CN110092729B - Crystallization method of L-lysine hydrochloride - Google Patents
Crystallization method of L-lysine hydrochloride Download PDFInfo
- Publication number
- CN110092729B CN110092729B CN201910470388.4A CN201910470388A CN110092729B CN 110092729 B CN110092729 B CN 110092729B CN 201910470388 A CN201910470388 A CN 201910470388A CN 110092729 B CN110092729 B CN 110092729B
- Authority
- CN
- China
- Prior art keywords
- lysine hydrochloride
- concentration
- crystallization
- lysine
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 title claims abstract description 82
- 238000002425 crystallisation Methods 0.000 title claims abstract description 56
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 16
- 238000007664 blowing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 29
- 238000007605 air drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 abstract description 33
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 24
- 239000004472 Lysine Substances 0.000 abstract description 19
- 229960003646 lysine Drugs 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 235000019766 L-Lysine Nutrition 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000005587 bubbling Effects 0.000 abstract description 5
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 10
- 235000018977 lysine Nutrition 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- GMKMEZVLHJARHF-UHFFFAOYSA-N (2R,6R)-form-2.6-Diaminoheptanedioic acid Natural products OC(=O)C(N)CCCC(N)C(O)=O GMKMEZVLHJARHF-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- GMKMEZVLHJARHF-SYDPRGILSA-N meso-2,6-diaminopimelic acid Chemical compound [O-]C(=O)[C@@H]([NH3+])CCC[C@@H]([NH3+])C([O-])=O GMKMEZVLHJARHF-SYDPRGILSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HOMROMWVNDUGRI-RVZXSAGBSA-N (2s)-2-aminopentanedioic acid;(2s)-2,6-diaminohexanoic acid Chemical compound NCCCC[C@H](N)C(O)=O.OC(=O)[C@@H](N)CCC(O)=O HOMROMWVNDUGRI-RVZXSAGBSA-N 0.000 description 2
- 108090000489 Carboxy-Lyases Proteins 0.000 description 2
- 102000001554 Hemoglobins Human genes 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 235000019789 appetite Nutrition 0.000 description 2
- 230000036528 appetite Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000020776 essential amino acid Nutrition 0.000 description 2
- 239000003797 essential amino acid Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000036039 immunity Effects 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 108030003594 Diaminopimelate decarboxylases Proteins 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241000588915 Klebsiella aerogenes Species 0.000 description 1
- 208000002720 Malnutrition Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 210000003792 cranial nerve Anatomy 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000020774 essential nutrients Nutrition 0.000 description 1
- 210000004051 gastric juice Anatomy 0.000 description 1
- 210000004602 germ cell Anatomy 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229960005337 lysine hydrochloride Drugs 0.000 description 1
- 230000001071 malnutrition Effects 0.000 description 1
- 235000000824 malnutrition Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 208000015380 nutritional deficiency disease Diseases 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- C07C227/42—Crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a crystallization method of L-lysine hydrochloride, which comprises the following steps: primarily concentrating the aqueous solution of L-lysine hydrochloride, adding an organic solvent, and cooling under the blowing of saturated steam to obtain L-lysine hydrochloride; according to the invention, through the combination of the three methods of concentration, organic solvent and steam bubbling, compared with a method of direct recrystallization or concentrated crystallization, the crystallization rate and the crystallization yield of the L-lysine hydrochloride can be improved on the premise of ensuring the crystallization purity, the crystallization yield can reach more than 80%, the precipitated crystal form is single, and the method has important significance and value for the production and market application of L-lysine.
Description
Technical Field
The invention belongs to the field of biological separation, and relates to a crystallization method of L-lysine hydrochloride.
Background
Lysine is one of the most important amino acids, is one of essential amino acids for human body, can promote human body development, enhance immunity, improve central nervous tissue function, improve intelligence, promote growth, and enhance body constitution. Promoting appetite, and improving malnutrition. Improving insomnia and memory. It helps to produce antibody, hormone and enzyme, improve immunity, and increase hemoglobin. Helps calcium absorption, and can be used for preventing osteoporosis, lowering triglyceride level in blood, and preventing cardiovascular and cerebrovascular diseases. Lysine is a basic essential amino acid. The cereal is called the first limiting amino acid because of its very low lysine content and its easy destruction and lack during processing.
Lysine is mainly used in food, medicine and feed. Used as a feed nutrition enhancer and is an essential nutrient component of livestock and poultry. Has the functions of enhancing the appetite of livestock and poultry, improving the disease resistance, promoting the healing of trauma and improving the quality of meat, can enhance the secretion of gastric juice, and is a necessary substance for synthesizing cranial nerves, germ cells, proteins and hemoglobin.
Although lysine can be extracted from hydrolysate of protein raw material (such as pig blood powder), currently used lysine is mainly lysine hydrochloride produced by fermentation, and L-lysine is obtained by extraction and fermentation. The fermentation methods include a two-step method using diaminopimelic acid and a one-step method using sugar as a raw material, and many sugar fermentation methods are used. The production process of the diaminopimelic acid method comprises the following steps: l-lysine biosynthesis by Escherichia coli is an important factor for improving efficiency by culturing a mutant strain of Escherichia coli which does not have a diaminopimelate decarboxylase function and cannot grow without lysine in a medium such as glycerol, corn steep liquor, or ammonium phosphate, wherein a large amount of diaminopimelate accumulates in the medium and the medium is kept neutral. Then, after a decarboxylase is eluted with toluene by using Aerobacter aerogenes or Escherichia coli having a decarboxylation function for diaminopimelic acid but not for lysine, L-lysine can be produced almost quantitatively by the action of the decarboxylase with diaminopimelic acid, and the L-lysine hydrochloride can be separated and purified by ion exchange resin to obtain L-lysine hydrochloride. It can be seen that the L-lysine finally obtained by purification is present as a hydrochloride.
At present, the research on the crystallization extraction method of L-lysine is less, and the extraction process mainly focuses on extracting by using macroporous adsorption resin after fermentation, and then directly crystallizing to obtain the L-lysine product after decoloring by using activated carbon. However, the yield of the extractive crystallization process is low.
CN108796026A discloses a production, extraction and purification process of lysine, wherein the extraction process comprises the following steps: adding hydrochloric acid into the fermentation liquor to adjust pH to 5.5, performing solid-liquid separation by using a disc centrifuge, collecting liquid, pumping into a decoloring tank for decoloring, adding active carbon accounting for 0.5-0.8% of the liquid mass into the decoloring tank, decoloring for 30min, then centrifuging to remove the active carbon, collecting supernatant, adding hydrochloric acid to adjust pH to 4.9, entering a concentration crystallizer for evaporation and concentration, controlling the temperature to be 40 ℃ and the vacuum degree to be-0.09 Mpa, performing centrifugal separation when the evaporation and concentration is carried out to one third to one fourth of the original volume, collecting wet crystals, and drying to obtain the product. The yield of the finally obtained lysine is only about 70 percent.
CN107325014A discloses an L-lysine L-glutamate crystalline powder and a preparation method thereof, the method comprises the step of putting crystals obtained after methanol water crystallization of L-lysine L-glutamate into ethanol for conversion, the problem of methanol residue accompanying the elution crystallization process is effectively solved, the methanol residue of the prepared crystalline powder can be controlled below 0.01 wt.%, the bulk density is more than 0.4g/mL, the tap density is more than 0.5g/mL, and the free water content is less than 0.1 wt.%, and the crystalline powder has good granularity, fluidity and stability, and can be better applied to the fields of food, cosmetics, biology and medicine. But the yield of this process is still low.
The existing production process of L-lysine and the crystallization method have low yield, and how to develop a method with high crystallization yield has important significance and value for reducing the production cost of L-lysine and large-scale application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for crystallizing L-lysine hydrochloride, which aims to solve the problems of low crystallization yield and low crystallization rate of the L-lysine hydrochloride in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a crystallization method of L-lysine hydrochloride, which comprises the following steps: and (3) primarily concentrating the aqueous solution of the L-lysine hydrochloride, adding an organic solvent, and cooling under the blowing of saturated steam to obtain the L-lysine hydrochloride.
According to the invention, through the combination of the three methods of concentration, organic solvent and steam bubbling, compared with a method of direct recrystallization or concentrated crystallization, the crystallization rate and the crystallization yield of the L-lysine hydrochloride can be improved on the premise of ensuring the crystallization purity, the crystallization yield can reach more than 80%, and the precipitated crystal form is single.
Preferably, the concentration of the aqueous solution of L-lysine hydrochloride is 60% to 70%, and may be, for example, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%, and the like.
In the present invention, the concentration of the aqueous solution of L-lysine hydrochloride refers to the mass fraction of L-lysine hydrochloride in water. This initial concentration has a certain reference value for saving production costs. If the initial concentration is too high, a large portion of L-lysine hydrochloride eventually cannot be crystallized out of water, resulting in a large loss; if the initial concentration is too low, more L-lysine hydrochloride can be crystallized in the subsequent production by using the same conditions, energy consumption and the like, but the concentration of the aqueous solution cannot be matched with the corresponding production conditions, so that the resource waste is caused.
Preferably, the temperature of the primary concentration is 78 to 85 ℃, and may be, for example, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, or 85 ℃.
Preferably, the initial concentration is to concentrate the aqueous solution of L-lysine hydrochloride to a concentration of 75% to 85%, for example, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, or the like.
In the actual production process, the temperature of concentration and the concentration after concentration have an influence on the final yield. Too high a concentration temperature will destroy the crystal form and structure of L-lysine hydrochloride, resulting in a decrease in yield, while too low a concentration temperature will cause incomplete concentration and a decrease in the rate of subsequent crystallization. The concentration of the one-time concentration is not too high, otherwise the subsequent precipitation of the L-lysine hydrochloride is not thorough, and the final yield is reduced.
Preferably, the organic solvent comprises any one of absolute ethyl alcohol, absolute methyl alcohol, acetone, dimethylformamide, isopropanol or n-butanol or a combination of at least two of the same; n-butanol is preferred.
In the invention, the influence of crystallization by different organic solvents on the yield is large, and the research of the invention finds that the n-butanol is used as the solvent for crystallization to improve the final yield to the maximum extent. Although other solvents can also realize crystallization, for example, the product is easy to agglomerate when ethanol is used for crystallization, and the filtration is difficult, so that the quality of the product is influenced; when methanol is used for crystallization, the problem of methanol residue is serious and is difficult to remove; and when the dimethylformamide is used as a crystallization solvent, the residue problem is more serious, the smell is serious, the toxicity is higher, and the dimethylformamide is not easy to apply. Therefore, the effect of n-butanol as a crystallization solvent is optimal.
The volume ratio of the organic solvent to the aqueous solution of L-lysine hydrochloride is preferably 1:3 to 20, and may be, for example, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20, and preferably 1:4 to 8.
The yield of the product is also affected by the proportion of the organic solvent, and the yield is reduced by over-high or over-low volume of the organic solvent.
Preferably, the temperature of the organic solvent is 70 to 75 ℃, for example, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃ or 75 ℃.
Preferably, the blowing time of the saturated steam is 20-30 min, for example, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30 min.
The bubbling of saturated steam can promote the precipitation of L-lysine hydrochloride.
Preferably, the temperature is reduced to 10-20 ℃, for example, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃ or 20 ℃.
Preferably, after the temperature reduction is finished, a drying step is further included.
Preferably, the drying is air drying using air.
Preferably, the air-drying temperature is 65-75 deg.C, such as 65 deg.C, 66 deg.C, 67 deg.C, 68 deg.C, 69 deg.C, 70 deg.C, 71 deg.C, 72 deg.C, 73 deg.C, 74 deg.C or 75 deg.C.
According to the invention, the effects of rapid precipitation and rapid drying of L-lysine hydrochloride are ensured by cooling at low temperature and then drying at high temperature, and the residual organic solvent can be thoroughly removed, so that the final yield, purity and the like of the product are kept at a higher level.
Preferably, the crystallization method comprises the steps of:
the method comprises the steps of firstly concentrating an L-lysine hydrochloride aqueous solution with the concentration of 60% -70% at 78-85 ℃, concentrating the concentration to 75% -85%, then adding an organic solvent with the temperature of 70-75 ℃, wherein the volume ratio of the organic solvent to the L-lysine hydrochloride aqueous solution is 1: 3-20, simultaneously cooling to 10-20 ℃ under the condition of blowing saturated steam for 20-30 min, filtering, and then air-drying with air with the temperature of 65-75 ℃ to obtain the L-lysine hydrochloride.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through the combination of the three methods of concentration, organic solvent and steam bubbling, compared with a method of direct recrystallization or concentrated crystallization, the crystallization rate and the crystallization yield of the L-lysine hydrochloride can be improved on the premise of ensuring the crystallization purity, the crystallization yield can reach more than 80%, the precipitated crystal form is single, and the method has important significance and value for the production and market application of L-lysine.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
In the following examples of the present invention, 1kg of an aqueous solution of L-lysine hydrochloride was used as a raw material.
Example 1
This example provides a crystallization method of L-lysine hydrochloride
Performing primary concentration on a 65% L-lysine hydrochloride aqueous solution at 80 ℃, concentrating the concentration to 80%, adding n-butyl alcohol at 73 ℃, reducing the temperature to 15 ℃ after blowing saturated steam for 25min, filtering, and performing air drying by using air at 70 ℃ to obtain the L-lysine hydrochloride, wherein the volume ratio of the n-butyl alcohol to the L-lysine hydrochloride aqueous solution is 1: 7.
Example 2
This example provides a crystallization method of L-lysine hydrochloride
Performing primary concentration on an L-lysine hydrochloride aqueous solution with the concentration of 70% at 85 ℃, concentrating the concentration to 85%, then adding absolute ethyl alcohol with the temperature of 70 ℃, wherein the volume ratio of the absolute ethyl alcohol to the L-lysine hydrochloride aqueous solution is 1:8, simultaneously blowing saturated steam for 30min, reducing the temperature to 10 ℃, filtering, and performing air drying by using air with the temperature of 75 ℃ to obtain the L-lysine hydrochloride.
Example 3
This example provides a crystallization method of L-lysine hydrochloride
Performing primary concentration on an L-lysine hydrochloride aqueous solution with the concentration of 60% at 78 ℃, concentrating the concentration to 75%, then adding anhydrous methanol with the temperature of 75 ℃, wherein the volume ratio of the anhydrous methanol to the L-lysine hydrochloride aqueous solution is 1:4, simultaneously cooling to 20 ℃ under the condition of blowing saturated steam for 20min, filtering, and performing air drying by using air with the temperature of 65 ℃ to obtain the L-lysine hydrochloride.
Example 4
This example provides a crystallization method of L-lysine hydrochloride
Firstly concentrating an aqueous solution of L-lysine hydrochloride with the concentration of 66% at 82 ℃, concentrating the concentration to 78%, then adding a mixed solution of absolute ethyl alcohol and absolute methanol with the temperature of 72 ℃, reducing the temperature to 15 ℃ after the mixed solution of the absolute ethyl alcohol and the absolute methanol and the aqueous solution of the L-lysine hydrochloride are mixed in a volume ratio of 1:3, simultaneously blowing saturated steam for 27min, filtering, and carrying out air drying by using air with the temperature of 70 ℃ to obtain the L-lysine hydrochloride.
Example 5
This example provides a crystallization method of L-lysine hydrochloride
Performing primary concentration on an aqueous solution of L-lysine hydrochloride with the concentration of 62% at 80 ℃, concentrating the concentration to 75%, then adding acetone with the temperature of 74 ℃, wherein the volume ratio of the acetone to the aqueous solution of the L-lysine hydrochloride is 1:16, simultaneously blowing saturated steam for 22min, reducing the temperature to 16 ℃, filtering, and performing air drying by using air with the temperature of 75 ℃ to obtain the L-lysine hydrochloride.
Example 6
This example is different from example 1 in that L-lysine hydrochloride was obtained in the same manner as in example 1 except that the temperature of the primary concentration was 72 ℃.
Example 7
This example differs from example 1 in that L-lysine hydrochloride was obtained in the same manner as in example 1 except that the temperature of the primary concentration was 90 ℃.
Example 8
This example differs from example 1 in that the concentration after the initial concentration was 70%, and L-lysine hydrochloride was obtained in the same manner as in example 1.
Example 9
This example differs from example 1 in that the concentration after the initial concentration was 89%, and L-lysine hydrochloride was obtained in the same manner as in example 1.
Example 10
This example is different from example 1 in that dimethylformamide was added as an organic solvent in this example, and L-lysine hydrochloride was obtained in the same manner as in example 1.
Example 11
This example is different from example 1 in that isopropanol was added as an organic solvent in this example, and L-lysine hydrochloride was obtained in the same manner as in example 1.
Example 12
This example is different from example 1 in that the volume ratio of n-butanol to the aqueous solution of L-lysine hydrochloride in this example is 1:20, and L-lysine hydrochloride was obtained in the same manner as in example 1.
Example 13
This example is different from example 1 in that the volume ratio of n-butanol to the aqueous solution of L-lysine hydrochloride in this example is 1:25, and L-lysine hydrochloride was obtained in the same manner as in example 1.
Comparative example 1
The comparative example is different from example 1 in that the comparative example does not perform primary concentration, but directly mixes the aqueous solution of L-lysine hydrochloride with the organic solvent to perform the subsequent step, and the rest is the same as example 1 to obtain L-lysine hydrochloride.
Comparative example 2
The comparative example is different from example 1 in that the subsequent step is performed by directly blowing saturated steam into an aqueous solution of L-lysine hydrochloride without adding an organic solvent, and L-lysine hydrochloride is obtained in the same manner as in example 1.
Comparative example 3
The comparison example and example 1 difference, in this comparison example does not blow saturated steam but directly cooled to 15 degrees C, the rest is the same as example 1 to obtain L-lysine hydrochloride.
The yields of L-lysine hydrochloride obtained in the above examples 1 to 13 and comparative examples 1 to 3 are shown in the following Table 1:
| sample (I) | Yield (%) |
| Example 1 | 95.5 |
| Example 2 | 82.5 |
| Example 3 | 81.3 |
| Example 4 | 83.5 |
| Example 5 | 86.7 |
| Example 6 | 85.3 |
| Example 7 | 87.1 |
| Example 8 | 82.5 |
| Example 9 | 84.4 |
| Example 10 | 76.5 |
| Example 11 | 80.1 |
| Example 12 | 89.8 |
| Example 13 | 91.5 |
| Comparative example 1 | 70.1 |
| Comparative example 2 | 65.9 |
| Comparative example 3 | 74.7 |
As is clear from comparison of examples 1 to 5 and examples 10 to 11, the yield of crystals was affected differently by different organic solvents, and the yield was as high as about 95% when n-butanol was used as the organic solvent.
As is clear from comparison of example 1 with examples 6 to 7, the final yield was high when the temperature for the first concentration was in the range of 78 to 85 ℃.
As is clear from comparison of example 1 with examples 8 to 9, the yield of L-lysine hydrochloride was the highest when the concentration after concentration was in the optimum range of 75% to 85%.
As can be seen from comparison of example 1 with examples 12 to 13, the yield of L-lysine hydrochloride can be optimized when the volume ratio of the organic solvent to the aqueous solution of L-lysine hydrochloride is 1:4 to 8.
It is understood from the comparison of example 1 with comparative examples 1 to 3 that the combination of the three methods of primary concentration, addition of an organic solvent and bubbling of saturated steam greatly increases the crystallization yield of L-lysine hydrochloride, and the absence of any one of the methods leads to a decrease in the crystallization yield, and particularly, the addition of an organic solvent is important for the final crystallization yield and has the greatest influence.
The applicant states that the present invention is illustrated by the above examples to the crystallization method of L-lysine hydrochloride of the present invention, but the present invention is not limited to the above detailed method, i.e., it does not mean that the present invention must be implemented by the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A crystallization method of L-lysine hydrochloride, comprising: primarily concentrating the aqueous solution of L-lysine hydrochloride, then adding an organic solvent, and cooling under the blowing of saturated steam to obtain L-lysine hydrochloride;
wherein the primary concentration is to concentrate the aqueous solution of L-lysine hydrochloride to the concentration of 75-85%; the organic solvent is n-butyl alcohol; the volume ratio of the organic solvent to the aqueous solution of L-lysine hydrochloride is 1: 4-8.
2. The crystallization method according to claim 1, wherein the concentration of the aqueous solution of L-lysine hydrochloride is 60 to 70%.
3. The crystallization method according to claim 1 or 2, wherein the temperature of the primary concentration is 78 to 85 ℃.
4. The crystallization method according to claim 1, wherein the temperature of the organic solvent is 70 to 75 ℃.
5. The crystallization method according to claim 1, wherein the blowing time of the saturated steam is 20 to 30 min.
6. The crystallization method according to claim 1, wherein the temperature is reduced to 10 to 20 ℃.
7. The crystallization method according to claim 1, further comprising a step of drying after the temperature reduction is completed.
8. The crystallization method according to claim 7, wherein the drying is air drying using air.
9. The crystallization method according to claim 8, wherein the temperature of the air drying is 65 to 75 ℃.
10. The crystallization method according to claim 1, characterized in that it comprises the steps of:
performing primary concentration on an L-lysine hydrochloride aqueous solution with the concentration of 60-70% at 78-85 ℃, concentrating the concentration to 75-85%, adding n-butyl alcohol with the temperature of 70-75 ℃, wherein the volume ratio of the n-butyl alcohol to the L-lysine hydrochloride aqueous solution is 1: 4-8, cooling to 10-20 ℃ after 20-30 min of saturated steam blowing, filtering, and performing air drying by using air with the temperature of 65-75 ℃ to obtain the L-lysine hydrochloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910470388.4A CN110092729B (en) | 2019-05-31 | 2019-05-31 | Crystallization method of L-lysine hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910470388.4A CN110092729B (en) | 2019-05-31 | 2019-05-31 | Crystallization method of L-lysine hydrochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110092729A CN110092729A (en) | 2019-08-06 |
| CN110092729B true CN110092729B (en) | 2022-06-28 |
Family
ID=67449819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910470388.4A Active CN110092729B (en) | 2019-05-31 | 2019-05-31 | Crystallization method of L-lysine hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110092729B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU891643A1 (en) * | 1979-06-08 | 1981-12-23 | Чаренцаванский Филиал Всесоюзного Научно-Исследовательского Института Генетики И Селекции Промышленных Микроорганизмов | Method of purifying commercial l-lisinmonohydrochloride |
| CN1037927A (en) * | 1988-02-03 | 1989-12-13 | 协和发酵工业株式会社 | Produce the method for L-Methionin |
| CN102875404A (en) * | 2012-10-12 | 2013-01-16 | 中粮生物化学（安徽）股份有限公司 | Production method and application of lysine hydrochloride crystals |
| CN104892437A (en) * | 2015-05-15 | 2015-09-09 | 南通荣泰生物科技有限公司 | Production technology for L-lysine hydrochloride |
-
2019
- 2019-05-31 CN CN201910470388.4A patent/CN110092729B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU891643A1 (en) * | 1979-06-08 | 1981-12-23 | Чаренцаванский Филиал Всесоюзного Научно-Исследовательского Института Генетики И Селекции Промышленных Микроорганизмов | Method of purifying commercial l-lisinmonohydrochloride |
| CN1037927A (en) * | 1988-02-03 | 1989-12-13 | 协和发酵工业株式会社 | Produce the method for L-Methionin |
| CN102875404A (en) * | 2012-10-12 | 2013-01-16 | 中粮生物化学（安徽）股份有限公司 | Production method and application of lysine hydrochloride crystals |
| CN104892437A (en) * | 2015-05-15 | 2015-09-09 | 南通荣泰生物科技有限公司 | Production technology for L-lysine hydrochloride |
Non-Patent Citations (1)
| Title |
|---|
| L-赖氨酸盐酸盐结晶过程研究;李倩;《中国优秀硕士学位论文全文数据库，工程科技I辑》;20100815;第B016-30页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110092729A (en) | 2019-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FI96122B (en) | Process for producing ethanol and collecting glycerol as a by-product | |
| CN107058416B (en) | Fermentation process for refining glutamic acid | |
| CN108299278B (en) | Method for extracting and separating L-tryptophan | |
| CN109504720B (en) | Green production process of glutamic acid | |
| CN105693592A (en) | Process method for efficiently extracting L-tryptophan from fermentation liquor through thallus carrying crystallization | |
| CN108285913B (en) | Process for preparing and extracting L-glutamine | |
| JP2001025368A (en) | Supplement for feed based on fermentation-treated liquid, its production, and use of l-lysin and/or salt thereof as supplement for feed | |
| CN104263793A (en) | Method for treating crystalline dextrose mother liquid | |
| CN110092729B (en) | Crystallization method of L-lysine hydrochloride | |
| CN113045610B (en) | Method for extracting glucosamine from N-acetylglucosamine fermentation liquor | |
| CN110963933A (en) | Process for extracting and purifying gamma-aminobutyric acid from tea | |
| CN109136299B (en) | Method for preparing, extracting and purifying threonine | |
| CN114287603A (en) | Method for improving color intensity of monosodium glutamate product | |
| JPS61212249A (en) | Composition for feed | |
| CN112979730A (en) | NMN extraction and purification method | |
| CN111139273A (en) | Method for preparing, separating and extracting L-tryptophan | |
| CN115851844A (en) | Production method of L-histidine hydrochloride | |
| CN118125930A (en) | Separation and purification method of L-isoleucine | |
| CN104212869B (en) | A kind of ultralow moisture content threonine production method | |
| CN114940664A (en) | Method for extracting L-histidine by using continuous cation exchange column | |
| CN108220351B (en) | Method for preparing L-arginine-alpha-ketoglutaric acid by biological enzyme method | |
| CN112553263A (en) | Method for extracting L-histidine by simulated moving bed chromatography | |
| CN114058653B (en) | Method for preparing gamma-aminobutyric acid by biological synthesis method | |
| KR20080085377A (en) | Method for preparing L-ornithine salt | |
| CN112430634A (en) | Process for preparing L-tryptophan by fermentation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |