CN114560783A - Method for extracting L-tyrosine from conversion solution - Google Patents
Method for extracting L-tyrosine from conversion solution Download PDFInfo
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- CN114560783A CN114560783A CN202210162122.5A CN202210162122A CN114560783A CN 114560783 A CN114560783 A CN 114560783A CN 202210162122 A CN202210162122 A CN 202210162122A CN 114560783 A CN114560783 A CN 114560783A
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- tyrosine
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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 50
- 238000000034 method Methods 0.000 title claims abstract description 34
- 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 48
- 239000000047 product Substances 0.000 claims abstract description 42
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012043 crude product Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 27
- 239000012452 mother liquor Substances 0.000 claims abstract description 24
- 239000000919 ceramic Substances 0.000 claims abstract description 23
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000019270 ammonium chloride Nutrition 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
- 238000004321 preservation Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 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 7
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 238000003825 pressing Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 230000009466 transformation Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- 230000008569 process 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 66
- 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 229940107700 pyruvic acid Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 230000002255 enzymatic 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
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 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
- 238000013459 approach Methods 0.000 description 1
- -1 aromatic amino acid Chemical class 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying 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
- 239000010413 mother solution Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 238000000926 separation method Methods 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 from a conversion solution, which comprises the following steps: (1) adding alkali liquor into the tyrosine conversion solution, and dissolving solid tyrosine contained in the tyrosine conversion solution by heat preservation; (2) filtering the dissolved conversion solution by using a ceramic membrane, preserving the temperature of the ceramic membrane filtrate, neutralizing the filtrate to pH5.0-5.5 by using dilute hydrochloric acid, crystallizing, and centrifugally collecting crude crystals; (3) adding the crude product into water, dissolving with dilute hydrochloric acid solution under heat preservation, and decolorizing with activated carbon; (4) neutralizing the decolored clear liquid with ammonia water, centrifuging and collecting fine products, namely L-tyrosine products; (5) and (3) decoloring the refined mother liquor by using a nanofiltration membrane to serve as ammonium chloride mother liquor, and adding the ammonium chloride mother liquor into a preparation raw material of the tyrosine conversion solution of the next batch. 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 from a conversion solution, belonging to the field of biochemical engineering.
Background
L-tyrosine is an aromatic amino acid, a non-essential amino acid. In medicine, L-tyrosine is a precursor raw material for synthesizing thyroxine, epinephrine, levodopa, and the like; it is also widely used as a functional food with sedative and antidepressant effects. There are four general approaches to the preparation of L-tyrosine, namely (1) extraction method, (2) direct fermentation method, (3) enzymatic conversion method and (4) organic synthesis method. The enzymatic conversion method takes phenol, ammonia and pyruvic acid as precursors and carries out conversion by beta-tyrosinase, and the method has the advantages of less pollution, high product quality and good industrial application value.
The extraction method of the L-tyrosinase conversion solution is different, a simple acid-soluble alkaline-precipitation treatment method is used in CN103343149A, tyrosine is obtained through one-time crystallization, although the process is simple, the yield is low, and the product quality is poor. In CN105441502A, a supercritical extraction technology, an ultrafiltration and nanofiltration membrane technology are combined to process a tyrosine conversion solution, and freeze drying is used to obtain crystals (fermentation liquor is centrifuged and ultrafiltered to obtain ultrafiltrate, the pH value and the ionic strength of the ultrafiltrate are adjusted, a 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, a back extraction water phase solution and an extraction product are added into the supercritical extractor to carry out supercritical back extraction, and the back extraction water phase is subjected to nanofiltration, crystallization and freeze drying to obtain purified L-tyrosine). CN103224972A adopts a similar acid-soluble alkaline precipitation process (10 mol/L sodium hydroxide is dripped to adjust the pH value to 12-13, the stirring temperature is increased 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 by once cooling crystallization, which is not beneficial to the separation of substrate phenol and may cause the residue of phenol in the product. CN105969819A (a method for producing L-tyrosine by an enzyme method) can remove impurities such as macromolecular protein, pigment and the like to a great extent by treating conversion liquid with a ceramic membrane, but the treatment of strong acid solution by a ceramic membrane device at a high temperature can cause the corrosion of stainless steel materials, and has adverse effects on the device and the product quality.
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 the method for extracting L-tyrosine from the conversion solution, which optimizes and improves the membrane pretreatment process, the crystallization control process and the mother solution recovery process and aims to reduce the production cost and improve the product quality.
The method for extracting L-tyrosine from the transformation liquid provided by the invention comprises the following steps:
(1) adding alkali liquor into the tyrosine conversion solution, and dissolving solid tyrosine contained in the tyrosine conversion solution by heat preservation;
(2) filtering the dissolved conversion solution by using a ceramic membrane, preserving the temperature of the ceramic membrane filtrate, neutralizing the filtrate to pH5.0-5.5 by using dilute hydrochloric acid, crystallizing, and centrifugally collecting crude crystals;
(3) adding the crude product into water, dissolving with dilute hydrochloric acid solution under heat preservation, and decolorizing with activated carbon;
(4) neutralizing the decolored clear liquid with ammonia water, centrifuging and collecting fine products, namely L-tyrosine products;
(5) and (3) decoloring the refined mother liquor by using a nanofiltration membrane to serve as ammonium chloride mother liquor, and adding the ammonium chloride mother liquor into a preparation raw material of the tyrosine conversion solution of the next batch.
In the step (1), the tyrosine conversion solution is prepared by using substrates such as pyruvic acid, ammonium chloride and the like catalyzed by a tyrosine phenol lyase, and the content of tyrosine in the conversion solution can be 130-150 g/L;
the alkali liquor can be a sodium hydroxide solution with the mass concentration of 5% -10%, the pH value of the tyrosine conversion solution is adjusted to 10-12 after the alkali liquor is added, and the temperature of heat preservation can be 70-80 ℃;
in the step (2), 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 dilute hydrochloric acid with the mass concentration of 3% -5%, and the temperature for heat preservation can be 70-75 ℃;
in the step (3), 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 until the crude product is completely dissolved;
the temperature of the heat preservation can be 70-75 ℃;
the adding amount of the active carbon is 10-15g/L,
adding active carbon, keeping the temperature at 70-75 ℃, stirring for 0.5h, and performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid;
in the step (4), the decolored clear liquid 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 refined products are collected by centrifugation when the clear liquid is hot.
In the step (5), the nanofiltration membrane is decolorized by adopting NF800 or NF500, the operating pressure is 1.0-1.5MPa, and the temperature is 40-45 ℃.
The method adopts the 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 (a stainless steel pipeline and a circulating pump) at high temperature;
tyrosine crystallization adopts an isoelectric point crystallization process, but because a small amount of phenol as a substrate is left in the tyrosine conversion process, the phenol is insoluble in cold water and slightly soluble in hot water, and can be mixed with water at the temperature of over 65 ℃, the high temperature is kept in the crystallization process and the crystal centrifugal collection process, so that the phenol residue in the tyrosine crystallization is reduced;
besides tyrosine of less than 1g/L, the refined mother liquor also contains ammonium chloride of which the concentration is 26.25-52.5g/L and the concentration is 0.5-1.0mol/L, wherein the ammonium chloride is a reaction substrate for preparing tyrosine, so the refined mother liquor can be recycled as a substrate solution for the next reaction after nanofiltration and decoloration treatment, thereby not only reducing the production cost, but also being beneficial to recycling the high ammonia nitrogen wastewater which needs environmental protection treatment, and greatly reducing the environmental protection pressure.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The L-tyrosine transformation solution used in the following examples was obtained by the following method:
and (3) conversion reaction:
keeping the temperature at 37 ℃ for reaction, feeding phenol and pyruvic acid during the reaction, controlling the content of the phenol and the pyruvic acid to be respectively not more than 8g/L and 10g/L, respectively adding 10g/L ammonium chloride (or recovered ammonium chloride solution, calculating the volume of the ammonium chloride solution by using 10g/L ammonium chloride to convert the ammonium chloride to pure) in 2, 4 and 6 hours, stopping feeding the substrate until the reaction time is 10 hours, and stopping the reaction until the content of the phenol is less than 0.5 g/L.
Because the solubility of tyrosine water is very low, obvious crystal precipitation can occur in the conversion solution after the conversion reaction is carried out for 10min, and the crystal is more and more along with the prolonging of the reaction time. After tyrosine in the conversion solution was completely dissolved, the tyrosine content in the reaction system was calculated from the volume change.
HPLC method for L-tyrosine content detection in the following examples
A chromatographic column: ODS C18 (4.6X 250mm, 5 μm)
Mobile phase: methanol and water 15:85
Flow rate: 1.0ml/min
Wavelength: 280nm
Column temperature: at 30 ℃.
Example 1
Heating L-tyrosine conversion solution (containing tyrosine 135.62g/L) with volume of 20L to 70 deg.C, adjusting pH to 12.0 with 5% sodium hydroxide solution, and stirring under constant temperature until tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at an operating pressure of 0.1MPa and a temperature of 70 deg.C; keeping the temperature at 60 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 3% to filter the clear solution to pH5.5, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1% of 10g/L active carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, keeping the temperature at 60 deg.C, and centrifuging to collect refined product. The dried refined product has a mass of 2457.4g, a yield of 90.6%, and an L-tyrosine content of 99.86% determined by HPLC.
And (3) decoloring the refined mother liquor by NF800, wherein the operating pressure is 1.0MPa, the temperature is 40 ℃, and the refined mother liquor is converted into ammonium chloride with the concentration of 42g/L after ammonia nitrogen is detected and is used as a substrate for converting tyrosine of the next batch.
Example 2
Heating L-tyrosine conversion solution (the content of tyrosine is 138.95g/L) with volume of 25L to 80 deg.C, adjusting pH to 11.5 with 10% sodium hydroxide solution, and stirring under heat preservation until tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at 0.15MPa and 75 deg.C; keeping the temperature at 70 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 5% to filter the clear solution to pH5.0, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water by volume, dropwise adding hydrochloric acid with the mass concentration of 15%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1.5% of 15g/L activated carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 15% ammonia water to pH5.5, keeping the temperature at 70 deg.C, and centrifuging to collect refined product. The dried product has the mass of 3168.1, the yield of 91.2 percent and the L-tyrosine content of 99.91 percent determined by HPLC.
The refined mother liquor is decolorized by NF500 under the operating pressure of 1.5MPa and the temperature of 45 ℃, and the concentration of ammonium chloride converted by ammonia nitrogen detection is 48.5g/L, and the refined mother liquor is used as a substrate for converting tyrosine of the next batch.
Comparative example 1
Heating L-tyrosine conversion solution (tyrosine content 132.5g/L) with volume of 20L to 70 deg.C, adjusting pH to 12 with 5% sodium hydroxide solution, and stirring under constant temperature until tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at an operating pressure of 0.1MPa and a temperature of 70 deg.C; keeping the temperature at 60 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 3% to filter the clear solution to pH4.5, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1% of 10g/L active carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, keeping the temperature at 60 deg.C, and centrifuging to collect refined product. The dried refined product has a mass of 2350.5g, a yield of 88.7%, and an L-tyrosine content of 99.87% by HPLC. Compared with example 1, the pH value of the primary neutralization crystallization is reduced, and the yield of the obtained product is obviously reduced.
The refined mother liquor is decolorized by NF800 at an operating pressure of 1.0MPa and a temperature of 40 ℃, and the concentration of ammonium chloride is converted to 41.2g/L after ammonia nitrogen is detected, and the refined mother liquor is used as a substrate for converting tyrosine of the next batch.
Comparative example 2
Heating L-tyrosine conversion solution (tyrosine content is 140.2g/L) with volume of 20L to 70 deg.C, adjusting pH to 12 with 5% sodium hydroxide solution, and stirring under heat preservation until tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at an operating pressure of 0.1MPa and a temperature of 70 deg.C; keeping the temperature at 60 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 3% to filter the clear solution to pH6.8, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1% of 10g/L active carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.8, keeping the temperature at 60 deg.C, and centrifuging to collect refined product. The dried refined product has a mass of 2593.7g, a yield of 93.5%, and an L-tyrosine content of 96.1% determined by HPLC. Compared with example 1, the pH value of the primary neutralization crystallization is increased, and the L-tyrosine content in the obtained product is obviously reduced. From comparative examples 1 and 2, it can be seen that the pH of the neutralized crystals has a significant effect on the quality of the L-tyrosine product.
The refined mother liquor is decolorized by NF800 at an operating pressure of 1.0MPa and a temperature of 40 ℃, and the concentration of ammonium chloride is converted to 49.3g/L after ammonia nitrogen is detected, and the refined mother liquor is used as a substrate for converting tyrosine of the next batch.
Comparative example 3
Heating L-tyrosine conversion solution (tyrosine content of 135.8g/L) with volume of 20L to 70 deg.C, adjusting pH to 12 with 5% sodium hydroxide solution, and stirring under heat preservation until tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at an operating pressure of 0.1MPa and a temperature of 70 deg.C; keeping the temperature at 60 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 8.0% to filter the clear solution to pH5.5, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1% of 10g/L active carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, keeping the temperature at 60 deg.C, and centrifuging to collect refined product. The dried refined product has a mass of 2447.1g, a yield of 90.1%, and an L-tyrosine content of 98.62% as determined by HPLC. Compared with the example 1, the mass concentration of the diluted hydrochloric acid used for primary neutralization is increased, and the content of the obtained product L-tyrosine is reduced.
The refined mother liquor is decolorized by NF800 and used as a substrate for the next tyrosine conversion.
Comparative example 4
Heating L-tyrosine conversion solution (the content of tyrosine is 136.8g/L) with a volume of 20L to 70 ℃, adjusting the pH value to 12 by using sodium hydroxide solution with a mass concentration of 5%, and keeping the temperature and stirring until the tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at an operating pressure of 0.1MPa and a temperature of 70 deg.C; keeping the temperature at 60 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 2.0% to filter the clear solution to pH5.5, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1% of 10g/L active carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 10% ammonia water to pH5.0, keeping the temperature at 60 deg.C, and centrifuging to collect refined product. The dried refined product has a mass of 2382.2g, a yield of 87.1%, and an L-tyrosine content of 99.79% as determined by HPLC. Compared with the example 1, the mass concentration of the dilute hydrochloric acid used for primary neutralization is reduced, and the yield of the obtained product is obviously reduced. From comparative examples 3 and 4, it can be seen that the concentration of hydrochloric acid used in one neutralization is critical to the quality of the L-tyrosine product.
The refined mother liquor is decolorized by NF800 and used as a substrate for the next tyrosine conversion.
Comparative example 5
Heating L-tyrosine conversion solution (tyrosine content of 135.6g/L) with volume of 20L to 70 deg.C, adjusting pH to 12.0 with 5% sodium hydroxide solution, and stirring under heat preservation until tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at an operating pressure of 0.1MPa and a temperature of 70 deg.C; keeping the temperature at 60 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 3% to filter the clear solution to pH5.5, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1% of 10g/L active carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with 5% ammonia water to pH5.0, keeping the temperature at 60 deg.C, and centrifuging to collect refined product. The dried refined product has a mass of 2294.7g, a yield of 84.6%, and an L-tyrosine content of 99.91% as determined by HPLC. Compared with the example 1, the mass concentration of the ammonia water used for the secondary neutralization is reduced, and the yield is obviously reduced.
The refined mother liquor is decolorized by NF800 and used as a substrate for the next tyrosine conversion.
Comparative example 6
Heating L-tyrosine conversion solution (containing tyrosine 135.71g/L) with volume of 20L to 70 deg.C, adjusting pH to 12.0 with 5% sodium hydroxide solution, and stirring under constant temperature until tyrosine solid is completely dissolved; filtering with 50nm ceramic membrane at an operating pressure of 0.1MPa and a temperature of 70 deg.C; keeping the temperature at 60 ℃, neutralizing the clear solution by using dilute hydrochloric acid with the mass concentration of 3% to filter the clear solution to pH5.5, and centrifugally collecting crystals to obtain a crude product; adding the crude product into 5 times of water, dropwise adding hydrochloric acid with the mass concentration of 10%, keeping the temperature at 70 ℃ to completely dissolve the crude product, adding 1% of 10g/L active carbon, keeping the temperature and stirring for 0.5 h; performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid; neutralizing the decolorized clear solution with ammonia water with the mass concentration of 18% to pH5.0, keeping the temperature at 60 ℃, and centrifuging while the solution is hot to collect a refined product. The dried refined product has a mass of 2538.8g, a yield of 93.6%, and an L-tyrosine content of 95.2% by HPLC. Compared with the embodiment 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.
From comparative examples 5 and 6, it is understood that the mass concentration of ammonia water 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 used as a substrate for the next tyrosine conversion.
The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced within a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific embodiments, it will be appreciated that the invention can be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (6)
1. A method for extracting L-tyrosine from a transformation liquid comprises the following steps:
(1) adding alkali liquor into the tyrosine conversion solution, and dissolving solid tyrosine contained in the tyrosine conversion solution by heat preservation;
(2) filtering the dissolved conversion solution by using a ceramic membrane, preserving the temperature of the ceramic membrane filtrate, neutralizing the filtrate to pH5.0-5.5 by using dilute hydrochloric acid, crystallizing, and centrifugally collecting crude crystals;
(3) adding the crude product into water, dissolving with dilute hydrochloric acid solution under heat preservation, and decolorizing with activated carbon;
(4) neutralizing the decolored clear liquid with ammonia water, centrifuging and collecting fine products, namely L-tyrosine products;
(5) and (3) decoloring the refined mother liquor by using a nanofiltration membrane to serve as ammonium chloride mother liquor, and adding the ammonium chloride mother liquor into a preparation raw material of the tyrosine conversion solution of the next batch.
2. The method of claim 1, wherein: in the step (1), the tyrosine content in the conversion solution is 130-150 g/L;
the alkali liquor is a sodium hydroxide solution with the mass concentration of 5% -10%, the pH value of the tyrosine conversion solution is adjusted to 10-12 after the alkali liquor is added, and the temperature of heat preservation is 70-80 ℃.
3. The method according to claim 1 or 2, characterized in that: in the step (2), the ceramic membrane is a 50nm ceramic membrane;
the operation pressure of the ceramic membrane filtration is 0.1-0.15MPa, and the temperature is 70-75 ℃;
the dilute hydrochloric acid is 3-5% in mass concentration, and the temperature for heat preservation is 70-75 ℃.
4. The method according to any one of claims 1-3, wherein: in the step (3), the volume of water is 3-5 times of the mass of the crude product;
the dilute hydrochloric acid solution is hydrochloric acid with the mass concentration of 10% -15%;
the temperature of the heat preservation is 70-75 ℃;
the adding amount of the active carbon is 10-15g/L,
adding active carbon, keeping the temperature at 70-75 ℃, stirring for 0.5h, and performing suction filtration or filter pressing to remove carbon to obtain decolorized clear liquid.
5. The method according to any one of claims 1-4, wherein: in the step (4), the decolored clear liquid 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 refined products are collected by centrifugation when the clear liquid is hot.
6. The method according to any one of claims 1-5, wherein: in the step (5), the nanofiltration membrane is decolorized by adopting NF800 or NF500, the operating pressure is 1.0-1.5MPa, and the temperature is 40-45 ℃.
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| CN115947662A (en) * | 2022-12-23 | 2023-04-11 | 江西唯铂莱生物制药有限公司 | Separation and purification method of L-tyrosine and preparation method thereof |
| CN116253657A (en) * | 2023-03-27 | 2023-06-13 | 天津科技大学 | Method for extracting L-tyrosine from fermentation liquor |
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| 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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| CN116253657A (en) * | 2023-03-27 | 2023-06-13 | 天津科技大学 | Method for extracting L-tyrosine from fermentation liquor |
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