CN117645559A - Methionine composition and preparation method and application thereof - Google Patents
Methionine composition and preparation method and application thereof Download PDFInfo
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- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 title claims abstract description 215
- 229930182817 methionine Natural products 0.000 title claims abstract description 215
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 239000012043 crude product Substances 0.000 claims description 40
- 238000001953 recrystallisation Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 241001465754 Metazoa Species 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006052 feed supplement Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims description 2
- 235000019730 animal feed additive Nutrition 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 78
- 238000006243 chemical reaction Methods 0.000 description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 49
- 239000001569 carbon dioxide Substances 0.000 description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 description 39
- SBKRXUMXMKBCLD-UHFFFAOYSA-N 5-(2-methylsulfanylethyl)imidazolidine-2,4-dione Chemical compound CSCCC1NC(=O)NC1=O SBKRXUMXMKBCLD-UHFFFAOYSA-N 0.000 description 25
- 229910021529 ammonia Inorganic materials 0.000 description 24
- 230000020477 pH reduction Effects 0.000 description 24
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 21
- 229940091173 hydantoin Drugs 0.000 description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- 238000006460 hydrolysis reaction Methods 0.000 description 18
- 239000000413 hydrolysate Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 description 13
- QHMWJBZUZWPWFB-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;potassium Chemical compound [K].CSCC[C@H](N)C(O)=O QHMWJBZUZWPWFB-WCCKRBBISA-N 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 11
- 239000012452 mother liquor Substances 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 235000011181 potassium carbonates Nutrition 0.000 description 9
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 150000003112 potassium compounds Chemical class 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SBKRXUMXMKBCLD-SCSAIBSYSA-N (R)-5-[2-(methylthio)ethyl]hydantoin Chemical compound CSCC[C@H]1NC(=O)NC1=O SBKRXUMXMKBCLD-SCSAIBSYSA-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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MWLKEJXYXYRWIH-UHFFFAOYSA-N 2-amino-4-methylsulfanylbutanenitrile Chemical compound CSCCC(N)C#N MWLKEJXYXYRWIH-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102100033538 Clusterin-associated protein 1 Human genes 0.000 description 1
- 101000945057 Danio rerio Clusterin-associated protein 1 homolog Proteins 0.000 description 1
- 101000945060 Homo sapiens Clusterin-associated protein 1 Proteins 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process 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
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000020997 lean meat Nutrition 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002742 methionines Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a methionine composition, a preparation method and application thereof. The methionine composition comprises methionine and a structural compound of formula (1);
Description
Technical Field
The invention belongs to the field of nutritional chemicals, and particularly relates to a methionine composition, a preparation method and application thereof.
Background
Methionine is one of the basic units constituting protein, is the only sulfur-containing amino acid in the essential amino acids of feed protein, is the first limiting amino acid of poultry feed, and is a raw material for synthesizing protein and cystine in addition to participating in the transfer of methyl groups and the metabolism of phosphorus and the synthesis of epinephrine, choline and creatine in animals. Methionine can not be synthesized in animals and needs to be taken from food, and the methionine can promote the growth of livestock, increase lean meat amount, shorten feeding period and the like by adding the methionine into the feed. The synthesis process of methionine has been studied and developed for many years, and the technology is relatively mature and mainly adopts chemical synthesis method for production.
In the process of acidifying potassium methionine solution obtained by potassium carbonate, potassium bicarbonate, potassium hydroxide and other potassium salts or alkaline hydrolysis of hydantoin with carbon dioxide to precipitate methionine, the crystallization mother liquor after methionine separation needs to be recycled due to the inclusion of potassium salt and non-precipitated methionine, which tends to cause enrichment of impurities in the recycling mother liquor and affect the quality of methionine obtained by subsequent separation. As reported in patent CN1589259a, methionine polymer impurities produced in the hydrolysis process of hydantoin have an influence on the crystal form of crystals precipitated in the crystallization process with carbon dioxide gas, and it is proposed that methionine with improved crystal form and bulk density can be obtained by controlling the methionine polymer content below a specific value; w02013030068 reports the presence of potassium formate in the circulating mother liquor, which is formed from residual hydrocyanic acid in hydantoin during the hydrolysis of hydantoin; patent CN112679401a proposes that in the reaction process, cyanohydrin is polymerized and decomposed into sulfur-containing impurities, hydantoin is polymerized into macropigment molecules and the like, and the sulfur-containing impurities and hydantoin are continuously accumulated in a system along with the circulation of mother liquor, and finally the crystallization yield and quality, appearance color and the like of methionine are directly affected.
In addition, methionine obtained by crystallization of methionine potassium salt through carbon dioxide acidification reaction is usually in the form of powdery or thinner flaky crystals, has poor morphology, low bulk density and poor dispersibility, causes difficulty in production and transportation, and often needs to be recrystallized to improve the crystal quality and improve the bulk density.
The prior art has no method for effectively solving the problems, so that development of a production process of high-quality methionine is urgently needed.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide a methionine composition having improved crystal quality and increased bulk density.
The invention also aims to provide a preparation method of the methionine composition, which is used for effectively controlling the content of specific impurities to obtain a methionine composition product with excellent quality.
The invention also provides the application of the methionine composition as an animal feed additive.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a methionine composition comprising methionine and a structural compound of formula (1);
wherein the structural compound of formula (1) is contained in an amount of 1 to 20ppm, for example, 1ppm, 3ppm, 5ppm, 8ppm, 10ppm, 15ppm, 20ppm, etc., based on the total mass of the methionine composition.
The inventors of the present application have unexpectedly found that the presence of a structural compound of formula (1) (characterized as follows) on the surface of methionine crystals in an amount of about 0.05-2wt% has an effect on product quality in relation to the crystal form and bulk density of the methionine product.
A structural compound of formula (1): 1H NMR (DMSO-d) 6 ，400MHz)δppm：10.06(s，1H)、8.01(s，1H)、4.83(t，1H)、4.53(t，1H)、2.60(t，4H)、2.32(q，4H)、2.14(s，6H)。m/z：306.0708。
The invention is based on the discovery that the content of the structural compound of the control formula (1) is between 1 and 20ppm, and the high-quality methionine composition can be obtained, and the composition has the advantages of improved crystal quality, improved bulk density, low color number of products and good stability.
In a second aspect, the present invention provides a method for preparing the above methionine composition, and it should be understood by those skilled in the art that the following preparation method is only an exemplary illustration of the manner in which the methionine composition of the present invention having the above characteristics is derived, but not limiting in any way. The methionine composition of the present invention is not limited to the preparation methods listed below, and the content of the structural compound of formula (1) in the methionine composition can be controlled to a certain extent, for example, by directly adding or using conventional separation and purification methods based on the existing methionine products.
The present invention provides a method for preparing the methionine composition, which comprises the steps of pre-treating a methionine crude product with ethanol, recrystallizing, controlling the content of the compound with the structure of formula (1) in the recrystallization solution, separating, washing and drying to obtain the methionine composition.
In a preferred embodiment, the present invention provides a method for producing the above methionine composition, comprising the steps of:
pretreating a methionine crude product by adopting ethanol, recrystallizing, separating methionine crystals, washing and drying to obtain a methionine composition;
wherein the recrystallization process controls the content of the compound of the formula (1) in the recrystallization solution to 5 to 200ppm, for example, 5ppm, 10ppm, 50ppm, 80ppm, 100ppm, 130ppm, 150ppm, 180ppm, 200ppm, etc.
In the method for pretreating the methionine crude product by using ethanol, the methionine crude product and the ethanol are mixed according to the mass ratio of 1:1-5 for example 1:1. 1:2. 1:3. 1: 4. 1:5, and the like, then stirring at 40-70 ℃ such as 40 ℃, 50 ℃, 60 ℃, 70 ℃ and the like for 30-60min such as 30min, 40min, 50min, 60min and the like, cooling to 0-5 ℃ such as 0 ℃, 1 ℃,2 ℃, 3 ℃, 4 ℃,5 ℃ and the like, precipitating methionine, filtering to separate methionine and ethanol, drying methionine, and then carrying out the next recrystallization; or alternatively
Preparing a methionine crude product into an aqueous solution with the concentration of 4-12wt%, such as 4wt%, 6wt%, 8wt%, 10wt%, 12wt%, and the like, then adding ethanol with the mass of 1-5 times, such as 1 time, 2 times, 3 times, 4 times, 5 times, and the like (based on the mass of the methionine crude product), stirring at 40-70 ℃ such as 40 ℃, 50 ℃, 60 ℃, 70 ℃ and the like for 30-60min, such as 30min, 40min, 50min, 60min, and the like, cooling to 0-5 ℃ such as 0 ℃, 1 ℃,2 ℃, 3 ℃, 4 ℃,5 ℃ and the like to precipitate methionine, separating methionine, drying, and then performing the next recrystallization;
the ethanol and ethanol water mixed solution used in the pretreatment can be reused; after pretreatment with ethanol, the content of the structural compound of formula (1) in methionine can be controlled to be less than 1wt%.
In the method for recrystallizing, methionine pretreated by the ethanol is mixed with pure water, the content of the structural compound of the formula (1) in the recrystallization solution is controlled to be 5-200ppm, such as 5ppm, 10ppm, 50ppm, 80ppm, 100ppm, 130ppm, 150ppm, 180ppm, 200ppm and the like, the recrystallization solution is prepared, and then the methionine composition is obtained by crystallizing at 80-10 ℃ such as 80 ℃, 60 ℃, 40 ℃, 20 ℃ and the like for 6-10 hours such as 6 hours, 7 hours, 8 hours, 9 hours and 10 hours, separating methionine crystals in the next step, washing and drying; the operations of separation, washing, drying and the like are all conventional technical means in the field, and the invention is not particularly limited;
preferably, the crystallization at 80-10 ℃ is carried out for 6-10h, namely the crystallization is carried out by cooling from 80 ℃ to 10 ℃ within 6-10h.
According to the preparation method, the content of the structural compound in the formula (1) in the methionine composition can be controlled to be 1-20ppm. Recrystallizing the methionine crude product after the pretreatment of ethanol, and controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 5-200ppm. When the content of the structural compound in the formula (1) in the methionine recrystallization solution is 5-200ppm, the bulk density of the recrystallized product is improved and the crystal form is improved; when the content of the compound shown in the formula (1) in the methionine recrystallization solution is more than 200ppm, no obvious effect is provided for improving the crystal form and improving the bulk density, and more than 20ppm of the compound shown in the formula (1) enters the recrystallization product, so that the methionine composition has obvious color number rising in the process of drying and long-term storage. When the content of the structural compound of formula (1) in the methionine recrystallization solution is less than 5ppm, the bulk density of the product is not improved.
In the present invention, the crude methionine product may be any methionine product containing the structural compound of formula (1), its source and the content of the structural compound of formula (1) are not limited, for example, the content of the structural compound of formula (1) may be higher than 20ppm, and it may be used for further reduction of the content of the structural compound of formula (1) in 1 to 20ppm. The methionine product prepared by any method may be used as a crude product, and commercially available methionine products satisfying the above characteristics may be purchased as crude products, and in some specific examples of the present invention, the source thereof includes, but is not limited to, methionine prepared by a hydantoin hydrolysis process, preferably crude methionine prepared by a 5- (2-methyl mercaptoethyl) hydantoin hydrolysis process, and particularly crude methionine obtained by precipitation of methionine salt solution through a carbon dioxide acidification step.
In the production of methionine, at least 1 metal compound (e.g., potassium compound) selected from the group consisting of metal hydroxide, metal carbonate and metal bicarbonate is generally used as an aqueous solution of hydantoin to be used as an intermediate for hydrolyzing methionine, and methionine product (i.e., crude methionine) is separated after acidification of the aqueous methionine solution with carbon dioxide, which is a method disclosed in the prior art, and the present invention is not particularly limited and can be prepared by, for example, the method disclosed in patent CN116102475A, CN1589259a and the like.
Based on the prior researches, the invention discovers an industrial scheme for preparing a methionine crude product, which can be implemented by reacting 2-hydroxy-4 (methylthio) butyronitrile with excessive carbon dioxide and ammonia to generate 5- (2-methyl mercapto ethyl) hydantoin (methionine hydantoin), hydrolyzing the 5- (2-methyl mercapto ethyl) hydantoin under alkaline conditions to generate a potassium methionine solution, and acidifying the potassium methionine solution by carbon dioxide to precipitate the methionine crude product.
In some specific examples, the invention provides a method for preparing a methionine crude product, comprising the following steps:
s1: 2-hydroxy-4 (methylthio) butyronitrile reacts with excess carbon dioxide and ammonia to form 5- (2-methyl mercaptoethyl) hydantoin;
s2: hydrolyzing 5- (2-methyl mercapto ethyl) hydantoin under the condition of potash containing to obtain a potassium methionine solution;
s3: introducing carbon dioxide into the potassium methionine solution of S2 to acidify and precipitate out a crude product of methionine.
In the present invention, the reaction conditions in the step S1 are not particularly limited, and the skilled person can select according to the need by the conventionally disclosed method, for example, the molar ratio of the 2-hydroxy-4 (methylthio) butyronitrile to the carbon dioxide to ammonia is 1 (1.2-3): 1.2-4, for example, 1: (1.2, 1.5, 2.0, 2.5, 3.0): (1.2, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0);
the reaction is preferably carried out in two stages, wherein the first stage reaction temperature is 50-90 ℃, e.g., 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, etc., for 30-50min, e.g., 30min, 35min, 40min, 45min, 50min, etc.; the second stage reaction temperature is 100-150deg.C, such as 100deg.C, 120deg.C, 130deg.C, 140deg.C, 150deg.C, etc., and the time is 50-90min, such as 50min, 60min, 70min, 80min, 90min, etc.
In the present invention, the reaction conditions related to step S2 are not particularly limited, and the skilled person may select by a conventionally disclosed method, for example, the potash-containing alkaline conditions in which the base is selected from one or more of alkaline potassium compounds, preferably potassium hydroxide, potassium carbonate, potassium bicarbonate, and preferably an aqueous solution, as required; preferably, the alkaline conditions are such that the molar ratio of 5- (2-methyl mercaptoethyl) hydantoin to potassium ion is controlled to be 1:2-4, for example 1:2. 1:3. 1:4, etc.;
the hydrolysis reaction is carried out at 120-180deg.C, such as 120deg.C, 130deg.C, 140deg.C, 150deg.C, 160deg.C, 170deg.C, 180deg.C, etc., for 1-2 hr, such as 1 hr, 1.5 hr, 2 hr, etc.
In the present invention, the reaction conditions related to step S3 are not particularly limited, and the skilled person may perform screening by a conventionally disclosed method, for example, the acidification precipitation at a temperature of 5 to 40℃such as 5℃10℃15℃20℃25℃30℃35℃40℃and the like, preferably 10 to 20 ℃; the acidification pressure is 0.1-1.0MPaA, for example 0.1MPaA, 0.3MPaA, 0.5MPaA, 0.7MPaA, 0.9MPaA, 1.0MPaA, etc., preferably 0.2-0.8MPaA; the acidification time is 0.5-2h, such as 0.5h, 1h, 1.5h, 2h, etc., preferably 1.0-1.5h;
preferably, the acidification reaction is stopped when the pH of the reaction solution drops to < 8.0, e.g. 8.0, 7.9, 7.8, 7.5, 7.0, etc.
Specifically, the preparation method of the methionine crude product comprises the following steps:
s1: adding 2-hydroxy-4 (methylthio) butyronitrile, carbon dioxide and ammonia gas into a reaction kettle according to the molar ratio of (1.2-3) (1.2-4), reacting for 30-50min at 50-90 ℃, and then rapidly heating to 100-150 ℃ for reacting for 50-90min. Removing excessive ammonia and carbon dioxide in the reaction liquid after the reaction is finished to obtain a 5- (2-methyl mercapto ethyl) hydantoin solution;
s2: adding a 5- (2-methyl mercapto ethyl) hydantoin solution into a hydrolysis kettle, adding an alkaline potassium compound aqueous solution with the concentration of about 50wt%, controlling the molar ratio of the 5- (2-methyl mercapto ethyl) hydantoin to potassium ions to be 1:2-4, carrying out hydrolysis reaction for 1-2h at 120-180 ℃, and removing redundant ammonia and carbon dioxide in the hydrolysate after the reaction is finished to obtain a methionine potassium solution;
s3: adding the potassium methionine solution into an acidification kettle, introducing carbon dioxide into the acidification kettle, controlling the temperature in the kettle to be 5-40 ℃, acidifying for 0.5-2h at 0.1-1.0MPaA in the kettle, stopping the reaction when the pH value of the reaction solution is reduced to be less than or equal to 8.0, and separating a methionine crude product and a methionine mother liquor.
In the process of hydrolyzing and acidifying with carbon dioxide based on potassium hydroxide, potassium carbonate, potassium bicarbonate and the like, the structural compound of formula (1) exists on the surface of the prepared methionine crystal, and the reason is probably due to the fact that in the process of preparing 5- (2-methyl mercapto ethyl) hydantoin by reacting 2-hydroxy-4 (methylthio) butyronitrile with carbon dioxide and ammonia or with substances capable of generating carbon dioxide and ammonia, 2-hydroxy-4 (methylthio) butyronitrile reacts with ammonia to generate 2-amino-4 (methylthio) butyronitrile, and then further reacts with carbon dioxide to generate structural intermediate of formula (2), and the intermediate is further internally cyclized to generate hydantoin. Under the conditions of high temperature and high pressure of hydantoin hydrolysis, a small amount of 2-hydroxy-4 (methylthio) butyronitrile is hydrolyzed to generate 2-hydroxy-4 (methylthio) butyric acid, and the 2-hydroxy-4 (methylthio) butyric acid reacts with an intermediate of the formula (2) to obtain the compound with the structure of the formula (1). In the process of precipitating methionine by using the carbonic acid acidified hydantoin hydrolysate, the structural compound shown in the formula (1) is adsorbed on the surface of methionine crystals and is precipitated along with the methionine crystals, so that the subsequent purification is negatively influenced, the indexes such as purity, crystal form, bulk density and the like of a crystallized product are influenced, and the quality of the product is influenced.
It should be noted that the above method disclosed in the present invention is only used to illustrate one crude source mode adopted to implement the preparation method of the present invention, and the crude source of methionine raw material of the present invention should not be limited by the steps and parameters in the above method.
Also, the method for producing the methionine composition of the present invention should not be limited by the above method.
In a third aspect, the present invention provides a use of the above methionine composition.
Use of a methionine composition prepared by the above method, or of a methionine composition as described above, as an animal feed supplement.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The precipitated crude methionine is acidified through ethanol pretreatment, the content of the crude methionine and the compound with the structure of formula (1) in the recrystallization solution is controlled, and thick block crystals can be obtained after recrystallization, so that the bulk density and the purity are improved.
(2) The methionine composition has excellent storage stability, and no significant color number increase in drying and long-term storage.
Detailed Description
The invention will now be further illustrated with reference to specific examples which are only intended to illustrate the invention and are not to be construed as limiting the scope of the invention or the method of practicing the invention.
The main raw material source information in the examples and comparative examples of the present invention are as follows, and others are obtained from common commercial sources unless specified otherwise:
2-hydroxy-4 (methylthio) butanenitrile, prepared according to the procedure disclosed in example 1 of patent CN108191720 a, > 99%;
ammonia, smoke floor Hua Sheng gas, > 99.99%;
carbon dioxide, smoke bench torch gas, > 99.99%;
ammonium carbonate, allatin, more than or equal to 98%;
ammonium bicarbonate, alatine, 98% or more;
potassium carbonate, enokie, 99% or more.
The performance test parameters and the corresponding test methods adopted in the embodiments of the invention are as follows:
color number: LCS-IV liquid color difference meter;
bulk density: intelligent powder characteristic tester BT-1001 (dandongbaite);
morphology: optical microscope, HU500M, dongguan QiLin science and technology Co.
Example 1
Preparing a methionine crude product:
2-hydroxy-4 (methylthio) butyronitrile, carbon dioxide, ammonia and water are added into a reaction kettle according to a molar ratio of 1:1.5:2:25, and after reacting for 30min at 50 ℃, the temperature is quickly raised to 110 ℃ and the reaction is carried out for 60min at 110 ℃. And (3) removing excessive ammonia and carbon dioxide in the reaction solution after the reaction is finished to obtain a 5- (2-methyl mercapto ethyl) hydantoin solution.
Adding a 5- (2-methyl mercapto ethyl) hydantoin solution into a hydrolysis kettle, adding a potassium carbonate aqueous solution with the concentration of 50wt%, controlling the molar ratio of the 5- (2-methyl mercapto ethyl) hydantoin to potassium ions to be 1:2, carrying out hydrolysis reaction for 2 hours at 120 ℃, and removing excessive ammonia and carbon dioxide in the hydrolysate after the reaction is finished to obtain hydantoin hydrolysate (potassium methionine solution).
Adding hydantoin hydrolysate into an acidification kettle, introducing carbon dioxide into the acidification kettle, controlling the temperature in the kettle to be 10 ℃, controlling the pressure in the kettle to be 0.5MPaA, and stopping the acidification reaction when the pH value of the reaction solution is reduced to 8.0. And (3) adding the obtained solid-liquid mixture into a centrifugal machine, and separating a methionine crude product and methionine mother liquor, wherein the content of the structural compound in the methionine crude product is 0.75wt%.
Preparation of methionine composition:
preparing the methionine crude product into an aqueous solution with the concentration of 5wt%, adding ethanol with the mass of 1 time, stirring for 30min at 50 ℃, cooling to 0 ℃ to separate out methionine, separating methionine, drying, and measuring that the content of the structural compound in the formula (1) in the methionine is 0.15wt%.
Mixing the methionine treated by the ethanol with pure water, controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 150ppm, preparing the recrystallization solution, then cooling and crystallizing for 6 hours at 80-10 ℃ for recrystallization, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained had a methionine content of 99.5wt%, a bulk crystal, and a bulk density of 0.71g/cm 3 The compound of formula (1) in the composition has a content of 10ppm and a color number of 3.0Hazen in a 2wt% aqueous solution.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number was increased from the original 3.0Hazen to 3.1Hazen.
Example 2
Preparing a methionine crude product:
2-hydroxy-4 (methylthio) butyronitrile, carbon dioxide, ammonia and water are added into a reaction kettle according to a molar ratio of 1:2:3:23, and after reacting for 40min at 60 ℃, the temperature is quickly raised to 100 ℃ and the reaction is carried out for 90min at 100 ℃. And (3) removing excessive ammonia and carbon dioxide in the reaction solution after the reaction is finished to obtain a 5- (2-methyl mercapto ethyl) hydantoin solution.
Adding a 5- (2-methyl mercapto ethyl) hydantoin solution into a hydrolysis kettle, adding a potassium carbonate aqueous solution with the concentration of 50wt%, controlling the molar ratio of the 5- (2-methyl mercapto ethyl) hydantoin to potassium ions to be 1:2.5, carrying out hydrolysis reaction for 1.5 hours at 130 ℃, and removing excessive ammonia and carbon dioxide in the hydrolysate after the reaction is finished to obtain hydantoin hydrolysate (potassium methionine solution).
Adding hydantoin hydrolysate into an acidification kettle, introducing carbon dioxide into the acidification kettle, controlling the temperature in the kettle to be 15 ℃, controlling the pressure in the kettle to be 0.6MPaA, and stopping the acidification reaction when the pH value of the reaction solution is reduced to 7.5. And (3) adding the obtained solid-liquid mixture into a centrifugal machine, and separating a methionine crude product and methionine mother liquor, wherein the content of the structural compound in the methionine crude product is 0.95wt%.
Preparation of methionine composition:
preparing the methionine crude product into an aqueous solution with the concentration of 6wt%, adding ethanol with the mass of 2 times into the aqueous solution, stirring the aqueous solution at 45 ℃ for 40min, cooling the aqueous solution to 5 ℃ to precipitate methionine, separating methionine, drying the methionine, and measuring that the content of the structural compound of the formula (1) in the methionine is 0.24wt%.
Mixing the methionine treated by the ethanol with pure water, controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 120ppm, preparing the recrystallization solution, then cooling and crystallizing for 7 hours at 80-10 ℃ for recrystallization, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained had a methionine content of 99.3wt%, a bulk crystal, and a bulk density of 0.70g/cm 3 The compound of formula (1) in the composition has a content of 8ppm and a color number of 3.0Hazen in a 2wt% aqueous solution.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number was increased from the original 3.0Hazen to 3.1Hazen.
Example 3
Preparing a methionine crude product:
2-hydroxy-4 (methylthio) butyronitrile, carbon dioxide, ammonia and water are added into a reaction kettle according to a molar ratio of 1:1:1:25, and after reaction for 30min at 70 ℃, the temperature is quickly raised to 120 ℃ and the reaction is carried out for 75min at 120 ℃. And (3) removing excessive ammonia and carbon dioxide in the reaction solution after the reaction is finished to obtain a 5- (2-methyl mercapto ethyl) hydantoin solution.
Adding a 5- (2-methyl mercapto ethyl) hydantoin solution into a hydrolysis kettle, adding a potassium carbonate aqueous solution with the concentration of 50wt%, controlling the molar ratio of the 5- (2-methyl mercapto ethyl) hydantoin to potassium ions to be 1:3, carrying out hydrolysis reaction for 1h at 140 ℃, and removing excessive ammonia and carbon dioxide in the hydrolysate after the reaction is finished to obtain hydantoin hydrolysate (potassium methionine solution).
Adding hydantoin hydrolysate into an acidification kettle, introducing carbon dioxide into the acidification kettle, controlling the temperature in the kettle to be 20 ℃, controlling the pressure in the kettle to be 0.8MPaA, and stopping the acidification reaction when the pH value of the reaction solution is reduced to 7.0. And (3) adding the obtained solid-liquid mixture into a centrifugal machine, and separating a methionine crude product and methionine mother liquor, wherein the content of the structural compound in the methionine crude product is 1.12wt%.
Preparation of methionine composition:
the methionine crude product is directly soaked in 3 times mass ethanol, stirred at 60 ℃ for 45min, cooled to 2 ℃ to separate out methionine, separated out methionine and dried, and the content of the structural compound of the formula (1) in the methionine is measured to be 0.15wt%.
Mixing the methionine treated by the ethanol with pure water, controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 100ppm, preparing the recrystallization solution, then cooling and crystallizing for 8 hours at 80-10 ℃ for recrystallization, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained had a methionine content of 99.2wt%, a bulk crystal, and a bulk density of 0.71g/cm 3 The compound of formula (1) in the composition has a content of 6ppm and a color number of 3.0Hazen in a 2wt% aqueous solution.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number increased from the original 3.0Hazen to 3.05Hazen.
Example 4
2-hydroxy-4 (methylthio) butyronitrile, carbon dioxide, ammonia and water are added into a reaction kettle according to a molar ratio of 1:2:4:25, and after reacting for 50min at 65 ℃, the temperature is quickly raised to 130 ℃ and the reaction is carried out for 80min at 130 ℃. And (3) removing excessive ammonia and carbon dioxide in the reaction solution after the reaction is finished to obtain a 5- (2-methyl mercapto ethyl) hydantoin solution.
Adding a 5- (2-methyl mercapto ethyl) hydantoin solution into a hydrolysis kettle, adding a potassium carbonate aqueous solution with the concentration of 50wt%, controlling the molar ratio of the 5- (2-methyl mercapto ethyl) hydantoin to potassium ions to be 1:3.5, carrying out hydrolysis reaction for 1h at 150 ℃, and removing excessive ammonia and carbon dioxide in the hydrolysate after the reaction is finished to obtain hydantoin hydrolysate (potassium methionine solution).
Adding hydantoin hydrolysate into an acidification kettle, introducing carbon dioxide into the acidification kettle, controlling the temperature in the kettle to be 30 ℃, controlling the pressure in the kettle to be 0.7MPaA, and stopping the acidification reaction when the pH value of the reaction solution is reduced to 7.8. And (3) adding the obtained solid-liquid mixture into a centrifugal machine, and separating a methionine crude product and methionine mother liquor, wherein the content of the structural compound in the methionine crude product is 0.84wt%.
Preparation of methionine composition:
the methionine crude product is directly soaked in ethanol with the mass being 4 times, stirred for 50min at 40 ℃, cooled to 5 ℃ to separate out methionine, separated out methionine and dried, and the content of the structural compound of the formula (1) in the methionine is measured to be 0.09wt%.
Mixing the methionine treated by the ethanol with pure water, controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 50ppm, preparing the recrystallization solution, then cooling and crystallizing for 8 hours at 80-10 ℃ for recrystallization, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained had a methionine content of 99.2wt%, a bulk crystal, and a bulk density of 0.69g/cm 3 The compound of formula (1) in the composition has a content of 3ppm and a color number of 3.0Hazen in a 2wt% aqueous solution.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number increased from the original 3.0Hazen to 3.03Hazen.
Example 5
2-hydroxy-4 (methylthio) butyronitrile, carbon dioxide, ammonia and water are added into a reaction kettle according to a molar ratio of 1:3:2.5:25, and after reaction for 30min at 80 ℃, the temperature is quickly raised to 140 ℃ and the reaction is carried out for 70min at 140 ℃. And (3) removing excessive ammonia and carbon dioxide in the reaction solution after the reaction is finished to obtain a 5- (2-methyl mercapto ethyl) hydantoin solution.
Adding a 5- (2-methyl mercapto ethyl) hydantoin solution into a hydrolysis kettle, adding a potassium carbonate aqueous solution with the concentration of 50wt%, controlling the molar ratio of the 5- (2-methyl mercapto ethyl) hydantoin to potassium ions to be 1:4, carrying out hydrolysis reaction for 1h at 160 ℃, and removing excessive ammonia and carbon dioxide in the hydrolysate after the reaction is finished to obtain hydantoin hydrolysate (potassium methionine solution).
Adding hydantoin hydrolysate into an acidification kettle, introducing carbon dioxide into the acidification kettle, controlling the temperature in the kettle to be 25 ℃, controlling the pressure in the kettle to be 0.5MPaA, and stopping the acidification reaction when the pH value of the reaction solution is reduced to 8.0. And (3) adding the obtained solid-liquid mixture into a centrifugal machine, and separating a methionine crude product and methionine mother liquor, wherein the content of the structural compound in the methionine crude product is 1.50wt%.
Preparation of methionine composition:
the methionine crude product is directly soaked in ethanol with the mass being 5 times that of the methionine crude product, the methionine is separated out after being stirred for 60min at 70 ℃, the temperature is reduced to 3 ℃, the methionine is separated out and dried, and the content of the structural compound of the formula (1) in the methionine is measured to be 0.08 weight percent.
Mixing the methionine treated by the ethanol with pure water, controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 80ppm, preparing the recrystallization solution, then cooling and crystallizing for 9 hours at 80-10 ℃ for recrystallization, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained had a methionine content of 99.1wt%, a bulk crystal, and a bulk density of 0.70g/cm 3 The compound of formula (1) in the composition has a content of 4ppm and a color number of 3.0Hazen in a 2wt% aqueous solution.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number increased from the original 3.0Hazen to 3.08Hazen.
Comparative example 1
Mixing the methionine crude product with pure water, which is the same as that in example 1, to prepare a recrystallization solution, controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 300ppm, recrystallizing, cooling and crystallizing at 80-10 ℃ for 9h, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained had a methionine content of 97.2wt%, a long and thin leaf crystal, and a bulk density of 0.28g/cm 3 The content of the structural compound of formula (1) in the composition was 29ppm, and its 2wt% aqueous solution had a color number of 3.0Hazen.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number increased from the original 3.0Hazen to 3.4Hazen.
Comparative example 2
Mixing the methionine crude product with pure water, which is the same as that in example 1, to prepare a recrystallization solution, controlling the content of the structural compound in the formula (1) in the recrystallization solution to be 500ppm, recrystallizing, cooling and crystallizing at 80-10 ℃ for 10h, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained had a methionine content of 97.5wt%, a long and thin leaf crystal, and a bulk density of 0.30g/cm 3 The content of the structural compound of formula (1) in the composition is 40ppm, and the color number of a 2wt% aqueous solution thereof is 3.0Hazen.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number increased from the original 3.0Hazen to 3.5Hazen.
Comparative example 3
The same methionine crude product as in example 1 is directly soaked in ethanol of 2 times mass, stirred at 45 ℃ for 30min, cooled to 5 ℃ to precipitate methionine, separated methionine and dried, and the content of the structural compound of the formula (1) in the methionine is measured to be less than 0.01wt%.
Mixing the methionine treated by the ethanol with pure water to prepare a recrystallization solution, controlling the content of the structural compound of the formula (1) in the recrystallization solution to be 4ppm, recrystallizing, cooling and crystallizing for 9 hours at 80-10 ℃, separating methionine crystals, washing and drying to obtain the methionine composition.
The methionine composition obtained has a methionine content of 99.4wt%, long needle-like crystals, and a bulk density of 0.20g/cm 3 The content of the structural compound of formula (1) in the composition is 0.5ppm, and the color number of a 2wt% aqueous solution thereof is 3.0Hazen.
After the prepared methionine composition was stored at 60℃for 5 months, it was formulated as a 2wt% aqueous solution, and its color number increased from the original 3.0Hazen to 3.05Hazen.
From the above examples and comparative examples, it is apparent that methionine composition having high purity and high bulk density can be obtained by using the process of the present invention for producing methionine.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible in view of the teachings herein. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (9)
1. A methionine composition comprising methionine and a structural compound of formula (1);
wherein the content of the structural compound of formula (1) is 1 to 20ppm based on the total mass of the methionine composition.
2. A method for producing the methionine composition according to claim 1, comprising the steps of:
pretreating a methionine crude product by adopting ethanol, recrystallizing, separating methionine crystals, washing and drying to obtain a methionine composition;
wherein the recrystallization process controls the content of the compound with the structure of the formula (1) in the recrystallization solution to be 5-200ppm.
3. The preparation method of claim 2, wherein the method for pretreating the methionine crude product with ethanol comprises the steps of mixing the methionine crude product with ethanol according to a mass ratio of 1:1-5, stirring at 40-70deg.C for 30-60min, cooling to 0-5deg.C, precipitating methionine, filtering, and separating methionine and ethanol.
4. The method according to claim 2, wherein the pretreatment of the crude methionine with ethanol is carried out by preparing the crude methionine into an aqueous solution having a concentration of 4-12wt%, adding 1-5 times of ethanol, stirring at 40-70 ℃ for 30-60min, cooling to 0-5 ℃ to precipitate methionine, and separating methionine.
5. The method according to claim 3 or 4, wherein the ethanol/ethanol water mixture used for pretreatment is reusable.
6. The method according to claim 3 or 4, wherein the content of the compound of formula (1) in methionine is controlled to be less than 1wt% after pretreatment with ethanol.
7. The method according to claim 2, wherein the method for recrystallization comprises mixing the ethanol-pretreated methionine with pure water, controlling the content of the compound of formula (1) in the recrystallization solution to 5-200ppm, preparing the recrystallization solution, and crystallizing at 80-10deg.C for 6-10h.
8. The method according to claim 7, wherein the crystallization at 80-10 ℃ is performed by cooling from 80 ℃ to 10 ℃ within 6-10 hours.
9. Use of the methionine composition of claim 1 or the methionine composition prepared by the method of any one of claims 2-8 as an animal feed supplement.
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