CN109678769B - Method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor - Google Patents
Method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor Download PDFInfo
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- CN109678769B CN109678769B CN201910113862.8A CN201910113862A CN109678769B CN 109678769 B CN109678769 B CN 109678769B CN 201910113862 A CN201910113862 A CN 201910113862A CN 109678769 B CN109678769 B CN 109678769B
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- methionine
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- mother liquor
- metal chelate
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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 170
- 229930182817 methionine Natural products 0.000 title claims abstract description 170
- 239000012452 mother liquor Substances 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 238000002425 crystallisation Methods 0.000 title claims abstract description 31
- 230000008025 crystallization Effects 0.000 title claims abstract description 31
- 239000013522 chelant Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 55
- 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 claims abstract description 47
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 40
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 230000009920 chelation Effects 0.000 claims abstract description 13
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 7
- 108010016626 Dipeptides Proteins 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229960000355 copper sulfate Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000004697 chelate complex Chemical class 0.000 claims 6
- 235000011181 potassium carbonates Nutrition 0.000 abstract description 18
- 239000011736 potassium bicarbonate Substances 0.000 abstract description 13
- 235000015497 potassium bicarbonate Nutrition 0.000 abstract description 13
- 229910000028 potassium bicarbonate Inorganic materials 0.000 abstract description 13
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 150000002742 methionines Chemical class 0.000 description 19
- 238000004042 decolorization Methods 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000011573 trace mineral Substances 0.000 description 8
- 235000013619 trace mineral Nutrition 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- SBKRXUMXMKBCLD-UHFFFAOYSA-N 5-(2-methylsulfanylethyl)imidazolidine-2,4-dione Chemical compound CSCCC1NC(=O)NC1=O SBKRXUMXMKBCLD-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229950006451 sorbitan laurate Drugs 0.000 description 3
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- -1 alkali metal bicarbonate Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229940038879 chelated zinc Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000006109 methionine Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- 235000019728 animal nutrition Nutrition 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- CFYDRTTUISZGNQ-WJXVXWFNSA-L dipotassium (2S)-2-amino-4-methylsulfanylbutanoic acid carbonate Chemical compound [K+].[K+].[O-]C([O-])=O.CSCC[C@H](N)C(O)=O CFYDRTTUISZGNQ-WJXVXWFNSA-L 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000020939 nutritional additive Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Abstract
The invention relates to a method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor, which takes the extracted methionine crystallization mother liquor as a raw material and comprises the following steps: (1) Heating and concentrating the extracted methionine crystallization mother liquor to obtain a potassium methionine and potassium carbonate mixed liquor, analyzing the contents of methionine and potassium ions in the mixed liquor, and adding a certain amount of methionine into the obtained mixed liquor to obtain a potassium methionine aqueous solution; (2) Adding the potassium methionine aqueous solution into the metal sulfate aqueous solution for chelation reaction, carrying out suction filtration, washing and drying to obtain a methionine metal chelate, concentrating and crystallizing filtrate to obtain potassium sulfate crystals. The method fully utilizes methionine and potassium bicarbonate in the extracted methionine crystallization mother liquor to produce methionine metal chelate, not only solves the aggregation of impurities in the methionine production process, but also plays a role in comprehensive utilization of wastes, and achieves win-win effect of economy and environment.
Description
Technical Field
The invention belongs to the field of organic complex preparation, and in particular relates to a method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor, wherein the methionine metal chelate is mainly used as an animal feed additive.
Background
The known main stream production method of methionine is that 5- (2-methylthioethyl) -hydantoin aqueous solution is hydrolyzed in the presence of potassium carbonate to obtain potassium methionine aqueous solution containing potassium carbonate, then carbon dioxide is introduced into the potassium methionine aqueous solution containing potassium carbonate for neutralization, and then methionine is crystallized and separated out, so as to obtain methionine wet product and potassium bicarbonate aqueous solution (filtrate) containing methionine respectively; the aqueous potassium bicarbonate solution (filtrate) containing methionine is concentrated and returned to the hydrolysis process of the aqueous 5- (2-methylthioethyl) -hydantoin solution.
U.S. patent No. 4069251 discloses a continuous production method of methionine, comprising the following production steps: the 5- (2-methylthioethyl) -hydantoin is hydrolyzed in an aqueous solution of alkali metal carbonate and/or bicarbonate, the methionine produced is separated by carbon dioxide, and the mother liquor containing alkali metal bicarbonate and methionine is recycled in production.
Since the mother liquor containing alkali metal bicarbonate and methionine is recycled, it is necessary to remove a certain amount of the mother liquor from the system, that is to say to perform a so-called partial washing, in order to avoid the accumulation of impurities and coloured substances in the mother liquor system. However, the mother liquor removed by partial washing still contains valuable methionine and potassium salt components, and if it is not treated, the mother liquor removed by partial washing is discharged, which is disadvantageous from the viewpoint of economy and environmental friendliness, and is usually treated simply and directly by incineration or, in order to separate methionine and bicarbonate formed, the mother liquor is partially neutralized with carbon dioxide at a temperature as low as possible and mixed with 2 to 3 times of a water-soluble solvent such as methanol and acetone, so that methionine and bicarbonate are sufficiently separated out for separation and recovery.
U.S. patent No. 4303621 discloses a method: if most of the mother liquor produced by the separation of methionine is concentrated and cooled to carbonation, methionine and potassium can be easily recovered in a filtered form from the circulating liquid in the potassium carbonate-methionine carbonation process, wherein the mother liquor is concentrated to have a titratable potassium content of at least 120 liters per liter and the carbonation is carried out at a carbon dioxide pressure of 0.5 to 20 atm.
Japanese patent JP-A-5-320124 discloses a method for producing methionine, which comprises separating and collecting a filtrate left from a mother liquor, adding isopropyl alcohol to the filtrate in an amount of 0.5 to 2 parts by weight per part by weight of the filtrate, saturating the filtrate with carbon dioxide under cooling conditions at 0.5 to 20 absolute atmospheres to precipitate methionine and potassium bicarbonate, and separating and recovering these precipitates.
However, according to these methods, the main impurities in the mother liquor are methionine dimer which is converted into methionine under alkaline conditions, and can be regarded as equivalent of methionine, but if the dimerization volume of methionine in the mother liquor is excessively increased, crystallization of methionine is affected, however, other substances added during crystallization of methionine such as polyvinyl alcohol, sorbitan laurate, hydroxypropyl methylcellulose and the like are accumulated along with circulation of the mother liquor, and the obtained methionine and potassium bicarbonate are entrained with these impurities as well, so that the mother liquor is not completely decomposed, and an effective method for fundamentally solving the problem is to partially extract the mother liquor for incineration treatment, thereby avoiding or solving the aggregation of impurities in the system. Of course, such treatment is carried out at the expense of environmental and economical aspects, since the mother liquor of incineration treatment also contains valuable methionine and potassium bicarbonate.
Microelements are very important nutritional additives, and the microelements commonly used in feed and premix at present mainly comprise inorganic salts such as sulfate, chloride, oxide and the like, and have a plurality of defects such as: the chemical reaction is complex in the animal nutrition, and is easily influenced by components such as phosphate, phytic acid and the like in the feed, so that insoluble precipitate is formed, the biological titer is reduced, and the absorption and utilization are influenced; in feed processing, inorganic salt generally contains crystal water and is easy to absorb moisture and agglomerate. The inorganic salt has strong damage to vitamins, grease and the like. Some feed factories adopt high-manganese high-zinc feed, the effect is not high, and the environment is seriously polluted.
The organic trace element chelate can be used as an additive to replace inorganic mineral salt, so that the problems of excessive addition of metal elements, low absorption and utilization rate and the like can be solved. The organic trace element chelate refers to a cyclic compound formed by coordination bond of metal ions and ligands, and the molecular weight is generally not more than 800. Research shows that the trace element amino acid chelate is a safer third-generation trace element additive, and compared with inorganic mineral salts, the trace element amino acid chelate has the following characteristics: (1) The chemical structure is stable, and trace elements are not easy to precipitate or adsorb; (2) The biological potency is high, the absorption is fast, and the energy consumption in the body is saved; (3) The effect of improving the growth performance and the anti-stress capability of the livestock is very obvious; (4) The absorption efficiency is high, the use amount is obviously reduced, and the pollution of heavy metal elements to the environment along with the discharge of the excrement can be greatly reduced.
A large number of experiments prove that the methionine trace element chelated metal salt combines animal necessary metal elements and methionine in a molar ratio of 1:2 according to the unique chemical structure, has stable molecular structure, has the highest biological potency and excellent chemical stability, avoids the mutual antagonism between minerals, and also eliminates the defect of oxidizing vitamins by inorganic salts. The methionine trace element chelated metal salt integrates economy, high efficiency and environmental protection, has the advantages of high digestion and absorption rate, interference resistance, no stimulation, no toxicity and the like, and is widely applied to the feed industry and the food industry.
As known in the art, the preparation method of methionine metal chelate generally takes commercial grade methionine and metal inorganic salt as raw materials, sodium hydroxide adjusts the pH value of a reaction system, the molar ratio of methionine to metal ions is 2:1, and sodium sulfate is a byproduct of the methionine metal chelate.
Aiming at the defects, through the production practice of the inventor for many years, a method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor is developed, and the method fully utilizes methionine and potassium bicarbonate in the extracted methionine crystallization mother liquor to produce the methionine metal chelate, thereby achieving comprehensive utilization of wastes and achieving win-win effect on economy and environment.
Disclosure of Invention
In order to solve these problems, the present inventors have found an effective method for recovering methionine and its methionine dimer from the discharged mother liquor and have conducted extensive studies. As a result, it was found that methionine and methionine dimer in the discharged mother liquor can be fully utilized by the following method, and thus win-win situation in economy and environmental protection can be achieved. And (3) carrying out heat treatment on the discharged mother liquor to hydrolyze methionine dimer into methionine, analyzing the molar ratio of methionine to potassium ions, adding methionine to convert potassium carbonate in the mother liquor subjected to heat treatment into potassium methionine, finally obtaining a potassium methionine aqueous solution, and carrying out chelation reaction on the potassium methionine aqueous solution and the metal sulfate aqueous solution to obtain methionine metal chelate and potassium sulfate respectively. The value of potassium sulfate is relatively high, and the potassium sulfate can be fully treated as fertilizer, and the market price of potassium sulfate and potassium carbonate is basically equivalent to that of potassium. The present invention has been completed based on the findings described above, which are based on comprehensive consideration of wastes and a great deal of experimental demonstration and consideration of the market value of by-products thereof.
The method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor provided by the invention takes the extracted methionine crystallization mother liquor as a raw material, and comprises the following steps:
(1) Heating and concentrating the extracted methionine crystallization mother liquor to obtain a potassium methionine and potassium carbonate mixed liquor, analyzing the contents of methionine and potassium ions in the mixed liquor, and adding a certain amount of methionine into the obtained mixed liquor to obtain a potassium methionine aqueous solution;
(2) Adding the potassium methionine aqueous solution into the metal sulfate aqueous solution for chelation reaction, carrying out suction filtration, washing and drying to obtain a methionine metal chelate, concentrating and crystallizing filtrate to obtain potassium sulfate crystals.
The invention is applied as a method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor, wherein the methionine crystallization mother liquor is as follows: in the potassium salt process, carbon dioxide is introduced to neutralize, and crystallization mother liquor is obtained after methionine is separated, wherein the mother liquor comprises methionine, potassium bicarbonate, potassium carbonate, methionine dipeptide and other organic matters such as polyvinyl alcohol, sorbitan laurate or hydroxypropyl methyl cellulose, wherein the methionine accounts for 4.0 wt-9.0 wt%, the potassium ion accounts for 4.0 wt-11.0 wt%, the methionine dipeptide accounts for 0.01-0.01 wt.0 wt%, the other organic matter impurities account for 0.01-0.01 wt.5 wt%, and the pH of the mother liquor accounts for 7.5-9.0. The extraction of the mother liquor is a necessary operation in the methionine production process to prevent the impurities in the mother liquor from gathering in the system, thereby affecting the quality of methionine products and methionine crystallization. In order to prevent the accumulation of impurities, the part of mother liquor is usually conventionally subjected to incineration treatment or addition of water-miscible organic solvents such as methanol, acetone and isopropanol to precipitate methionine and potassium bicarbonate, however, only incineration truly solves the problem of impurity accumulation, and the problem that methionine and potassium bicarbonate in the mother liquor cannot be recycled to cause loss of methionine and potassium bicarbonate is caused, so that not only is economic loss, but also environmental pollution is caused by incineration treatment, and pollutants such as sulfur dioxide and the like are generated.
The impurity in the mother liquor is partially generated by the reaction, and the methionine dimer is necessarily the product of incomplete hydrolysis of raw material 5- (2-methylthioethyl) -hydantoin during hydrolysis, and although the impurity is insufficient to influence the quality of methionine products, the enrichment of methionine dimer can lead to difficult crystallization of methionine, and particularly when carbon dioxide is introduced, a large amount of foaming phenomenon occurs, so that the defects of low bulk density of the obtained methionine, more powder materials and the like are caused. But it is notable that methionine dimer is convertible to methionine under alkaline conditions at high temperatures.
Therefore, further, in order to convert methionine dimer in the mother liquor into methionine, the heating temperature of the methionine crystallization mother liquor in the step (1) is 140 to 200 ℃, preferably 160 to 185 ℃, particularly preferably 175 to 180 ℃, the concentration is carried out until the potassium ion concentration is 12.0 to 20wt%, the molar ratio of potassium ion to methionine is 2 to 6:1, the molar ratio of potassium ion to methionine is 0.90 to 1.0:1 after the methionine is added, the methionine concentration is 25.0 to 48.0wt%, and the pH of the potassium methionine aqueous solution is 12 to 14.
For additional organic impurities such as polyvinyl alcohol, sorbitan laurate or hydroxypropyl methylcellulose, etc., these organic substances are added to obtain methionine crystals with high bulk density during methionine crystallization, so as to prevent excessive powder from occurring, and part of such impurities remain in the mother liquor after methionine crystallization is caused by the necessary operation, thus forming enrichment. The best method for treating the impurities (including colored impurities) is to decolorize the activated carbon, wherein the consumption of the activated carbon is about one thousandth of that of the mother solution, the decolorization temperature is 40-60 ℃, the decolorization time is 30-60 min, and the removal rate of the impurities can reach more than 90%.
In the invention, the molar ratio of potassium methionine to metal sulfate in the step (2) is 2:1, the chelation reaction temperature is 40-90 ℃, preferably 60-85 ℃, particularly preferably 65-75 ℃, the chelation reaction time is 30-180 min, preferably 60-120 min, particularly preferably 60-90 min, and the addition sequence is that the potassium methionine aqueous solution is added into the metal sulfate aqueous solution, or the potassium methionine and the metal sulfate are simultaneously added into water.
Further, the metal sulfate in the step (2) is a solid or aqueous solution of zinc sulfate, ferrous sulfate, manganese sulfate, nickel sulfate, copper sulfate, preferably a saturated aqueous solution, particularly preferably a saturated aqueous solution.
Further, the molecular structural formula of the methionine metal chelate is as follows:
in the molecular structural formula of methionine metal chelate, the molar ratio of methionine to metal M is 2:1, and the methionine metal chelate is anhydrous compound or hydrate.
The invention has the advantages and positive effects that: the method fully utilizes methionine and potassium bicarbonate in the extracted methionine crystallization mother liquor to produce methionine metal chelate, not only solves the aggregation of impurities in the methionine production process, avoids the waste of resources and a large amount of energy consumption caused by the traditional incineration treatment or the treatment method of adding water-miscible organic solvent, plays a role in comprehensive utilization of wastes, fully utilizes methionine and methionine dimer and potassium bicarbonate in the mother liquor, achieves win-win effect on economy and environment, has low production cost, high product purity, simple production and easy operation, and has high industrial application value.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
Example 1
Adding 500 kg of methionine crystal mother liquor into a high-pressure reaction kettle with zirconium material, wherein the mass percent of methionine is 7.5wt%, the mass percent of methionine dimer is 0.5wt%, the mass percent of potassium ion is 9.5wt%, the mass percent of other organic matters is 0.02wt%, and the pH value of the mother liquor is 8.7; the mother liquor was heated to 185℃and carbon dioxide gas generated during the heating was properly released, and stirred at 185℃for 30 minutes to obtain an aqueous solution of potassium methionine and potassium carbonate, in which methionine dimer was analyzed and not detected.
And (3) cooling the obtained potassium methionine and potassium carbonate mixed solution to 90 ℃, concentrating under reduced pressure until the mass percent of methionine is 15wt%, the potassium ions are 19wt%, adding 142.98 kg of 99wt% methionine, heating to 120 ℃, and stirring to completely react to obtain 393.0 kg of potassium methionine aqueous solution, wherein the mass percent of methionine is 46wt%, the mass percent of potassium ions is 12.08wt%, and the pH value of the solution is 13.5. 0.4 kg of active carbon is added into the aqueous solution for decolorization treatment, the decolorization temperature is 60 ℃, the decolorization time is 60 minutes, and the active carbon is filtered by suction to obtain the light yellow potassium methionine aqueous solution.
Adding 225.38 kg of zinc sulfate saturated aqueous solution (60 ℃ and 42.98 wt%) into a chelating reaction kettle, slowly adding the obtained potassium methionine aqueous solution under stirring, heating to 80 ℃ after the addition, and preserving heat and stirring for 70 minutes; after the reaction, cooling to 25 ℃, carrying out suction filtration and water washing to obtain white powder of methionine chelated zinc, and carrying out drying treatment at 110 ℃ to obtain 213.63 kg of powder of methionine chelated zinc, wherein the yield is 97%, the purity is 99%, the chelation rate of zinc is 99%, the methionine content is 82.1wt% and the mass percentage of zinc is 17.9wt%; the product was taken for solubility analysis, which was 0.04 g/100 ml water (37 ℃). Concentrating and crystallizing the filtrate to obtain the byproduct potassium sulfate.
Example 2
Adding 500 kg of methionine crystal mother liquor into a high-pressure reaction kettle with zirconium material, wherein the mass percent of methionine is 8.0wt%, the mass percent of methionine dimer is 0.1wt%, the mass percent of potassium ion is 9.0wt%, the mass percent of other organic matters is 0.01wt%, and the pH value of the mother liquor is 8.5; the mother liquor was heated to 185℃and carbon dioxide gas generated during the heating was properly released, and stirred at 185℃for 30 minutes to obtain an aqueous solution of potassium methionine and potassium carbonate, in which methionine dimer was analyzed and not detected.
And cooling the obtained potassium methionine and potassium carbonate mixed solution to 90 ℃, concentrating under reduced pressure until the mass percent of methionine is 16wt%, the potassium ions are 18wt%, then adding 133.85 kg of 99wt% methionine, heating to 120 ℃, and stirring to completely react to obtain 400.0 kg of potassium methionine aqueous solution, wherein the mass percent of methionine is 43.6wt%, the mass percent of potassium ions is 11.25wt%, and the pH value of the solution is 13.0. 0.4 kg of active carbon is added into the aqueous solution for decolorization treatment, the decolorization temperature is 60 ℃, the decolorization time is 60 minutes, and the active carbon is filtered by suction to obtain the light yellow potassium methionine aqueous solution.
Adding 308.29 kg of ferrous sulfate saturated aqueous solution (60 ℃ and 28.60 wt%) into a chelating reaction kettle, slowly adding the obtained potassium methionine aqueous solution under stirring, heating to 80 ℃ after the addition, and preserving heat and stirring for 70 minutes; after the reaction is finished, cooling to 25 ℃, carrying out suction filtration and water washing to obtain brown yellow powder of methionine chelated ferrous, and carrying out drying treatment at 110 ℃ to obtain 203.25 kg of powdery methionine chelated ferrous, wherein the yield is 98%, the purity is 99%, the zinc chelation rate is 99%, the methionine content is 84.20wt% and the ferrous mass percentage is 15.80wt%; the product was taken for solubility analysis, which was 0.035 g/100 ml water (37 ℃). Concentrating and crystallizing the filtrate to obtain the byproduct potassium sulfate.
Example 3
Adding 500 kg of methionine crystal mother liquor into a high-pressure reaction kettle with zirconium material, wherein the mass percent of methionine is 7.5wt%, the mass percent of methionine dimer is 0.5wt%, the mass percent of potassium ion is 9.5wt%, the mass percent of other organic matters is 0.02wt%, and the pH value of the mother liquor is 8.7; the mother liquor was heated to 185℃and carbon dioxide gas generated during the heating was properly released, and stirred at 185℃for 30 minutes to obtain an aqueous solution of potassium methionine and potassium carbonate, in which methionine dimer was analyzed and not detected.
And (3) cooling the obtained potassium methionine and potassium carbonate mixed solution to 90 ℃, concentrating under reduced pressure until the mass percent of methionine is 15wt%, the potassium ions are 19wt%, adding 142.98 kg of 99wt% methionine, heating to 120 ℃, and stirring to completely react to obtain 393.0 kg of potassium methionine aqueous solution, wherein the mass percent of methionine is 46wt%, the mass percent of potassium ions is 12.08wt%, and the pH value of the solution is 13.5. 0.4 kg of active carbon is added into the aqueous solution for decolorization treatment, the decolorization temperature is 60 ℃, the decolorization time is 60 minutes, and the active carbon is filtered by suction to obtain the light yellow potassium methionine aqueous solution.
Adding 342.00 kg of saturated aqueous solution of copper sulfate (60 ℃ C., 28.36 wt%) into a chelating reaction kettle, slowly adding the obtained aqueous solution of potassium methionine under stirring, heating to 80 ℃ after the addition, and keeping the temperature for 70 minutes; after the reaction, cooling to 25 ℃, carrying out suction filtration and water washing to obtain methionine chelated copper blue powder, and carrying out drying treatment at 110 ℃ to obtain 218.212 kg of powdery methionine chelated copper, wherein the yield is 98%, the purity is 99%, the copper chelation rate is 99%, the methionine content is 82.5wt% and the copper mass percentage is 17.5wt%; the product was taken for solubility analysis, which was 0.04 g/100 ml water (37 ℃). Concentrating and crystallizing the filtrate to obtain the byproduct potassium sulfate.
Example 4
Adding 500 kg of methionine crystal mother liquor into a high-pressure reaction kettle with zirconium material, wherein the mass percent of methionine is 8.0wt%, the mass percent of methionine dimer is 0.1wt%, the mass percent of potassium ion is 9.0wt%, the mass percent of other organic matters is 0.01wt%, and the pH value of the mother liquor is 8.5; the mother liquor was heated to 185℃and carbon dioxide gas generated during the heating was properly released, and stirred at 185℃for 30 minutes to obtain an aqueous solution of potassium methionine and potassium carbonate, in which methionine dimer was analyzed and not detected.
And cooling the obtained potassium methionine and potassium carbonate mixed solution to 90 ℃, concentrating under reduced pressure until the mass percent of methionine is 16wt%, the potassium ions are 18wt%, then adding 133.85 kg of 99wt% methionine, heating to 120 ℃, and stirring to completely react to obtain 400.0 kg of potassium methionine aqueous solution, wherein the mass percent of methionine is 43.6wt%, the mass percent of potassium ions is 11.25wt%, and the pH value of the solution is 13.0. 0.4 kg of active carbon is added into the aqueous solution for decolorization treatment, the decolorization temperature is 60 ℃, the decolorization time is 60 minutes, and the active carbon is filtered by suction to obtain the light yellow potassium methionine aqueous solution.
Adding 225.08 kg of the obtained potassium methionine aqueous solution and manganese sulfate saturated aqueous solution (25 ℃ and 38.91wt% of manganese sulfate) into a chelating reaction kettle at the same time, and heating to 80 ℃ after the adding is completed under the stirring state, and preserving heat and stirring for 70 minutes; after the reaction, cooling to 25 ℃, carrying out suction filtration and water washing to obtain gray brown powder of methionine chelated manganese, and carrying out drying treatment at 110 ℃ to obtain 202.91 kg of powdery methionine chelated manganese, wherein the yield is 98%, the purity is 99%, the chelation rate of manganese is 99%, the methionine content is 84.50wt% and the mass percentage of manganese is 15.50wt%; the product was taken for solubility analysis, which was 0.04 g/100 ml water (37 ℃). Concentrating and crystallizing the filtrate to obtain the byproduct potassium sulfate.
Example 5
Adding 500 kg of methionine crystal mother liquor into a high-pressure reaction kettle with zirconium material, wherein the mass percent of methionine is 8.0wt%, the mass percent of methionine dimer is 0.1wt%, the mass percent of potassium ion is 9.0wt%, the mass percent of other organic matters is 0.01wt%, and the pH value of the mother liquor is 8.5; the mother liquor was heated to 185℃and carbon dioxide gas generated during the heating was properly released, and stirred at 185℃for 30 minutes to obtain an aqueous solution of potassium methionine and potassium carbonate, in which methionine dimer was analyzed and not detected.
And cooling the obtained potassium methionine and potassium carbonate mixed solution to 90 ℃, concentrating under reduced pressure until the mass percent of methionine is 16wt%, the potassium ions are 18wt%, then adding 133.85 kg of 99wt% methionine, heating to 120 ℃, and stirring to completely react to obtain 400.0 kg of potassium methionine aqueous solution, wherein the mass percent of methionine is 43.6wt%, the mass percent of potassium ions is 11.25wt%, and the pH value of the solution is 13.0. 0.4 kg of active carbon is added into the aqueous solution for decolorization treatment, the decolorization temperature is 60 ℃, the decolorization time is 60 minutes, and the active carbon is filtered by suction to obtain the light yellow potassium methionine aqueous solution.
Adding 251.21 kg of the obtained potassium methionine aqueous solution and nickel sulfate saturated aqueous solution (25 ℃ and 35.73 wt%) into a chelating reaction kettle at the same time, and heating to 80 ℃ after the addition is completed under the stirring state, and preserving heat and stirring for 70 minutes; after the reaction, cooling to 25 ℃, carrying out suction filtration and water washing to obtain light green powder of methionine chelate nickel, and carrying out drying treatment at 110 ℃ to obtain 202.94 kg of powder of methionine chelate nickel, wherein the yield is 97%, the purity is 99%, the chelation rate of nickel is 99%, the methionine content is 84.00wt% and the nickel mass percentage is 16.00wt%; the product was taken for solubility analysis, which was 0.04 g/100 ml water (37 ℃). Concentrating and crystallizing the filtrate to obtain the byproduct potassium sulfate.
Claims (6)
1. A method for producing methionine metal chelate by comprehensively utilizing methionine crystallization mother liquor is characterized by comprising the following steps:
(1) Heating and concentrating methionine crystallization mother liquor which is extracted in the production process of potassium methionine as a raw material to obtain a potassium methionine and potassium carbonate mixed solution, and adding methionine into the obtained mixed solution to obtain a potassium methionine aqueous solution;
(2) Adding the potassium methionine aqueous solution into the metal sulfate aqueous solution for chelation reaction, carrying out suction filtration, washing and drying to obtain a methionine metal chelate, concentrating and crystallizing filtrate to obtain potassium sulfate crystals;
The methionine crystallization mother liquor is as follows: in the potassium salt process, carbon dioxide is introduced for neutralization, and crystallization mother liquor is obtained after methionine is separated, wherein the mother liquor comprises 4.0 to wt weight percent of methionine, 9.0 weight percent of potassium carbonate, 4.0 to 11.0 weight percent of methionine dipeptide, 0.01 to wt weight percent of methionine dipeptide, 0.01 to wt.5 weight percent of other organic matter impurities.
2. The method for producing methionine metal chelate complex by comprehensively utilizing methionine crystallization mother liquor according to claim 1, wherein the heating temperature of the methionine crystallization mother liquor in the step (1) is 140-200 ℃, the concentration is carried out until the potassium ion concentration is 12.0-20wt%, the molar ratio of the potassium ion to methionine is 2-6:1, the molar ratio of the potassium ion to methionine is 0.90-1.0:1 after the methionine is added, and the methionine concentration is 25.0-48.0wt%.
3. The method for producing methionine metal chelate complex by comprehensively utilizing methionine crystallization mother liquor according to claim 1, wherein the molar ratio of potassium methionine to metal sulfate in the step (2) is 2:1, the chelation reaction temperature is 40-90 ℃, the chelation reaction time is 30-180 min, and the addition sequence is that the potassium methionine aqueous solution is added into the metal sulfate aqueous solution, or the potassium methionine and the metal sulfate are simultaneously added into water.
4. The method for producing methionine metal chelate complex by comprehensively utilizing methionine crystallization mother liquor according to claim 1, wherein the metal sulfate in the step (2) is zinc sulfate, ferrous sulfate, manganese sulfate, nickel sulfate or copper sulfate.
5. The method for producing methionine metal chelate according to claim 1, wherein the methionine metal chelate has the following molecular structural formula:
。
6. The method for producing methionine metal chelate complex by comprehensively utilizing methionine crystal mother liquor according to claim 5, wherein the molar ratio of methionine to metal M in the molecular structural formula of methionine metal chelate complex is 2:1, and the methionine metal chelate complex is anhydrous compound or hydrate.
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| CN102702050A (en) * | 2011-03-28 | 2012-10-03 | 住友化学株式会社 | Process for producing methionine |
| CN103224461A (en) * | 2013-04-22 | 2013-07-31 | 广州天科生物科技有限公司 | Preparation method of large granule crystal form methionine metal chelate and application thereof |
| CN104058844A (en) * | 2014-06-09 | 2014-09-24 | 李学春 | Method for preparing multielement chelate fertilizer by use of threonine mother liquor |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101602700A (en) * | 2008-06-09 | 2009-12-16 | 住友化学株式会社 | Produce the method for methionine(Met) |
| CN102399177A (en) * | 2010-09-15 | 2012-04-04 | 李宽义 | Environment-friendly and clean process method for continuous synthesis of methionine |
| CN102702050A (en) * | 2011-03-28 | 2012-10-03 | 住友化学株式会社 | Process for producing methionine |
| CN103224461A (en) * | 2013-04-22 | 2013-07-31 | 广州天科生物科技有限公司 | Preparation method of large granule crystal form methionine metal chelate and application thereof |
| CN104058844A (en) * | 2014-06-09 | 2014-09-24 | 李学春 | Method for preparing multielement chelate fertilizer by use of threonine mother liquor |
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