CN114560783B - Extraction method of L-tyrosine in conversion solution - Google Patents
Extraction method of L-tyrosine in conversion solution Download PDFInfo
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- CN114560783B CN114560783B CN202210162122.5A CN202210162122A CN114560783B CN 114560783 B CN114560783 B CN 114560783B CN 202210162122 A CN202210162122 A CN 202210162122A CN 114560783 B CN114560783 B CN 114560783B
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- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 title claims abstract description 133
- 229960004441 tyrosine Drugs 0.000 title claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 55
- 238000000605 extraction Methods 0.000 title claims description 10
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims abstract description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000047 product Substances 0.000 claims abstract description 42
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 22
- 239000012452 mother liquor Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000001728 nano-filtration Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 19
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 50
- 239000000758 substrate Substances 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229940107700 pyruvic acid Drugs 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 108091000100 Tyrosine Phenol-Lyase Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 aromatic amino acid Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QVKZWRGZMUGTLO-QRPNPIFTSA-N (2s)-2-amino-3-(4-hydroxyphenyl)propanoic acid;hydrate Chemical compound O.OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 QVKZWRGZMUGTLO-QRPNPIFTSA-N 0.000 description 1
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 description 1
- 229930182837 (R)-adrenaline Natural products 0.000 description 1
- XUIIKFGFIJCVMT-GFCCVEGCSA-N D-thyroxine Chemical compound IC1=CC(C[C@@H](N)C(O)=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-GFCCVEGCSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 229960005139 epinephrine Drugs 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940034208 thyroxine Drugs 0.000 description 1
- XUIIKFGFIJCVMT-UHFFFAOYSA-N thyroxine-binding globulin Natural products IC1=CC(CC([NH3+])C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for extracting L-tyrosine in a conversion solution, which comprises the following steps: (1) Adding alkali liquor into the tyrosine conversion solution, and preserving heat to dissolve solid tyrosine contained in the tyrosine conversion solution; (2) Filtering the dissolved conversion solution with ceramic membrane, maintaining the temperature of the ceramic membrane filtrate, neutralizing with dilute hydrochloric acid to pH5.0-5.5, crystallizing, centrifuging, and collecting crude crystals; (3) Adding the crude product into water, dissolving with dilute hydrochloric acid solution at a constant temperature, and decolorizing with active carbon; (4) Neutralizing the decolorized clear liquid with ammonia water, and centrifuging to collect refined product, namely L-tyrosine product; (5) The refined mother liquor is decolorized by a nanofiltration membrane and then is used as ammonium chloride mother liquor to be added into the preparation raw material of the next batch of tyrosine conversion solution. The invention optimizes and improves the membrane pretreatment process, the crystallization control process and the mother liquor recovery process, and aims to reduce the production cost and improve the product quality.
Description
Technical Field
The invention relates to a method for extracting L-tyrosine in a conversion solution, belonging to the field of biochemical engineering.
Background
L-tyrosine is an aromatic amino acid, which is a non-essential amino acid. In medicine, L-tyrosine is a precursor raw material for synthesizing thyroxine, epinephrine, levodopa and the like; the application of the product as a functional food with sedative and antidepressant effects is also becoming widespread. There are generally four routes for preparing L-tyrosine, namely (1) extraction (2) direct fermentation (3) enzymatic conversion (4) organic synthesis. The enzyme conversion method uses phenol, ammonia and pyruvic acid as precursors, and converts the precursor by beta-tyrosinase, so that the method has less pollution, high product quality and good industrial application value.
The extraction modes of the L-tyrosinase conversion liquid are different, a simple acid-dissolution and alkali-precipitation treatment method is adopted in CN103343149A, tyrosine is obtained by primary crystallization, and the process is simple, but the yield is low and the product quality is poor. In CN105441502A, the tyrosine conversion solution is treated by combining the supercritical extraction technology with the ultrafiltration and nanofiltration membrane technology, and the crystal is obtained by freeze drying (the fermentation liquor is centrifuged and ultrafiltered to obtain ultrafiltrate, the pH value and the ionic strength of the ultrafiltrate are regulated, the surfactant and the ultrafiltrate are added into a supercritical extractor, the surfactant and the supercritical fluid form a supercritical fluid reverse micelle system to carry out supercritical extraction on L-tyrosine, the reverse extraction aqueous phase solution and the extraction product are added into the supercritical extractor to carry out supercritical reverse extraction, and the water phase is subjected to nanofiltration, crystallization and freeze drying after the reverse extraction to obtain purified L-tyrosine). In CN103224972A, a similar acid-soluble alkali-soluble separation process (10 mol/L sodium hydroxide is added dropwise to adjust the pH value to 12-13, stirring is carried out and the temperature is raised to 80 ℃, the pH value of filtrate is adjusted to 6 by 6mol/L hydrochloric acid, and the required L-tyrosine is obtained after drying), and the product is obtained through one-step cooling crystallization, so that the separation of substrate phenol is not facilitated, and the phenol may be remained in the product. In CN105969819A (a method for producing L-tyrosine by an enzymatic method), the conversion solution is treated by a ceramic membrane, so that impurities such as macromolecular proteins, pigments and the like can be removed to a great extent, but the corrosion of stainless steel materials can be caused by the treatment of strong acid solution by ceramic membrane equipment at high temperature, and the adverse effects on equipment and product quality are caused.
Disclosure of Invention
Aiming at the defects in the prior art and the increasingly strict requirements on the quality of tyrosine products in the market, the invention provides a method for extracting L-tyrosine in conversion liquid, which optimizes and improves a membrane pretreatment process, a crystallization control process and a mother liquor recovery process, and aims at reducing the production cost and improving the product quality.
The extraction method of L-tyrosine in the conversion solution provided by the invention comprises the following steps:
(1) Adding alkali liquor into the tyrosine conversion solution, and preserving heat to dissolve solid tyrosine contained in the tyrosine conversion solution;
(2) Filtering the dissolved conversion solution with ceramic membrane, maintaining the temperature of the ceramic membrane filtrate, neutralizing with dilute hydrochloric acid to pH5.0-5.5, crystallizing, centrifuging, and collecting crude crystals;
(3) Adding the crude product into water, dissolving with dilute hydrochloric acid solution at a constant temperature, and decolorizing with active carbon;
(4) Neutralizing the decolorized clear liquid with ammonia water, and centrifuging to collect refined product, namely L-tyrosine product;
(5) The refined mother liquor is decolorized by a nanofiltration membrane and then is used as ammonium chloride mother liquor to be added into the preparation raw material of the next batch of tyrosine conversion solution.
In the step (1) of the method, the tyrosine conversion solution is prepared by using tyrosine phenol lyase to catalyze substrates such as pyruvic acid, ammonium chloride and the like, and the content of tyrosine in the conversion solution can be 130-150g/L;
the alkali liquor can be sodium hydroxide solution with the mass concentration of 5% -10%, the pH value of the tyrosine conversion solution is regulated to 10-12 after the alkali liquor is added, and the temperature for heat preservation can be 70 ℃ -80 ℃;
in the step (2) of the method, the ceramic film is a 50nm ceramic film;
the operating pressure of the ceramic membrane filtration can be 0.1-0.15MPa, and the temperature can be 70-75 ℃;
The dilute hydrochloric acid can be specifically dilute hydrochloric acid with the mass concentration of 3-5%, and the temperature for heat preservation can be 70-75 ℃;
in the step (3) of the method, the volume of water is 3-5 times of the mass of the crude product;
the dilute hydrochloric acid solution can be hydrochloric acid with the mass concentration of 10-15%;
adding dilute hydrochloric acid solution into the crude product to be fully dissolved;
the temperature of the heat preservation can be 70-75 ℃;
the addition amount of the activated carbon is 10-15g/L,
Adding active carbon, preserving heat at 70-75 ℃, stirring for 0.5h, and carrying out suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid;
in the step (4), the decolorized clear solution is neutralized to pH5.0-5.5 by ammonia water with mass concentration of 10-15%, and the temperature is kept at 60-70 ℃ and the refined product is collected by centrifugation while the solution is hot.
In the step (5), the nanofiltration membrane is decolored by NF800 or NF500, the operation pressure is 1.0-1.5MPa, and the temperature is 40-45 ℃.
The invention adopts alkali liquor to dissolve a large amount of solid tyrosine contained in the tyrosine conversion solution, thereby avoiding the corrosion of strong acid (sulfuric acid and hydrochloric acid) to a ceramic membrane system (stainless steel pipeline and circulating pump) at high temperature;
The tyrosine crystallization adopts an isoelectric point crystallization process, but a small amount of substrate phenol remains in the tyrosine conversion process, the phenol is insoluble in cold water and slightly soluble in hot water, and the phenol can be mixed with water at a temperature above 65 ℃, so that the high temperature is maintained in the crystallization process and the centrifugal collection process of crystals, thereby being beneficial to reducing the phenol residues in the tyrosine crystallization;
Besides less than 1g/L of tyrosine, the refined mother solution also contains 0.5-1.0mol/L of ammonium chloride, namely 26.25-52.5g/L, and the ammonium chloride is a reaction substrate for preparing the tyrosine, so that the refined mother solution can be recycled and used as a substrate solution for the next batch of reaction after nanofiltration decoloration treatment, the production cost can be reduced, and the method is more beneficial to recycling and recycling the high ammonia nitrogen wastewater needing environmental protection treatment, so that the environmental protection pressure is greatly reduced.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The L-tyrosine conversion solution used in the following examples was obtained by the following method:
conversion reaction:
Keeping the temperature at 37 ℃ for reaction, controlling the contents of phenol and pyruvic acid to be not more than 8g/L and 10g/L respectively, adding 10g/L ammonium chloride (or recovered ammonium chloride solution, calculated by the pure ammonium chloride of 10 g/L) in 2, 4 and 6 hours respectively, stopping adding substrate until the reaction time is 10 hours, and stopping the reaction until the phenol content is lower than 0.5 g/L.
Since the solubility of tyrosine water is very low, obvious crystals are precipitated in the conversion solution after the conversion reaction is carried out for 10min, and the crystals are more and more increased along with the extension of the reaction time. After all tyrosine in the conversion solution is dissolved, the tyrosine content in the reaction system is converted according to volume change.
L-tyrosine content detection HPLC method in the following examples
Chromatographic column: ODS C18 (4.6X250 mm,5 μm)
Mobile phase: methanol: water=15:85
Flow rate: 1.0ml/min
Wavelength: 280nm of
Column temperature: 30 ℃.
Example 1
L-tyrosine conversion solution (the content of tyrosine is 135.62 g/L), the volume is 20L, the temperature is raised to 70 ℃, the pH value is regulated to be 12.0 by using sodium hydroxide solution with the mass concentration of 5%, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 70deg.C under 0.1 MPa; preserving heat at 60 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with the mass concentration of 3% to filter the clear liquid until the pH value is 5.5, centrifuging and collecting crystals to obtain a crude product; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve, adding active carbon with the mass concentration of 1% being 10g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, maintaining the temperature at 60deg.C, and centrifuging while hot to collect the refined product. The quality of the obtained refined product is 2457.4g after drying, the yield is 90.6%, and the L-tyrosine content is 99.86% by HPLC.
The refined mother liquor is decolored by NF800, the operating pressure is 1.0MPa, the temperature is 40 ℃, and the ammonia nitrogen is detected and converted into the ammonium chloride with the concentration of 42g/L, so that the refined mother liquor is used as a substrate for the next tyrosine conversion.
Example 2
L-tyrosine conversion solution (the content of tyrosine is 138.95 g/L), the volume is 25L, the temperature is raised to 80 ℃, the pH value is regulated to 11.5 by 10% sodium hydroxide solution with mass concentration, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 75 deg.c and operation pressure of 0.15 MPa; preserving heat at 70 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with mass concentration of 5% to filter the clear liquid to pH5.0, centrifuging and collecting crystals to obtain crude products; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 15%, keeping the temperature at 70 ℃ to enable the hydrochloric acid to be completely dissolved, adding active carbon with the mass concentration of 1.5% which is 15g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 15% ammonia water to pH5.5, maintaining the temperature at 70deg.C, and centrifuging while hot to collect the refined product. The quality after drying is 3168.1, the yield is 91.2%, and the L-tyrosine content is 99.91% by HPLC.
The refined mother liquor is decolored by NF500, the operating pressure is 1.5MPa, the temperature is 45 ℃, and the ammonia nitrogen detection is converted into the concentration of ammonium chloride to be 48.5g/L, and the ammonium chloride is used as a substrate for the next tyrosine conversion.
Comparative example 1
L-tyrosine conversion solution (the content of tyrosine is 132.5 g/L), the volume is 20L, the temperature is raised to 70 ℃, the pH value is regulated to be 12 by a sodium hydroxide solution with the mass concentration of 5%, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 70deg.C under 0.1 MPa; preserving heat at 60 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with the mass concentration of 3% to filter the clear liquid until the pH value is 4.5, centrifuging and collecting crystals to obtain a crude product; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve, adding active carbon with the mass concentration of 1% being 10g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, maintaining the temperature at 60deg.C, and centrifuging while hot to collect the refined product. The quality of the obtained refined product is 2350.5g after drying, the yield is 88.7%, and the L-tyrosine content is 99.87% by HPLC. The pH of the primary neutralization crystallization was lowered and the yield of the obtained product was significantly lowered as compared with example 1.
The refined mother liquor is decolored by NF800, the operating pressure is 1.0MPa, the temperature is 40 ℃, and the ammonia nitrogen is detected and converted into the ammonium chloride with the concentration of 41.2g/L, so that the refined mother liquor is used as a substrate for the next tyrosine conversion.
Comparative example 2
L-tyrosine conversion solution (the content of tyrosine is 140.2 g/L), the volume is 20L, the temperature is raised to 70 ℃, the pH value is regulated to be 12 by a sodium hydroxide solution with the mass concentration of 5%, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 70deg.C under 0.1 MPa; preserving heat at 60 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with the mass concentration of 3% to filter the clear liquid to pH6.8, centrifuging and collecting crystals to obtain a crude product; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve, adding active carbon with the mass concentration of 1% being 10g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.8, maintaining the temperature at 60deg.C, and centrifuging while hot to collect the refined product. The quality of the obtained refined product is 2593.7g after drying, the yield is 93.5%, and the L-tyrosine content is 96.1% by HPLC. Compared with example 1, the pH value of the primary neutralization crystallization is increased, and the L-tyrosine content of the obtained product is obviously reduced. From comparative examples 1 and 2, it was found that the pH of the neutralization crystals had a significant effect on the quality of the L-tyrosine product.
The refined mother liquor is decolored by NF800, the operating pressure is 1.0MPa, the temperature is 40 ℃, and the ammonia nitrogen is detected and converted into the ammonium chloride with the concentration of 49.3g/L, so that the refined mother liquor is used as a substrate for the next tyrosine conversion.
Comparative example 3
L-tyrosine conversion solution (the content of tyrosine is 135.8 g/L), the volume is 20L, the temperature is raised to 70 ℃, the pH value is regulated to be 12 by a sodium hydroxide solution with the mass concentration of 5%, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 70deg.C under 0.1 MPa; preserving heat at 60 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with the mass concentration of 8.0% to filter the clear liquid until the pH value is 5.5, centrifuging and collecting crystals to obtain a crude product; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve, adding active carbon with the mass concentration of 1% being 10g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, maintaining the temperature at 60deg.C, and centrifuging while hot to collect the refined product. The quality of the obtained refined product is 2447.1g after drying, the yield is 90.1%, and the L-tyrosine content is 98.62% by HPLC. Compared with example 1, the mass concentration of the dilute hydrochloric acid used for one neutralization is increased, and the L-tyrosine content of the obtained product is reduced.
The refined mother liquor is decolorized by NF800 and then used as a substrate for the next tyrosine conversion.
Comparative example 4
L-tyrosine conversion solution (the content of tyrosine is 136.8 g/L), the volume is 20L, the temperature is raised to 70 ℃, the pH value is regulated to be 12 by a sodium hydroxide solution with the mass concentration of 5%, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 70deg.C under 0.1 MPa; preserving heat at 60 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with the mass concentration of 2.0% to filter the clear liquid until the pH value is 5.5, centrifuging and collecting crystals to obtain a crude product; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve, adding active carbon with the mass concentration of 1% being 10g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, maintaining the temperature at 60deg.C, and centrifuging while hot to collect the refined product. The quality of the obtained refined product is 2382.2g after drying, the yield is 87.1%, and the L-tyrosine content is 99.79% by HPLC. The mass concentration of the diluted hydrochloric acid used for the primary neutralization is reduced compared with that of example 1, and the yield of the obtained product is obviously reduced. From comparative examples 3 and 4, it was found that the concentration of hydrochloric acid used for one neutralization was critical to the quality of the L-tyrosine product.
The refined mother liquor is decolorized by NF800 and then used as a substrate for the next tyrosine conversion.
Comparative example 5
L-tyrosine conversion solution (the content of tyrosine is 135.6 g/L), the volume is 20L, the temperature is raised to 70 ℃, the pH value is regulated to be 12.0 by using sodium hydroxide solution with the mass concentration of 5%, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 70deg.C under 0.1 MPa; preserving heat at 60 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with the mass concentration of 3% to filter the clear liquid until the pH value is 5.5, centrifuging and collecting crystals to obtain a crude product; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve, adding active carbon with the mass concentration of 1% being 10g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 5% ammonia water to pH5.0, maintaining the temperature at 60deg.C, and centrifuging while hot to collect refined product. The quality of the obtained refined product is 2294.7g after drying, the yield is 84.6%, and the L-tyrosine content is 99.91% by HPLC. Compared with example 1, the mass concentration of the ammonia water used for secondary neutralization is reduced, and the yield is obviously reduced.
The refined mother liquor is decolorized by NF800 and then used as a substrate for the next tyrosine conversion.
Comparative example 6
L-tyrosine conversion solution (the content of tyrosine is 135.71 g/L), the volume is 20L, the temperature is raised to 70 ℃, the pH value is regulated to be 12.0 by using sodium hydroxide solution with the mass concentration of 5%, and the temperature is kept and the stirring is carried out until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 70deg.C under 0.1 MPa; preserving heat at 60 ℃, neutralizing the ceramic membrane with dilute hydrochloric acid with the mass concentration of 3% to filter the clear liquid until the pH value is 5.5, centrifuging and collecting crystals to obtain a crude product; adding the crude product into water with the volume of 5 times, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve, adding active carbon with the mass concentration of 1% being 10g/L, keeping the temperature and stirring for 0.5h; filtering or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 18% ammonia water to pH5.0, maintaining the temperature at 60deg.C, and centrifuging while hot to collect the refined product. The quality of the obtained refined product is 2538.8g after drying, the yield is 93.6%, and the L-tyrosine content is 95.2% by HPLC. Compared with the example 1, the mass concentration of the ammonia water used for secondary neutralization is increased, the content is obviously reduced, and the influence on the product quality is larger.
As can be seen from comparative examples 5 and 6, the mass concentration of the aqueous ammonia used for the secondary neutralization is also critical to the quality of the L-tyrosine product.
The refined mother liquor is decolorized by NF800 and then used as a substrate for the next tyrosine conversion.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the application and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains.
Claims (5)
1. The extraction method of L-tyrosine in the conversion liquid comprises the following steps:
(1) Adding alkali liquor into the tyrosine conversion solution, and preserving heat to dissolve solid tyrosine contained in the tyrosine conversion solution;
(2) Filtering the dissolved conversion solution with ceramic membrane, maintaining the temperature of the ceramic membrane filtrate, neutralizing with dilute hydrochloric acid to pH5.0-5.5, crystallizing, centrifuging, and collecting crude crystals;
(3) Adding the crude product into water, dissolving with dilute hydrochloric acid solution at a constant temperature, and decolorizing with active carbon;
(4) Neutralizing the decolorized clear liquid with ammonia water, and centrifuging to collect refined product, namely L-tyrosine product;
(5) Decolorizing the refined mother liquor by a nanofiltration membrane to obtain ammonium chloride mother liquor, and adding the ammonium chloride mother liquor into the preparation raw material of the next batch of tyrosine conversion solution;
In the step (1), the pH value of the tyrosine conversion solution is regulated to 10-12 after alkali liquor is added;
In the step (2), the dilute hydrochloric acid is dilute hydrochloric acid with the mass concentration of 3% -5%;
In the step (3), the dilute hydrochloric acid solution is hydrochloric acid with the mass concentration of 10% -15%;
In the step (4), the decolorized clear solution is neutralized to pH5.0-5.5 by ammonia water with the mass concentration of 10-15%, the temperature is kept at 60-70 ℃, and the refined product is collected by centrifugation while the decolorized clear solution is hot.
2. The method according to claim 1, characterized in that: in the step (1), the content of tyrosine in the conversion solution is 130-150g/L;
the alkali liquor is sodium hydroxide solution with the mass concentration of 5% -10%, and the temperature of heat preservation is 70 ℃ -80 ℃.
3. The method according to claim 1, characterized in that: in the step (2), the ceramic film is a 50nm ceramic film;
the operating pressure of the ceramic membrane filtration is 0.1-0.15MPa, and the temperature is 70-75 ℃;
the temperature of the heat preservation is 70-75 ℃.
4. The method according to claim 1, characterized in that: in the step (3), the volume of water is 3-5 times of the mass of the crude product;
The temperature of the heat preservation is 70-75 ℃;
the addition amount of the activated carbon is 10-15g/L,
Adding active carbon, maintaining the temperature at 70-75 ℃, stirring for 0.5h, and carrying out suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid.
5. The method according to claim 1, characterized in that: in the step (5), the nanofiltration membrane is decolored by NF800 or NF500, the operation pressure is 1.0-1.5MPa, and the temperature is 40-45 ℃.
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| US3787287A (en) * | 1970-07-17 | 1974-01-22 | Kyowa Hakko Kogyo Kk | Process for the production of l-tyrosine |
| JPH04360859A (en) * | 1991-06-07 | 1992-12-14 | Ajinomoto Co Inc | Purification of tyrosine by hydrochloride crystallization method |
| JP2005287436A (en) * | 2004-04-01 | 2005-10-20 | Mitsui Chemicals Inc | Method for producing l-tyrosine |
| CN110950769A (en) * | 2019-12-17 | 2020-04-03 | 天津科技大学 | Method for centrifugally extracting tyrosine from fermentation liquor |
| CN111039808A (en) * | 2019-12-06 | 2020-04-21 | 天津科技大学 | Method for extracting tyrosine from fermentation liquor |
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Patent Citations (5)
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|---|---|---|---|---|
| US3787287A (en) * | 1970-07-17 | 1974-01-22 | Kyowa Hakko Kogyo Kk | Process for the production of l-tyrosine |
| JPH04360859A (en) * | 1991-06-07 | 1992-12-14 | Ajinomoto Co Inc | Purification of tyrosine by hydrochloride crystallization method |
| JP2005287436A (en) * | 2004-04-01 | 2005-10-20 | Mitsui Chemicals Inc | Method for producing l-tyrosine |
| CN111039808A (en) * | 2019-12-06 | 2020-04-21 | 天津科技大学 | Method for extracting tyrosine from fermentation liquor |
| CN110950769A (en) * | 2019-12-17 | 2020-04-03 | 天津科技大学 | Method for centrifugally extracting tyrosine from fermentation liquor |
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