CN112028784A - Preparation method of free L-lysine solid - Google Patents
Preparation method of free L-lysine solid Download PDFInfo
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- CN112028784A CN112028784A CN202010925450.7A CN202010925450A CN112028784A CN 112028784 A CN112028784 A CN 112028784A CN 202010925450 A CN202010925450 A CN 202010925450A CN 112028784 A CN112028784 A CN 112028784A
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- 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
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Abstract
The invention discloses a preparation method of free L-lysine solid, which comprises the following steps: dissolving L-lysine hydrochloride with water, washing an L-lysine solution by a cation exchange resin column, washing by purified water until no chloride ions exist, then washing the cation exchange resin by ammonia water, eluting the L-lysine, concentrating the eluent to obtain water, adding a crystallization solvent for crystallization, filtering and drying to obtain an L-lysine alkali solid. The free L-lysine solid prepared by the method has good unicity, easy storage and transportation and good solid stability, and is very suitable for industrial production. Meanwhile, the method has the advantages of simple operation, low cost of raw and auxiliary materials, little environmental pollution, high product purity and the like.
Description
Technical Field
The invention relates to a novel method for preparing free L-lysine solid from L-lysine hydrochloride, belonging to the technical field of preparation and production of the free L-lysine solid.
Background
L-lysine is one of essential amino acids for human body, and has been fully determined in nutritive value, so that it is widely used as food nutrition enhancer, animal feed additive, medicine and medicine adjuvant, etc., and becomes the second largest product in amino acid industrial production, which is second to glutamic acid in yield. At present, lysine is prepared mainly by a fermentation method in mature and industrial production, and L-lysine belongs to micromolecular basic amino acid, so that L-lysine is extremely easy to deliquesce, absorb carbon dioxide in air and be easily oxidized, and L-lysine hydrochloride is mainly used in the market.
The literature reports that the preparation is mainly performed on the preparation of lysine L-lysine hydrochloride, and almost no preparation process for preparing free L-lysine solid is reported.
Among them, the fine organic chemical technical manual (the following brochure), scientific press, first edition in 1992, page 1027, teaches a method for preparing lysine free: dissolving lysine hydrochloride with water, adsorbing with cation exchange resin to remove chlorine, eluting with ammonia water, and distilling the eluate to obtain free base. This data only describes how to prepare the free base and does not describe in detail how to make free L-lysine solid, so that according to the data it is not possible to prepare L-lysine solid and the process is not advisable.
The patent application with publication No. CN1283402A mentions that the production method and application of lysine alkali dry powder require spray drying of free lysine, and the content of lysine prepared by the method is only about 90%, so the production cost is high, and the product quality is difficult to reach high-purity lysine, so the process is not desirable in production scale-up.
Patent application publication No. CN103787904 mentions a process for preparing L-lysine base solution by passing L-lysine hydrochloride solution through an anion exchange resin to convert lysine hydrochloride to L-lysine base effluent resin, collecting L-lysine base solution and adjusting the pH, and then directly transferring to an ampoule. In the method, the quality of the resin column cannot be controlled, so that the quality stability of the product cannot be guaranteed, in addition, the concentration of the solution cannot be accurately determined by the L-lysine solution, so that the operation is not easy, and the L-lysine aqueous solution is difficult to store and transport, so that the method is not preferable.
The patent application with publication No. CN102584614A also uses cation exchange resin to remove hydrochloric acid, and first dissolves L-lysine hydrochloride with water, then adds the L-lysine hydrochloride into the resin, and uses ammonia water to elute L-lysine, then concentrates most of water in the eluent, and then cools and crystallizes. However, this method has a disadvantage that the yield is very low and the process is not preferable when water is used for the crystallization because L-lysine is easily soluble in water.
Disclosure of Invention
The invention aims to overcome the defects of the existing crystallization technology and provide the preparation method of the L-lysine solid, which has the advantages of easily obtained raw materials, simple process, higher yield, high purity, stability and easy storage.
In order to achieve the purpose, the invention adopts the following technical means:
the preparation method of the free L-lysine solid comprises the following steps:
(1) adding L-lysine hydrochloride into purified water, stirring and dissolving to obtain an L-lysine hydrochloride aqueous solution, wherein the mass ratio of the purified water to the L-lysine hydrochloride is 1: 1-15: 1;
(2) adding the L-lysine hydrochloride aqueous solution into the activated cation exchange resin column, slowly washing the resin column, wherein the mass ratio of the cation exchange resin to the L-lysine hydrochloride is 10:1-3:1, and then continuously washing the resin column by using purified water until the resin column is neutral and free of chloride ions;
(3) eluting L-lysine by using ammonia water, wherein the concentration of the ammonia water is 3-10% v/v, the mass ratio of the ammonia water converted into strong ammonia water to the L-lysine hydrochloride is optimally 1:1-5:1, and receiving eluent with the pH value more than 10;
(4) concentrating the eluent under reduced pressure, and concentrating water and ammonia gas until no liquid drops are concentrated, wherein the concentration temperature is 50-70 ℃, and the concentration pressure is-0.06-0.1 MPa;
(5) adding a pulping solvent into the concentrate for pulping, pulping for 1-5h for crystal transformation, filtering out a solid, and performing vacuum drying, wherein the drying vacuum degree is-0.06-0.1 MPa, the drying temperature is 30-120 ℃, the drying time is 2-10 h, and the pulping solvent is selected from one or a mixture of more than one of absolute ethyl alcohol, methanol, isopropanol, n-butanol, ethyl acetate, n-hexane, n-heptane and petroleum ether;
(6) and (5) cooling the solid obtained in the step (5) to room temperature, filling the solid into a sealing bag, sealing and storing the solid in a shade place to obtain free L-lysine solid.
Wherein, the mass ratio of the water to the L-lysine hydrochloride in the step (1) is preferably 3: 1-8: 1, and is preferably 5: 1.
Among them, it is preferable that the cation exchange resin in the step (2) is a strongly acidic cation exchange resin, and the mass ratio of the cation exchange resin to the L-lysine hydrochloride is 12: 5.
Of these, it is preferable that the L-lysine hydrochloride aqueous solution is added to the activated cation exchange resin column in the step (2), and the resin column is slowly washed for 0.5 to 3 hours, more preferably 2 to 3 hours.
Wherein, the concentration of the ammonia water in the step (3) is preferably 4-6%, and the washing time is 2-3 h.
Wherein, the concentration temperature in the step (4) is preferably 55-65 ℃.
Preferably, the dosage of the pulping solvent in the step (5) is 3-12 times, more preferably 5-8 times, of the mass of the L-lysine, the pulping temperature is 0-45 ℃, preferably 15-35 ℃, and the pulping time is 2-4 hours.
Among them, the preferable pulping solvent in step (5) is absolute ethyl alcohol, isopropanol, ethyl acetate, and more preferable is absolute ethyl alcohol.
Wherein, the vacuum drying temperature in the step (5) is preferably 50-120 ℃, more preferably 80-100 ℃, and the drying time is 3-6 h.
Among them, preferably, the obtained free L-lysine solid has an X-ray powder diffraction spectrum having characteristic peaks at 2 θ of 4.89 °, 9.98 °, 18.36 °, 19.33 °, 20.26, 23.46 °, 25.44 ° and 30.67 °.
Compared with the prior art, the invention has the beneficial effects that:
the free L-lysine solid prepared by the method has good unicity, easy storage and transportation and good solid stability, and is very suitable for industrial production. Meanwhile, the method has the advantages of simple operation, low cost of raw and auxiliary materials, little environmental pollution, high product purity and the like.
Drawings
FIG. 1 is a solid phase diagram of free L-lysine obtained in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of free L-lysine obtained in example 1 of the present invention;
FIG. 3 is a mass spectrum of free L-lysine solid obtained in example 1 of the present invention;
FIG. 4 is a diffraction pattern of solid XRD crystal powder of free L-lysine obtained in example 1 of the present invention;
FIG. 5 is a solid Thermogram (TGA) of free L-lysine obtained in example 1 of the present invention;
FIG. 6 is a solid phase diagram of free L-lysine obtained in example 2 of the present invention.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following experiments in conjunction with examples, which are to be understood as being illustrative only and not limiting in any way to the scope of the present invention. Those skilled in the art will recognize that many changes, modifications, and equivalents may be made thereto without departing from the spirit and scope of the invention, which is set forth in the claims below.
Example 1: preparation of free L-lysine solid
Weighing 1.00kg of L-lysine hydrochloride, adding the L-lysine hydrochloride into 5.0L of purified water, stirring, dissolving and clarifying, adding the solution onto 7.20kg of activated strong acid cation exchange resin column, slowly washing the resin column, washing for 2-3h, and continuously washing with purified water until the solution is neutral and free of chloride ions (0.1mol/L of silver nitrate monitoring and wide pH test paper). Adding 11.1kg of 5% v/v ammonia water to the resin column, slowly washing the resin column for about 2-3h, and starting to collect alkaline eluent when the pH value is detected to be greater than 10 in the washing process until the pH value is reduced to about 10, and stopping collecting.
Concentrating the collected solution at 60 deg.C (-0.10-0.08 Mpa) under reduced pressure, concentrating to obtain water and ammonia gas until no liquid drops drop out, and concentrating to obtain whiteAdding 8L of absolute ethyl alcohol into a solid, continuing pulping and crystallizing, pulping for 3h, separating out all solids, centrifugally filtering out the solids until no liquid drops drip out, spreading a filter cake on an enamel tray, performing vacuum drying (60 +/-5 ℃ and-0.08 to-0.1 Mpa) for 8h, cooling the product to room temperature, filling the product into a sealing bag, sealing and storing in a shade place to obtain 776g of free L-lysine solid, wherein the yield is 96.95%, and the purity is as follows: 99.62%, HNMR (D)2O):3.223-3.188(CHN)、2.848-2.794(2H/CH2N)、1.542-1.523、1.276(-CH2CH2 CH2-)。LCMS(M+1):147.1127。
FIG. 1 is a solid phase diagram of free L-lysine obtained in example 1 of the present invention; FIG. 2 is a nuclear magnetic resonance spectrum of free L-lysine obtained in example 1 of the present invention; FIG. 3 is a mass spectrum of free L-lysine solid obtained in example 1 of the present invention; FIG. 4 is a diffraction pattern of solid XRD crystal powder of free L-lysine obtained in example 1 of the present invention; FIG. 5 is a solid Thermogram (TGA) of free L-lysine obtained in example 1 of the present invention.
Example 2: preparation of free L-lysine solid
Weighing 1.00kg of L-lysine hydrochloride, adding the L-lysine hydrochloride into 5.0L of purified water, stirring, dissolving and clarifying, adding the solution onto 7.20kg of activated strong acid cation exchange resin column, slowly washing the resin column, washing for 2-3h, and continuously washing with purified water until the solution is neutral and free of chloride ions (0.1mol/L of silver nitrate monitoring and wide pH test paper). Adding 11.1kg of 5% v/v ammonia water to the resin column, slowly washing the resin column for about 2-3h, and starting to collect alkaline eluent when the pH value is detected to be greater than 10 in the washing process until the pH value is reduced to about 10, and stopping collecting.
Concentrating the collected solution at 60 ℃ (-0.10 to-0.08 Mpa), concentrating the effluent and ammonia until no liquid drops drop out, continuing to concentrate to obtain white solid, adding 6L of isopropanol into the system, pulping, crystallizing, stirring and pulping for 3h, separating out all solids, centrifugally filtering out the solids, washing the filter cake with isopropanol for 2 times, continuing to centrifuge until no liquid drops drop out, spreading the filter cake on an enamel tray, vacuum drying (60 +/-5 ℃ to-0.08 to-0.1 Mpa) for 8h, cooling the product to room temperature, filling the product into a sealed bag, sealing and storing in the shade to obtain 784g of free L-lysine solid, wherein the yield is 97.95% and the purity is 99.43%.
FIG. 6 is a solid phase diagram of free L-lysine obtained in example 2 of the present invention.
The above examples are detailed descriptions of preferred embodiments of the present patent, but the patent is not limited to the above embodiments, and various process variations can be made within the scope of the ordinary skill in the art and the spirit of the patent.
Claims (10)
1. A method for preparing a free L-lysine solid, comprising the steps of:
(1) adding L-lysine hydrochloride into purified water, stirring and dissolving to obtain an L-lysine hydrochloride aqueous solution, wherein the mass ratio of the purified water to the L-lysine hydrochloride is 1: 1-15: 1;
(2) adding the L-lysine hydrochloride aqueous solution into the activated cation exchange resin column, slowly washing the resin column, wherein the mass ratio of the cation exchange resin to the L-lysine hydrochloride is 10:1-3:1, and then continuously washing the resin column by using purified water until the resin column is neutral and free of chloride ions;
(3) eluting L-lysine by using ammonia water, wherein the concentration of the ammonia water is 3-10% v/v, the mass ratio of the ammonia water converted into strong ammonia water to the L-lysine hydrochloride is optimally 1:1-5:1, and receiving eluent with the pH value more than 10;
(4) concentrating the eluent under reduced pressure, and concentrating water and ammonia gas until no liquid drops are concentrated, wherein the concentration temperature is 50-70 ℃, and the concentration pressure is-0.06-0.1 MPa;
(5) adding a pulping solvent into the concentrate for pulping, pulping for 1-5h for crystal transformation, filtering out a solid, and performing vacuum drying, wherein the drying vacuum degree is-0.06-0.1 MPa, the drying temperature is 30-120 ℃, the drying time is 2-10 h, and the pulping solvent is selected from one or a mixture of more than one of absolute ethyl alcohol, methanol, isopropanol, n-butanol, ethyl acetate, n-hexane, n-heptane and petroleum ether;
(6) and (5) cooling the solid obtained in the step (5) to room temperature, filling the solid into a sealing bag, sealing and storing the solid in a shade place to obtain free L-lysine solid.
2. The method according to claim 1, wherein the mass ratio of water to L-lysine hydrochloride in step (1) is 3:1 to 8:1, preferably 5: 1.
3. The method according to claim 1, wherein the cation exchange resin in step (2) is a strongly acidic cation exchange resin, and the mass ratio of the cation exchange resin to the L-lysine hydrochloride is 12: 5.
4. The process according to claim 1, wherein in step (2), the L-lysine hydrochloride aqueous solution is fed to the activated cation exchange resin column, and the resin column is slowly washed for a period of time of 0.5 to 3 hours, preferably for a period of time of 2 to 3 hours.
5. The method of claim 1, wherein the concentration of ammonia in step (3) is 4% to 6% v/v and the washing time is 2 to 3 hours.
6. The method of claim 1, wherein the concentration temperature in step (4) is 55 to 65 ℃.
7. The method of claim 1, wherein the amount of the beating solvent used in the step (5) is 3 to 12 times, preferably 5 to 8 times, the mass of the L-lysine, the beating temperature is 0 to 45 ℃, preferably 15 to 35 ℃, and the beating time is 2 to 4 hours.
8. The method of claim 1, wherein the pulping solvent in step (5) is absolute ethanol, isopropanol, ethyl acetate, preferably absolute ethanol.
9. The method of claim 1, wherein the vacuum drying temperature in step (5) is 50-120 ℃, preferably 80-100 ℃, and the drying time is 3-6 h.
10. The process of claim 1, wherein the resulting solid free L-lysine has an X-ray powder diffraction spectrum characterized by peaks 2 Θ of 4.89 °, 9.98 °, 18.36 °, 19.33 °, 20.26, 23.46 °, 25.44 °, and 30.67 °.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023221978A1 (en) * | 2022-05-17 | 2023-11-23 | 北京诺康达医药科技股份有限公司 | Polylysine salt, preparation method therefor, and purification method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184054A (en) * | 1984-03-03 | 1985-09-19 | Ajinomoto Co Inc | Method for purifying optically active lysine |
| CN102584614A (en) * | 2011-12-30 | 2012-07-18 | 宁波海硕生物科技有限公司 | Preparation method of L-lysine |
| CN104520266A (en) * | 2012-08-03 | 2015-04-15 | 味之素株式会社 | Method for producing basic amino acid or basic amino acid salt |
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2020
- 2020-09-03 CN CN202010925450.7A patent/CN112028784A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184054A (en) * | 1984-03-03 | 1985-09-19 | Ajinomoto Co Inc | Method for purifying optically active lysine |
| CN102584614A (en) * | 2011-12-30 | 2012-07-18 | 宁波海硕生物科技有限公司 | Preparation method of L-lysine |
| CN104520266A (en) * | 2012-08-03 | 2015-04-15 | 味之素株式会社 | Method for producing basic amino acid or basic amino acid salt |
Non-Patent Citations (1)
| Title |
|---|
| 江立新: "L-赖氨酸的结晶研究", 《万方学术期刊数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023221978A1 (en) * | 2022-05-17 | 2023-11-23 | 北京诺康达医药科技股份有限公司 | Polylysine salt, preparation method therefor, and purification method therefor |
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