CN109678769A - A method of comprehensive utilization methionine crystalline mother solution produces methionine metal chelate - Google Patents
A method of comprehensive utilization methionine crystalline mother solution produces methionine metal chelate Download PDFInfo
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- CN109678769A CN109678769A CN201910113862.8A CN201910113862A CN109678769A CN 109678769 A CN109678769 A CN 109678769A CN 201910113862 A CN201910113862 A CN 201910113862A CN 109678769 A CN109678769 A CN 109678769A
- Authority
- CN
- China
- Prior art keywords
- methionine
- potassium
- mother solution
- crystalline mother
- metal chelate
- Prior art date
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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 212
- 229930182817 methionine Natural products 0.000 title claims abstract description 212
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000013522 chelant Substances 0.000 title claims abstract description 36
- 239000010413 mother solution Substances 0.000 title claims abstract description 31
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 61
- 239000011591 potassium Substances 0.000 claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 39
- 238000004519 manufacturing process 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000012452 mother liquor Substances 0.000 claims description 43
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 17
- 229910001414 potassium ion Inorganic materials 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- 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 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- ZYTPOUNUXRBYGW-UHFFFAOYSA-N methionyl-methionine Chemical compound CSCCC(N)C(=O)NC(C(O)=O)CCSC ZYTPOUNUXRBYGW-UHFFFAOYSA-N 0.000 claims description 4
- 108010085203 methionylmethionine Proteins 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 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
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 150000002742 methionines Chemical class 0.000 description 18
- 235000011181 potassium carbonates Nutrition 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000004061 bleaching Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011573 trace mineral Substances 0.000 description 5
- 235000013619 trace mineral Nutrition 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000009920 chelation Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 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
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940038879 chelated zinc Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001413 amino acids 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000019621 digestibility Nutrition 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
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 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 1
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229940029985 mineral supplement Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000020939 nutritional additive Nutrition 0.000 description 1
- 238000013021 overheating Methods 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
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research 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
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Materials Engineering (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods of comprehensive utilization methionine crystalline mother solution production methionine metal chelate, this method is using the methionine crystalline mother solution of extraction as raw material, the following steps are included: the methionine crystalline mother solution of (1) extraction carries out heating concentration, obtain methionine potassium and potassium carbonate mixed liquor, analyze the methionine and potassium content in mixed liquor, a certain amount of methionine is added into obtained mixed liquor, obtains methionine aqueous solutions of potassium；(2) methionine aqueous solutions of potassium is added in metal sulfate saline solution and carries out chelatropic reaction, filtered, washing, drying, obtain methionine metal chelate, concentrating filter liquor, crystallization obtain potassium sulfate crystal.This method makes full use of methionine and saleratus production methionine metal chelate in the methionine crystalline mother solution of extraction, not only solves the aggregation of impurity in methionine production process, and play the comprehensive utilization of waste, has reached economy and environment two-win.
Description
Technical field
The invention belongs to the complex compound preparation field that organises, especially a kind of comprehensive utilization methionine crystalline mother solution produces egg
The method of propylhomoserin metallo-chelate, methionine metal chelate are mainly used for animal feed additive.
Background technique
5-(2- methylmercaptoethyl is hydrolyzed under the conditions of the mainstream production method of known methionine is existing for the potassium carbonate)-
Hydantoins aqueous solution obtains the methionine aqueous solutions of potassium containing potassium carbonate, then water-soluble to the methionine potassium containing potassium carbonate
Being passed through after carbon dioxide neutralizes in liquid makes the crystallization of its methionine be precipitated, separate, and respectively obtains methionine wet product and contains methionine
Potassium bicarbonate aqueous solution (filtrate)；Potassium bicarbonate aqueous solution (filtrate) containing methionine is back to 5- by concentration
(2-methylmercaptoethyl)-hydantoins aqueous hydrolysis process.
United States Patent (USP) US4069251 discloses a kind of methionine continuous producing method, including following production stage: 5-(2-
Methylmercaptoethyl)-hydantoins hydrolyzes in alkali carbonate and/or bicarbonate aqueous solution, utilize carbon dioxide separation
The methionine of production, and include that the mother liquor of alkali metal hydrogencarbonate and methionine is recycled in production.
Since the mother liquor of alkali metal containing bicarbonate and methionine is recycled, it is therefore necessary to by a certain amount of mother liquor from
It is removed in system, that is to say, that carry out so-called part cleaning, such operation purpose is to avoid the impurity in mother liquor system
With gathering for coloring matter.However, the mother liquor removed by part cleaning still includes valuable methionine and sylvite component, such as
Fruit discharges the mother liquor removed by part cleaning without handling it, is unfavorable from the perspective of economical and environmental-friendly
, and usually simple direct processing mode is exactly burning disposal, or in order to separate the methionine of formation and bicarbonate, it will
Mother liquor fraction in alap temperature carbon dioxide and, and with 2 to 3 times two of water-soluble solvent such as methanol and acetone and
Mixing, its methionine and bicarbonate is precipitated sufficiently, to achieve the purpose that separation and recovery.
United States Patent (USP) US4303621 discloses a kind of method: if isolating mother liquor quilt caused by most of methionine
Concentration and cooling carbonating, then methionine and potassium can be easily in the form of filtering from potassium carbonate-methionine carbonating process
Circulation fluid in recycle, wherein mother liquor be concentrated at least be containing titratable potassium content 120 can be every liter, and carbonate in dioxy
Changing carbon pressure power is that the pressure of 0.5~20 strict atmospheric carries out.
Japan Patent JP-A-5-320124 discloses a kind of method for producing methionine, including from mother liquor point
From the filtrate left with collection methionine, isopropanol is added with the amount of 0.5~2 part of weight of every part of weight filtrate into filtrate,
Cooling condition carbon dioxide precipitates its methionine and saleratus with 0.5~20 strict atmospheric pressure saturation filtrate and separates
Recycle these precipitatings.
However according to these methods, main impurity is methionine dimer in mother liquor, and methionine dimer is in alkalinity
Under the conditions of can be converted into methionine, the equivalent for methionine is considered as, only such as two of methionine in fruit mother liquor
Aggressiveness accumulation is excessive, other substances such as polyethylene that will affect the crystallization of methionine, however be added in methionine crystallization process
Alcohol, sorbitan lauric acid rouge, hydroxypropyl methyl cellulose etc. can be accumulated, either above-mentioned side with the circulation of mother liquor
Method is added organic solvent miscible with water and carries out precipitate methionine and potassium and saleratus, and obtained methionine and saleratus are same
These impurity can be carried secretly, to can be brought into system again, this method is fundamentally that can't resolve impurity in mother liquor in fact
Accumulation, fundamentally solve effective method and be exactly that part extraction mother liquor carries out burning disposal, thus avoid or
Solve the aggregation of impurity in systems.Certainly, such processing is carried out under the premise of sacrificialing environment and economy, because burning
It burns in the mother liquor of processing also containing valuable considerable methionine and saleratus.
Microelement is highly important nutritive additive, the micro member generally used in feed, premix at present
Plain additive is mainly the inorganic salts such as sulfate, chlorate, oxide, they have many defects, such as: in Animal nutrition due to
It chemically reacts complicated in digestion process, vulnerable to the influence of the ingredients such as phosphate, phytic acid in feed, and forms infusible precipitate,
Biological value is reduced, affects and is absorbed and utilized；Inorganic salts generally have the crystallization water, easy moisture absorption agglomeration in feed processing.
Inorganic salts are stronger to destructions such as vitamin and greases.Some feed factories use high manganese high zinc diets, produce effects not high, and serious
Pollute environment.
Organic trace element chelating object replace inorganic mineral salt as additive can solve metallic element excess addition with
The problems such as absorption rate is low.Organic trace element chelating object refers to what metal ion was formed by coordinate bond and ligands
Cyclic compound, molecular weight are usually no more than 800.Research shows that microelement amino acid chelate object is the safer third generation
Trace mineral supplement, compared with inorganic mineral salt, microelements aminophenol chelated has the following characteristics that (1) chemical structure
Stablize, microelement is not easy to be made to precipitate or be adsorbed；(2) biological value is high, not only absorbs fastly, but also saves energy i (in vivo) and disappear
Consumption；(3) improve growth of animals or poultry performance and anti-stress ability effect is fairly obvious；(4) absorption efficiency is high, and usage amount significantly reduces,
Heavy metal element can be substantially reduced to be discharged with excrement to pollution caused by environment.
Many experiments confirm the trace element chelated metal salt of methionine with its unique chemical structure, the necessary gold of animal
Belong to element and methionine to combine with the molar ratio of 1:2, molecular structure stabilized has highest biological value and excellent change
Stability is learned, the drawbacks of not only having avoided the mutual antagonism between minerals, but also eliminated inorganic salts phylloquinone oxide K1.Egg ammonia
The trace element chelated metal salt of acid integrates economy, high efficiency, the feature of environmental protection, high, anti-interference with digestibility,
The advantages that non-stimulated and nonhazardous, is widely used in feed, food service industry.
It is well known that the preparation method of methionine metal chelate is usually to be with commodity grade methionine and metal inorganic salt
The molar ratio of raw material, the pH of sodium hydroxide adjusting reaction system, methionine and metal ion is 2:1, obtained methionine metal
Chelate, by-product sodium sulphate.
In view of the above-mentioned deficiencies, by the production practices of inventor's many years, a kind of comprehensive utilization methionine crystallization is developed
The method that mother liquor produces methionine metal chelate, this method make full use of methionine and carbon in the methionine crystalline mother solution of extraction
Potassium hydrogen phthalate produces methionine metal chelate, plays the comprehensive utilization of waste, has reached economy and environment two-win.
Summary of the invention
In order to solve these problems, present inventor have found one effectively from the mother liquor of discharge recycle methionine and its
The method of methionine dimer is widely studied.As a result, it has been found that the egg in the mother liquor that it can by the following method discharged
Propylhomoserin and methionine dimer are fully utilized, and reach the two-win on economical and environmentally friendly.Heat is carried out to the mother liquor discharged
Processing, makes its methionine dimer be hydrolyzed to methionine, then analyzes the molar ratio of wherein methionine and potassium ion, and egg ammonia is added
Acid makes potassium carbonate in its mother liquor after Overheating Treatment be converted into methionine potassium, finally obtains methionine aqueous solutions of potassium, methionine
Aqueous solutions of potassium and metal sulfate saline solution carry out chelatropic reaction, respectively obtain methionine metal chelate and potassium sulfate.Sulfuric acid
The value of potassium be it is relatively high, can be used as chemical fertilizer processing completely, it is base that the market price of potassium sulfate and potassium carbonate, which is scaled potassium,
It is equivalent in sheet.The present invention is accomplished according to above-mentioned discovery, it is such be the discovery that based on to waste comprehensively consider and
A large amount of experimental demonstration and its by-product market value consider and obtain.
A kind of side of comprehensive utilization methionine crystalline mother solution production methionine metal chelate provided by according to the present invention
Method, this method are using the methionine crystalline mother solution of extraction as raw material, comprising the following steps:
(1) the methionine crystalline mother solution produced carries out heating concentration, obtains methionine potassium and potassium carbonate mixed liquor, analyzes mixed liquor
In methionine and potassium content, a certain amount of methionine is added into obtained mixed liquor, obtains methionine aqueous solutions of potassium；
(2) methionine aqueous solutions of potassium is added in metal sulfate saline solution and carries out chelatropic reaction, filtered, washing, drying, obtain
To methionine metal chelate, concentrating filter liquor, crystallization obtain potassium sulfate crystal.
The present invention produces the method for methionine metal chelate as a kind of comprehensive utilization methionine crystalline mother solution and is able to
Using wherein the methionine crystalline mother solution are as follows: in sylvite technique, be passed through carbon dioxide neutralization, obtained after separation methionine
Crystalline mother solution, the mother liquor group become methionine, saleratus, potassium carbonate, methionylmethionine, other organic matters such as polyvinyl alcohol,
Sorbitan lauric acid rouge or hydroxypropyl methyl cellulose, wherein methionine is 4.0 wt %~9.0wt%, potassium ion 4.0
Wt %~11.0wt%, methionylmethionine be 0.01 wt %~1.0wt%, other organic impurities be 0.01 wt %~
0.5wt%, the pH of mother liquor are 7.5~9.0.The extraction of such mother liquor is necessary operation in methionine production process, to prevent
Impurity in mother liquor is assembled in system, to influence the quality and methionine crystallization of methionine product.And impurity in order to prevent
Accumulate the partial mother liquid of extraction often the measure taken of tradition be carry out burning disposal be either added it is miscible with water organic molten
Agent such as methanol, acetone, isopropanol etc. carries out that methionine and saleratus is precipitated, however only burns the real impurity that solves and gather
Collection problem, the problem of can burning institute's band are that the methionine and saleratus in mother liquor can not recycle, cause methionine and
The loss of saleratus, this is not only economic loss, and burning disposal also brings pollution environmentally, generates dioxy
Change the pollutants such as sulphur.
Impurity in mother liquor is partly due to caused by reaction that inevitable methionine dimer is exactly raw material 5-(2- first sulphur
Base ethyl) hydrolysis of-hydantoins when endless fully hydrolyzed product, although such impurity is not enough to influence the matter of methionine product
Amount, but the enrichment of methionine dimer will lead to methionine crystallization difficulty, when being especially passed through carbon dioxide, occur a large amount of
Foamed phenomenon, cause to obtain the disadvantages of methionine bulk density is low, and powder is more.It would be appreciated that methionine dimerization
Body can be converted into methionine under alkaline condition, by high temperature.
Therefore, further, in order to make methionine dimer in its mother liquor be converted into methionine, egg ammonia in the step (1)
Acid crystal mother liquor heating temperature is 140 DEG C~200 DEG C, preferably 160 DEG C~185 DEG C, particularly preferred 175 DEG C~180 DEG C, described dense
Potassium concentration is reduced to as 12.0wt%~20wt%, the molar ratio of potassium ion and methionine is 2~6:1, after methionine is added, potassium
The molar ratio of ion and methionine is 0.90~1.0:1, and methionine concentration is 25.0wt%~48.0wt%, methionine aqueous solutions of potassium
PH be 12~14.
For additional organic impurities such as such as polyvinyl alcohol, sorbitan lauric acid rouge or hydroxypropyl methyl cellulose
Deng these organic matters are added to obtain the methionine crystal of high-bulk-density in methionine crystallization process, prevent excessive
Powder occur, it is such must operate cause methionine crystallize after, impurity as part has stayed in mother liquor, so as to form
Enrichment.Handling these impurity (including foreign pigment) optimal methods is to carry out active carbon decoloring, and the dosage of active carbon is mother liquor
One thousandth of amount or so, bleaching temperature are 40 DEG C~60 DEG C, and bleaching time is 30~60min, and the removal rate of impurity can reach
To 90% or more.
In the present invention, the molar ratio of methionine potassium and metal sulfate is 2:1 in the step (2), and chelating is anti-
Answer temperature be 40 DEG C~90 DEG C, preferably 60 DEG C~85 DEG C, particularly preferred 65 DEG C~75 DEG C, the chelatropic reaction time be 30~
180min, preferably 60~120min, particularly preferred 60~90min, addition sequence are that methionine aqueous solutions of potassium is added to metal
In sulfate solution, or methionine potassium is added to the water simultaneously with metal sulfate.
Further, metal sulfate is zinc sulfate, ferrous sulfate, manganese sulfate, nickel sulfate, copper sulphate in the step (2)
Solid or aqueous solution, preferred saturated aqueous solution, particularly preferred saturated aqueous solution.
Further, the molecular structural formula of the methionine metal chelate is as follows:
In the molecular structural formula of above-mentioned methionine metal-chelating, the molar ratio of methionine and metal M are 2:1, methionine metal chelating
Closing object is anhydrous compound or hydrate.
The advantages and positive effects of the present invention are: the method for the present invention makes full use of egg ammonia in the methionine crystalline mother solution of extraction
Acid and saleratus produce methionine metal chelate, not only solve the aggregation of impurity in methionine production process, avoid passing
Burning disposal of uniting or the wasting of resources of method bring and a large amount of energy consumption that organic solvent processing miscible with water is added,
The comprehensive utilization of waste is played, the methionine and its methionine dimer and saleratus in mother liquor have all obtained abundant benefit
With having reached economy and environment two-win, production cost is low, and product purity is high, and production is simple easily operated, has very high work
Industry application value.
Specific embodiment
The present invention is described in further detail below by specific embodiment, it is not to limit that following embodiment, which is descriptive,
Property, this does not limit the scope of protection of the present invention.
Embodiment 1
500 kilograms of methionine crystalline mother solution is added in the autoclave with zirconium material, wherein the quality percentage of methionine
Content is 7.5wt%, and the mass percentage of methionine dimer is 0.5wt%, and the mass percentage of potassium ion is 9.5wt%,
The mass percentage of other organic matters is 0.02wt%, and the pH of mother liquor is 8.7；Be heated to 185 DEG C to mother liquor, it is heated
The carbon dioxide gas that generation is suitably discharged in journey keeps the temperature 30 minutes in 185 DEG C of stirrings, obtains methionine potassium and potassium carbonate is water-soluble
Liquid is analyzed wherein methionine dimer, is not detected.
Methionine potassium obtained above and potassium carbonate mixed liquor are cooled to 90 DEG C, carry out the matter for being concentrated under reduced pressure into methionine
Amount percentage composition is 15wt%, potassium ion 19wt%, and 142.98 kilograms of methionine of 99wt% are then added, are warming up to 120 DEG C,
Stirring completely reaction, obtain 393.0 kilograms of methionine aqueous solutions of potassium, wherein the mass percentage of methionine be 46wt%, potassium from
The mass percentage of son is 12.08wt%, and the pH of solution is 13.5.0.4 kilogram of active carbon is added in the aqueous solution to carry out
Decolorization, bleaching temperature are 60 DEG C, and bleaching time is 60 minutes, filters active carbon, and it is yellowish for obtaining methionine aqueous solutions of potassium
Color.
225.38 kilograms of zinc sulfate saturated aqueous solution (60 DEG C, zinc sulfate 42.98wt%) are added in chelatropic reaction kettle, so
It is stirred under state, is slowly added into methionine aqueous solutions of potassium obtained above, after adding, be warming up to 80 DEG C of insulated and stirreds 70 and divide
Clock；After having reacted, 25 DEG C are cooled to, then filters, wash, obtain Methionine Chelated Zinc white powder, dried by 110 DEG C
Processing obtains 213.63 kilograms of powdered Methionine Chelated Zinc, and yield 97%, purity 99%, the chelation percent of zinc is 99%,
Wherein methionine content is 82.1wt%, and the mass percentage of zinc is 17.9wt%；Product is taken to carry out solubility analysis, dissolution
Degree is 0.04 gram/100 milliliters water (37 DEG C).Filtrate passes through concentration, and crystallization obtains by-product potassium sulfate.
Embodiment 2
500 kilograms of methionine crystalline mother solution is added in the autoclave with zirconium material, wherein the quality percentage of methionine
Content is 8.0wt%, and the mass percentage of methionine dimer is 0.1wt%, and the mass percentage of potassium ion is 9.0wt%,
The mass percentage of other organic matters is 0.01wt%, and the pH of mother liquor is 8.5；Be heated to 185 DEG C to mother liquor, it is heated
The carbon dioxide gas that generation is suitably discharged in journey keeps the temperature 30 minutes in 185 DEG C of stirrings, obtains methionine potassium and potassium carbonate is water-soluble
Liquid is analyzed wherein methionine dimer, is not detected.
Methionine potassium obtained above and potassium carbonate mixed liquor are cooled to 90 DEG C, carry out the matter for being concentrated under reduced pressure into methionine
Amount percentage composition is 16wt%, potassium ion 18wt%, and 133.85 kilograms of methionine of 99wt% are then added, are warming up to 120 DEG C,
Stirring reaction completely, obtains 400.0 kilograms of methionine aqueous solutions of potassium, and wherein the mass percentage of methionine is 43.6wt%, potassium
The mass percentage of ion is 11.25wt%, and the pH of solution is 13.0.In the aqueous solution be added 0.4 kilogram active carbon into
Row decolorization, bleaching temperature are 60 DEG C, and bleaching time is 60 minutes, filters active carbon, and it is light for obtaining methionine aqueous solutions of potassium
Yellow.
It is public that ferrous sulfate saturated aqueous solution (60 DEG C, ferrous sulfate 28.60wt%) 308.29 are added in chelatropic reaction kettle
Jin, is so stirred under state, is slowly added into methionine aqueous solutions of potassium obtained above, after adding, be warming up to 80 DEG C of insulated and stirreds
70 minutes；After having reacted, 25 DEG C are cooled to, then filters, wash, obtain methionine chelate ferrous iron brownish-yellow powder shape, pass through
110 DEG C of drying and processings obtain 203.25 kilograms powdered of methionine chelate ferrous iron, yield 98%, purity 99%, the chela of zinc
Conjunction rate is 99%, and wherein methionine content is 84.20wt%, and ferrous mass percentage is 15.80wt%；Product is taken to carry out molten
Xie Du analysis, solubility are 0.035 gram/100 milliliters water (37 DEG C).Filtrate passes through concentration, and crystallization obtains by-product sulphur
Sour potassium.
Embodiment 3
500 kilograms of methionine crystalline mother solution is added in the autoclave with zirconium material, wherein the quality percentage of methionine
Content is 7.5wt%, and the mass percentage of methionine dimer is 0.5wt%, and the mass percentage of potassium ion is 9.5wt%,
The mass percentage of other organic matters is 0.02wt%, and the pH of mother liquor is 8.7；Be heated to 185 DEG C to mother liquor, it is heated
The carbon dioxide gas that generation is suitably discharged in journey keeps the temperature 30 minutes in 185 DEG C of stirrings, obtains methionine potassium and potassium carbonate is water-soluble
Liquid is analyzed wherein methionine dimer, is not detected.
Methionine potassium obtained above and potassium carbonate mixed liquor are cooled to 90 DEG C, carry out the matter for being concentrated under reduced pressure into methionine
Amount percentage composition is 15wt%, potassium ion 19wt%, and 142.98 kilograms of methionine of 99wt% are then added, are warming up to 120 DEG C,
Stirring completely reaction, obtain 393.0 kilograms of methionine aqueous solutions of potassium, wherein the mass percentage of methionine be 46wt%, potassium from
The mass percentage of son is 12.08wt%, and the pH of solution is 13.5.0.4 kilogram of active carbon is added in the aqueous solution to carry out
Decolorization, bleaching temperature are 60 DEG C, and bleaching time is 60 minutes, filters active carbon, and it is yellowish for obtaining methionine aqueous solutions of potassium
Color.
342.00 kilograms of copper sulphate saturated aqueous solution (60 DEG C, zinc sulfate 28.36wt%) are added in chelatropic reaction kettle, so
It is stirred under state, is slowly added into methionine aqueous solutions of potassium obtained above, after adding, be warming up to 80 DEG C of insulated and stirreds 70 and divide
Clock；After having reacted, 25 DEG C are cooled to, then filters, wash, obtain Methionine chelate copper blue powder shape, dried by 110 DEG C
Processing obtains 218.212 kilograms of powdered Methionine chelate copper, and yield 98%, purity 99%, the chelation percent of copper is 99%,
Wherein methionine content is 82.5wt%, and the mass percentage of copper is 17.5wt%；Product is taken to carry out solubility analysis, dissolution
Degree is 0.04 gram/100 milliliters water (37 DEG C).Filtrate passes through concentration, and crystallization obtains by-product potassium sulfate.
Embodiment 4
500 kilograms of methionine crystalline mother solution is added in the autoclave with zirconium material, wherein the quality percentage of methionine
Content is 8.0wt%, and the mass percentage of methionine dimer is 0.1wt%, and the mass percentage of potassium ion is 9.0wt%,
The mass percentage of other organic matters is 0.01wt%, and the pH of mother liquor is 8.5；Be heated to 185 DEG C to mother liquor, it is heated
The carbon dioxide gas that generation is suitably discharged in journey keeps the temperature 30 minutes in 185 DEG C of stirrings, obtains methionine potassium and potassium carbonate is water-soluble
Liquid is analyzed wherein methionine dimer, is not detected.
Methionine potassium obtained above and potassium carbonate mixed liquor are cooled to 90 DEG C, carry out the matter for being concentrated under reduced pressure into methionine
Amount percentage composition is 16wt%, potassium ion 18wt%, and 133.85 kilograms of methionine of 99wt% are then added, are warming up to 120 DEG C,
Stirring reaction completely, obtains 400.0 kilograms of methionine aqueous solutions of potassium, and wherein the mass percentage of methionine is 43.6wt%, potassium
The mass percentage of ion is 11.25wt%, and the pH of solution is 13.0.In the aqueous solution be added 0.4 kilogram active carbon into
Row decolorization, bleaching temperature are 60 DEG C, and bleaching time is 60 minutes, filters active carbon, and it is light for obtaining methionine aqueous solutions of potassium
Yellow.
By methionine aqueous solutions of potassium obtained above, manganese sulfate saturated aqueous solution (25 DEG C, manganese sulfate 38.91wt%)
225.08 kilograms are added in chelatropic reaction kettle simultaneously, are so stirred under state, after adding, are warming up to 80 DEG C of insulated and stirreds 70 and divide
Clock；After having reacted, 25 DEG C are cooled to, then filters, wash, obtain methionine chelate manganese grey-brown powder shape, dried by 110 DEG C
Dry-cure, obtains 202.91 kilograms of powdered methionine chelate manganese, and the chelation percent of yield 98%, purity 99%, manganese is
99%, wherein methionine content is 84.50wt%, and the mass percentage of manganese is 15.50wt%；Product is taken to carry out solubility analysis,
Its solubility is 0.04 gram/100 milliliters water (37 DEG C).Filtrate passes through concentration, and crystallization obtains by-product potassium sulfate.
Embodiment 5
500 kilograms of methionine crystalline mother solution is added in the autoclave with zirconium material, wherein the quality percentage of methionine
Content is 8.0wt%, and the mass percentage of methionine dimer is 0.1wt%, and the mass percentage of potassium ion is 9.0wt%,
The mass percentage of other organic matters is 0.01wt%, and the pH of mother liquor is 8.5；Be heated to 185 DEG C to mother liquor, it is heated
The carbon dioxide gas that generation is suitably discharged in journey keeps the temperature 30 minutes in 185 DEG C of stirrings, obtains methionine potassium and potassium carbonate is water-soluble
Liquid is analyzed wherein methionine dimer, is not detected.
Methionine potassium obtained above and potassium carbonate mixed liquor are cooled to 90 DEG C, carry out the matter for being concentrated under reduced pressure into methionine
Amount percentage composition is 16wt%, potassium ion 18wt%, and 133.85 kilograms of methionine of 99wt% are then added, are warming up to 120 DEG C,
Stirring reaction completely, obtains 400.0 kilograms of methionine aqueous solutions of potassium, and wherein the mass percentage of methionine is 43.6wt%, potassium
The mass percentage of ion is 11.25wt%, and the pH of solution is 13.0.In the aqueous solution be added 0.4 kilogram active carbon into
Row decolorization, bleaching temperature are 60 DEG C, and bleaching time is 60 minutes, filters active carbon, and it is light for obtaining methionine aqueous solutions of potassium
Yellow.
By methionine aqueous solutions of potassium obtained above, nickel sulfate saturated aqueous solution (25 DEG C, nickel sulfate 35.73wt%)
251.21 kilograms are added in chelatropic reaction kettle simultaneously, are so stirred under state, after adding, are warming up to 80 DEG C of insulated and stirreds 70 and divide
Clock；After having reacted, 25 DEG C are cooled to, then filters, wash, obtain methionine chelate nickel shallow green powder shape, dried by 110 DEG C
Dry-cure, obtains 202.94 kilograms of powdered methionine chelate nickel, and the chelation percent of yield 97%, purity 99%, nickel is
99%, wherein methionine content is 84.00wt%, and the mass percentage of nickel is 16.00wt%；Product is taken to carry out solubility analysis,
Its solubility is 0.04 gram/100 milliliters water (37 DEG C).Filtrate passes through concentration, and crystallization obtains by-product potassium sulfate.
Claims (7)
1. it is a kind of comprehensive utilization methionine crystalline mother solution production methionine metal chelate method, which is characterized in that including with
Lower step:
(1) it is heated and is concentrated as raw material using the methionine crystalline mother solution produced in methionine sylvite production process, obtain egg ammonia
Sour potassium and potassium carbonate mixed liquor, are added methionine into obtained mixed liquor, obtain methionine aqueous solutions of potassium；
(2) methionine aqueous solutions of potassium is added in metal sulfate saline solution and carries out chelatropic reaction, filtered, washing, drying, obtain
To methionine metal chelate, concentrating filter liquor, crystallization obtain potassium sulfate crystal.
2. a kind of side of comprehensive utilization methionine crystalline mother solution production methionine metal chelate according to claim 1
Method, which is characterized in that the methionine crystalline mother solution are as follows: in sylvite technique, be passed through carbon dioxide neutralization, obtained after separating methionine
The crystalline mother solution arrived, the mother liquor group become methionine, saleratus, potassium carbonate, methionylmethionine, other organic matters such as polyethylene
Alcohol, sorbitan lauric acid rouge or hydroxypropyl methyl cellulose, wherein methionine is 4.0 wt %~9.0wt%, and potassium ion is
4.0 wt %~11.0wt%, methionylmethionine be 0.01 wt %~1.0wt%, other organic impurities be 0.01 wt %~
0.5wt%。
3. a kind of side of comprehensive utilization methionine crystalline mother solution production methionine metal chelate according to claim 2
Method, which is characterized in that methionine crystalline mother solution heating temperature is 140 DEG C~200 DEG C in the step (1), described to be concentrated into potassium
Ion concentration is 12.0wt%~20wt%, and the molar ratio of potassium ion and methionine is 2~6:1, after methionine is added, potassium ion with
The molar ratio of methionine is 0.90~1.0:1, and methionine concentration is 25.0wt%~48.0wt%.
4. a kind of side of comprehensive utilization methionine crystalline mother solution production methionine metal chelate according to claim 2
Method, which is characterized in that the molar ratio of methionine potassium and metal sulfate is 2:1, chelatropic reaction temperature in the step (2)
It is 40 DEG C~90 DEG C, the chelatropic reaction time is 30~180min, and addition sequence is that methionine aqueous solutions of potassium is added to metal sulphur
In acid salt aqueous solution, or methionine potassium is added to the water simultaneously with metal sulfate.
5. a kind of side of comprehensive utilization methionine crystalline mother solution production methionine metal chelate according to claim 2
Method, which is characterized in that metal sulfate is zinc sulfate, ferrous sulfate, manganese sulfate, nickel sulfate, copper sulphate in the step (2).
6. a kind of side of comprehensive utilization methionine crystalline mother solution production methionine metal chelate according to claim 1
Method, which is characterized in that the molecular structural formula of the methionine metal chelate is as follows:
。
7. a kind of side of comprehensive utilization methionine crystalline mother solution production methionine metal chelate according to claim 6
Method, which is characterized in that in the molecular structural formula of the methionine metal-chelating, the molar ratio of methionine and metal M are 2:1, egg
Propylhomoserin metallo-chelate is anhydrous compound or hydrate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606335A (en) * | 2020-05-27 | 2020-09-01 | 天宝动物营养科技股份有限公司 | Method for comprehensively utilizing clean potassium salt-containing mother liquor |
| CN111978221A (en) * | 2020-08-18 | 2020-11-24 | 宁夏紫光天化蛋氨酸有限责任公司 | Preparation method of feed additive DL-methionine complex copper |
| CN114249352A (en) * | 2020-09-25 | 2022-03-29 | 沈阳化工研究院有限公司 | Method for treating wastewater generated in production of 6-methoxy tetralone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 and application of large-particle crystal form methionine metal chelate |
| CN104058844A (en) * | 2014-06-09 | 2014-09-24 | 李学春 | Method for preparing multielement chelate fertilizer by use of threonine mother liquor |
-
2019
- 2019-02-14 CN CN201910113862.8A patent/CN109678769B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 and application of large-particle crystal form methionine metal chelate |
| CN104058844A (en) * | 2014-06-09 | 2014-09-24 | 李学春 | Method for preparing multielement chelate fertilizer by use of threonine mother liquor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606335A (en) * | 2020-05-27 | 2020-09-01 | 天宝动物营养科技股份有限公司 | Method for comprehensively utilizing clean potassium salt-containing mother liquor |
| CN111978221A (en) * | 2020-08-18 | 2020-11-24 | 宁夏紫光天化蛋氨酸有限责任公司 | Preparation method of feed additive DL-methionine complex copper |
| CN114249352A (en) * | 2020-09-25 | 2022-03-29 | 沈阳化工研究院有限公司 | Method for treating wastewater generated in production of 6-methoxy tetralone |
| CN114249352B (en) * | 2020-09-25 | 2023-07-28 | 沈阳化工研究院有限公司 | Method for treating wastewater generated in production of 6-methoxy tetralone |
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