloration flocculation is 45-60 min.
Further, in the step S5, the nanofiltration temperature is less than or equal to 40 ℃, the water content of the nanofiltration solution is 20-30%, and the nanofiltration wastewater is reused.
Further, in the step S6, the diameter of the extraction column is 30-60 cm, the ratio of the height to the diameter of the extraction column is 12: 1-8: 1, the number of the extraction columns connected in series is 3-4, the extracting agent is ethyl acetate, the flow ratio of the hydrolysate to the extracting agent is 1: 1-1: 1.5, and the optical rotation of the raffinate at the end of extraction is less than or equal to 0.2.
Further, in the step S7, the concentration vacuum degree is more than 0.09MPa, the initial concentration temperature is 30-40 ℃, and the final concentration temperature is 60-70 ℃.
Further, step S3, adding 2% 767 medicinal activated carbon and 1% polyaluminium chloride into DL-pantoic acid lactone solution, controlling the temperature at 30 + -2 deg.C, decolorizing and flocculating for 60min, and coarse filtering and fine filtering the solution to obtain decolorized solution.
Further, in the step S5, the nanofiltration temperature is 10-30 ℃, and the water content of the nanofiltration solution is 25 +/-2%.
The method has the advantages that the D-pantoic acid is prepared by adopting continuous catalysis of enzyme, nanofiltration concentration and continuous multistage countercurrent extraction, wherein the production efficiency of hydrolyzing DL-pantoic acid lactone by continuous catalysis of enzyme is high, the post-treatment is simple, the enzyme loss is less, the efficiency of nanofiltration concentration and water removal is high, the energy consumption is low, the efficiency of multistage countercurrent extraction is high, the extraction is sufficient, and the quality and the yield are favorably improved; the combined use of the three sets of process technologies also solves the problems of heavy smell, solvent volatilization, large amount of waste water and the like in the production field, and has the characteristics of environmental protection, simple operation, low cost and the like.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is a schematic of the present invention.
Detailed Description
Example one
As shown in FIG. 1, the present invention provides a method for continuous catalytic preparation of D-pantoic acid, comprising the steps of:
s1, filling the immobilized enzyme into a group of resin columns 6 connected in series, connecting a storage tank 7 between two adjacent resin columns, washing with deionized water until the effluent liquid turns from light black to yellow and finally turns to colorless, stopping washing with water, controlling the flow rate of washing with water at 0.3Bv/h, and loosening after washing with water for later use;
s2, adding 350kg of DL-pantolactone (depurate) and deionized water into a 1500L dissolving and decoloring kettle 1, uniformly stirring, controlling the temperature to be 30 +/-2 ℃, and adjusting the pH value of the DL-pantolactone solution to be 7.5 by using a phosphate buffer solution;
s3, adding 7kg 767 kg of medicinal activated carbon and 3.5kg of polyaluminium chloride into a dissolving and decoloring kettle 1, decoloring and flocculating for 60min, after decoloring and flocculating, roughly filtering the solution by a square meter plate and frame filter 2 (filter cloth 800 meshes) and a fine filter 3 (3 filter core 5 micron polypropylene filter core), and finely filtering to obtain decoloring solution;
s4, pumping the decolorized solution into a resin column 6 for enzymatic hydrolysis, controlling the temperature to be 30 +/-2 ℃, adjusting the pH value to be 7.5 on line by using a phosphate buffer solution when the hydrolysate enters a storage tank, and then pumping the hydrolysate into the next resin column, wherein the flow rate of the hydrolysate is controlled to be 0.5 Bv/h; performing optical rotation on the hydrolysate flowing out of the third resin column for 5.9, and putting the hydrolysate into a storage tank;
s5, controlling the temperature to be 10-30 ℃, and carrying out nanofiltration concentration on the hydrolysate by using a nanofiltration device 9 until the moisture of the nanofiltration solution is 25%;
s6, pumping the nanofiltration liquid into a group of extraction columns 10 connected in series, performing four-stage countercurrent extraction by using ethyl acetate, recycling the extraction liquid, wherein the flow rate ratio is 1:1, and the optical rotation of the raffinate is 0;
s7, controlling the vacuum degree to be more than 0.095Mpa, concentrating at the temperature of 60-70 ℃, and concentrating the raffinate to remove moisture to obtain the D-pantoic acid, wherein the purity is 97.5%, and the content of DL-pantoic acid lactone is 2%.
Example two
As shown in FIG. 1, the present invention provides a method for continuous catalytic preparation of D-pantoic acid, comprising the steps of:
s1, filling the immobilized enzyme into a group of resin columns 6 connected in series, connecting a storage tank 7 between two adjacent resin columns, washing with deionized water until the effluent liquid turns from light black to yellow and finally turns to colorless, stopping washing with water, controlling the flow rate of washing with water at 0.3Bv/h, and loosening after washing with water for later use;
s2, adding 350kg of DL-pantolactone (depurate) and deionized water into a 1500L dissolving and decoloring kettle 1, uniformly stirring, controlling the temperature to be 30 +/-2 ℃, and adjusting the pH value of the DL-pantolactone solution to be 7.0 by using a phosphate buffer solution;
s3, adding 7kg 767 kg of medicinal activated carbon and 3.5kg of polyaluminium chloride into a dissolving and decoloring kettle 1, decoloring and flocculating for 60min, after decoloring and flocculating, roughly filtering the solution by a square meter plate and frame filter 2 (filter cloth 800 meshes) and a fine filter 3 (3 filter core 5 micron polypropylene filter core), and finely filtering to obtain decoloring solution;
s4, pumping the decolorized solution into a resin column 6 for enzymatic hydrolysis, controlling the temperature to be 30 +/-2 ℃, adjusting the pH value to be 7.0 on line by using a phosphate buffer solution when the hydrolysate enters a storage tank, and then pumping the hydrolysate into the next resin column, wherein the flow rate of the hydrolysate is controlled to be 1 Bv/h; performing optical rotation on the hydrolysate flowing out of the fourth resin column for 5.7, and putting the hydrolysate into a storage tank;
s5, controlling the temperature to be 10-30 ℃, and carrying out nanofiltration concentration on the hydrolysate by using a nanofiltration device 9 until the moisture of the nanofiltration solution is 25%;
s6, pumping the nanofiltration liquid into a group of extraction columns 10 connected in series, performing four-stage countercurrent extraction by using ethyl acetate, recycling the extraction liquid, wherein the flow rate ratio is 1:1.2, and the optical rotation of the raffinate is 0.11;
s7, controlling the vacuum degree to be more than 0.095Mpa, concentrating at the temperature of 60-70 ℃, and concentrating the raffinate to remove moisture to obtain the D-pantoic acid with the purity of 96.6% and the DL-pantoic acid lactone content of 3%.
EXAMPLE III
As shown in FIG. 1, the present invention provides a method for continuous catalytic preparation of D-pantoic acid, comprising the steps of:
s1, filling the immobilized enzyme into a group of resin columns 6 connected in series, connecting a storage tank 7 between two adjacent resin columns, washing with deionized water until the effluent liquid turns from light black to yellow and finally turns to colorless, stopping washing with water, controlling the flow rate of washing with water at 0.3Bv/h, and loosening after washing with water for later use;
s2, adding 350kg of DL-pantolactone (depurate) and deionized water into a 1500L dissolving and decoloring kettle 1, uniformly stirring, controlling the temperature to be 30 +/-2 ℃, and adjusting the pH value of the DL-pantolactone solution to be 6.5 by using a phosphate buffer solution;
s3, adding 7kg 767 kg of medicinal activated carbon and 3.5kg of polyaluminium chloride into a dissolving and decoloring kettle 1, decoloring and flocculating for 60min, after decoloring and flocculating, roughly filtering the solution by a square meter plate and frame filter 2 (filter cloth 800 meshes) and a fine filter 3 (3 filter core 5 micron polypropylene filter core), and finely filtering to obtain decoloring solution;
s4, pumping the decolorized solution into a resin column 6 for enzymatic hydrolysis, controlling the temperature to be 30 +/-2 ℃, adjusting the pH value to be 6.5 on line by using a phosphate buffer solution when the hydrolysate enters a storage tank, and then pumping the hydrolysate into the next resin column, wherein the flow rate of the hydrolysate is controlled to be 1 Bv/h; performing optical rotation on the hydrolysate flowing out of the fifth resin column for 5.6, and putting the hydrolysate into a storage tank;
s5, controlling the temperature to be 10-30 ℃, and carrying out nanofiltration concentration on the hydrolysate by using a nanofiltration device 9 until the moisture of the nanofiltration solution is 25%;
s6, pumping the nanofiltration liquid into a group of extraction columns 10 connected in series, performing four-stage countercurrent extraction by using ethyl acetate, recycling the extraction liquid, wherein the flow rate ratio is 1:1.5, and the optical rotation of the raffinate is 0.18;
s7, controlling the vacuum degree to be more than 0.095Mpa, concentrating at the temperature of 60-70 ℃, and concentrating the raffinate to remove moisture to obtain the D-pantoic acid, wherein the purity is 95.7%, and the content of DL-pantoic acid lactone is 3.6%.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; those skilled in the art can make numerous possible variations and modifications to the present teachings, or modify equivalent embodiments to equivalent variations, without departing from the scope of the present teachings, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (9)
1. A method for preparing D-pantoic acid by continuous catalysis, which is characterized by comprising the following steps:
s1, filling the immobilized enzyme into a group of resin columns connected in series, connecting a storage tank between two adjacent resin columns, and washing with deionized water until the effluent liquid is colorless;
s2, dissolving DL-pantolactone in deionized water, and adjusting the pH value of the DL-pantolactone solution to 6.5-7.5 by using a phosphate buffer solution;
s3, adding activated carbon and a flocculating agent into the DL-pantoic acid lactone solution for decoloring and flocculating to obtain a decoloring solution;
s4, pumping the decolorized solution into a resin column to perform enzymatic hydrolysis reaction to obtain a hydrolysate; adjusting the temperature of the hydrolysate to be 30 +/-2 ℃ on line through a storage tank, wherein the pH value of the hydrolysate is 6.5-7.5;
s5, pumping the hydrolysate into a nanofiltration system, and concentrating and dewatering to obtain nanofiltration solution;
s6, pumping the nanofiltration liquid into a group of extraction columns connected in series, performing multi-stage countercurrent extraction, and recycling the extraction liquid;
s7, and concentrating the raffinate in vacuum to obtain D-pantoic acid.
2. The continuous catalytic preparation method of D-pantoic acid according to claim 1, wherein the diameter of the resin column in step S1 is 40-100 cm, the ratio of the height to the diameter of the resin column is 8: 1-3: 1, and the number of the resin columns connected in series is 3-5; the volume of the storage tank is 250-1000L.
3. The method for continuously and catalytically preparing D-pantoic acid according to claim 1, wherein the concentration of the DL-pantoic acid lactone solution in step S2 is 20-40%; the phosphate buffer solution is a mixed solution of disodium hydrogen phosphate and sodium dihydrogen phosphate in any proportion.
4. The method for continuously and catalytically preparing D-pantoic acid according to claim 1, wherein the activated carbon in step S3 is needle activated carbon or powdered activated carbon, the flocculating agent is polyaluminium chloride, the amount of the activated carbon is 1-3% by weight of DL-pantoic acid lactone, the amount of the flocculating agent is 0.5-1.5% by weight of DL-pantoic acid lactone, and the decoloring and flocculating steps are 45-60 min.
5. The method for continuously catalytically preparing D-pantoic acid according to claim 1, wherein the nanofiltration temperature of step S5 is not more than 40 ℃, the water content of the nanofiltration solution is 20-30%, and the nanofiltration wastewater is used indiscriminately.
6. The method of claim 1, wherein the diameter of the extraction column in step S6 is 30-60 cm, the ratio of the height to the diameter of the extraction column is 12: 1-8: 1, the number of the extraction columns connected in series is 3-4, the extractant is ethyl acetate, the flow ratio of the hydrolysate to the extractant is 1: 1-1: 1.5, and the end point of the extraction is that the optical rotation of the raffinate is less than or equal to 0.2.
7. The method for continuously and catalytically preparing D-pantoic acid according to claim 1, wherein the concentration degree of vacuum of step S7 is more than 0.09MPa, the initial concentration temperature is 30 to 40 ℃, and the final concentration temperature is 60 to 70 ℃.
8. The method for continuously catalytic preparation of D-pantoic acid according to claim 4, wherein step S3 is adding 2% 767 pharmaceutical activated carbon and 1% polyaluminium chloride to DL-pantoic acid lactone solution, controlling the temperature at 30 ± 2 ℃, decolorizing and flocculating for 60min, and coarse and fine filtering the solution to obtain decolorized solution.
9. The method for continuously catalytically preparing D-pantoic acid according to claim 5, wherein the nanofiltration temperature of step S5 is 10-30 ℃, and the nanofiltration liquid has a water content of 25 ± 2%.
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| JPH04335890A (en) * | 1991-05-08 | 1992-11-24 | Tanabe Seiyaku Co Ltd | Reaction process using immobilized biocatalyst and apparatus therefor |
| US6214609B1 (en) * | 1997-05-01 | 2001-04-10 | Monsanto Company | Method and apparatus for preparation of chiral beta amino acids using penicilln G acylase |
| CN1313402A (en) * | 2001-02-21 | 2001-09-19 | 浙江鑫富生化股份有限公司 | Process for preparing D-lactone valerate by microbe enzyme method |
| CN101538564A (en) * | 2009-04-29 | 2009-09-23 | 河北宝利药业有限公司 | Immobilization method of D-pantoic acid lactone hydrolase |
| CN111979288A (en) * | 2019-05-24 | 2020-11-24 | 重庆桑禾动物药业有限公司 | Method for continuously decomposing mixed pantolactone by enzymolysis through fixed bed device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04335890A (en) * | 1991-05-08 | 1992-11-24 | Tanabe Seiyaku Co Ltd | Reaction process using immobilized biocatalyst and apparatus therefor |
| US6214609B1 (en) * | 1997-05-01 | 2001-04-10 | Monsanto Company | Method and apparatus for preparation of chiral beta amino acids using penicilln G acylase |
| CN1313402A (en) * | 2001-02-21 | 2001-09-19 | 浙江鑫富生化股份有限公司 | Process for preparing D-lactone valerate by microbe enzyme method |
| CN101538564A (en) * | 2009-04-29 | 2009-09-23 | 河北宝利药业有限公司 | Immobilization method of D-pantoic acid lactone hydrolase |
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